Filament, structure, resin composition, and method for producing filament

Abstract

Provided are a filament including a polyamide resin, wherein the filament has high strength and a high retention rate of mechanical properties after water absorption; a structure; a resin composition; and a method for producing a filament. The filament includes a polyamide resin; the polyamide resin is constituted from diamine-derived constituent units and dicarboxylic acid-derived constituent units; 70 mol% or more of the diamine-derived constituent units are derived from a xylylene diamine; 70 mol% or more of the dicarboxylic acid-derived constituent units are derived from a C11-14 α,ω-straight-chain aliphatic dicarboxylic acid; the content of compounds having a molecular weight of from 310 to 1000 is from 0.1 mass% to 1.5 mass%; and the content of compounds having a molecular weight of less than 310 is 0.1 mass% or less.

Description

[Technical Field]

[0001] The present invention relates to a filament, a structure containing the filament, a resin composition suitable as a raw material for the filament, and a method for producing the filament, and more particularly to a filament made primarily of polyamide resin. [Background technology]

[0002] Filaments made primarily of polyamide resin have been used for various applications. Such polyamide filaments are highly useful due to their high strength. Therefore, the use of polyamide filaments as structures such as nonwoven fabrics, adsorbents, filter cloths, filter papers, and filters has been investigated. However, conventional polyamide filaments (for example, polyamide filaments made primarily of polyamide 66) lose strength significantly due to water absorption, and when used as a filter for treating aqueous chemical solutions, the strength significantly decreases from the initial state.

[0003] Furthermore, polyamide filaments made primarily from a polyamide resin composed of metaxylylenediamine and adipic acid have also been disclosed (Patent Document 1). However, this is not sufficient in terms of the reduction in strength after water absorption. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2019 / 163062 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention aims to solve the above-mentioned problems, and aims to provide a filament containing a polyamide resin, which has high strength and a high retention rate of mechanical properties after absorbing water, a structure, a resin composition, and a method for manufacturing the filament. [Means for solving the problem]

[0006] In view of the above problems, the present inventors have conducted research and found that the above problems can be solved by using a specific polyamide resin and precisely adjusting the amount of low-molecular-weight components. Specifically, the above problems were solved by the following means. <1> A filament comprising a polyamide resin, the polyamide resin being composed of diamine-derived structural units and dicarboxylic acid-derived structural units, 70 mol % or more of the diamine-derived structural units being derived from xylylenediamine, 70 mol % or more of the dicarboxylic acid-derived structural units being derived from an α,ω-linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms, the content of compounds having a molecular weight of 310 or more and 1000 or less being 0.1 mass % or more and 1.5 mass % or less, and the content of compounds having a molecular weight of less than 310 being 0.1 mass % or less. <2> It is stretched, <1> The filament according to claim 1. <3> the compound having a molecular weight of 310 or more and 1000 or less includes a cyclic compound formed from one molecule of xylylenediamine and one molecule of an α,ω-linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms; <1> or <2> The filament according to claim 1. <4> 30 to 100 mol % of the diamine-derived structural units are derived from meta-xylylenediamine, and 0 to 70 mol % are derived from para-xylylenediamine. <1> ~ <3> The filament according to any one of the preceding claims. <5> 70 mol% or more of the structural units derived from the dicarboxylic acid are 1,12-dodecanedioic acid. <1> ~ <4> The filament according to any one of the preceding claims. <6> The filament is conditioned for one week in an environment of 23°C and 50% relative humidity, and then immersed in hydrochloric acid with a concentration of 10% by mass for one week, and the retention of tensile strength from before immersion in the chemical solution is 90% or more; and the filament is conditioned for one week in an environment of 23°C and 50% relative humidity, and then immersed in an aqueous sodium hydroxide solution with a concentration of 10% by mass for one week, and the retention of tensile strength from before immersion in the chemical solution is 90% or more. <1> ~ <5> The filament according to any one of the preceding claims. <7> Single yarn fineness is 2.0 x 10 -5 ~50dtex, <1> ~ <6> The filament according to any one of the preceding claims. <8> It is a multifilament <1> ~ <7> The filament according to any one of the preceding claims. <9> <1> ~ <8> A structure comprising the filament according to any one of claims 1 to 4. <10> The structure is a nonwoven fabric, an adsorbent, a filter cloth, a filter paper, or a filter; <9> The structure described in <11> A resin composition comprising a polyamide resin and a compound having a molecular weight of 310 or more and 1000 or less, wherein the polyamide resin is composed of diamine-derived structural units and dicarboxylic acid-derived structural units, wherein 70 mol % or more of the diamine-derived structural units are derived from xylylenediamine and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from an α,ω-linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms, the content of the compound having a molecular weight of 310 or more and 1000 or less is 0.1 mass % or more and 1.5 mass % or less, and further wherein the content of the compound having a molecular weight of less than 310 is 0.1 mass % or less. <12> For filaments, nonwoven fabrics, adsorbents, filter cloths, filter papers or filters, <11> The resin composition according to claim 1. <13> <11> The resin composition according to claim 1 is spun by a melt spinning method or an electrospinning method. <1> ~ <8> 10. A method for producing a filament according to any one of the preceding claims. [Effects of the Invention]

[0007] The present invention makes it possible to provide a filament containing a polyamide resin, which has high strength and a high retention rate of mechanical properties after absorbing water, a structure, a resin composition, and a method for producing the filament. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, an embodiment for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only this embodiment. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit. In this specification, various physical properties and characteristic values ​​are those at 23°C unless otherwise specified.

[0009] The filament of this embodiment contains a polyamide resin, the polyamide resin being composed of diamine-derived structural units and dicarboxylic acid-derived structural units, wherein 70 mol % or more of the diamine-derived structural units are derived from xylylenediamine, 70 mol % or more of the dicarboxylic acid-derived structural units are derived from an α,ω-linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms, the content of compounds having a molecular weight of 310 to 1000 being 0.1% by mass to 1.5% by mass, and the content of compounds having a molecular weight of less than 310 being 0.1% by mass or less. This configuration allows for the production of filaments with high strength and high retention of mechanical properties after water absorption. More specifically, the filaments have excellent linear strength and high retention of elastic modulus and tensile strength after water absorption. Furthermore, the filaments also have excellent continuous productivity and chemical resistance. The reason for this is presumed to be as follows. Specifically, in the filament of this embodiment, xylylenediamine and an α,ω-linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms are used as raw material monomers for the polyamide resin. By using a polyamide resin composed of such raw materials, the filament is less likely to absorb water, suppressing a decrease in mechanical properties. It is also presumed that hydrolysis is less likely to occur, resulting in low chemical resistance. Furthermore, by setting the content of compounds having a molecular weight of 310 to 1000 in this polyamide resin to 0.1% by mass to 1.5% by mass, it is presumed that stretchability is improved and the strength of the filament can be increased. Additionally, it is presumed that compounds having a molecular weight of 310 to 1000 are significantly less likely to come off after immersion in water than compounds having a molecular weight of less than 310, thereby maintaining high mechanical properties after water absorption.

[0010] <Polyamide resin> The polyamide resin used in this embodiment is composed of diamine-derived structural units and dicarboxylic acid-derived structural units, wherein 70 mol % or more of the diamine-derived structural units are derived from xylylenediamine, and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from an α,ω-linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms, and the content of compounds having a molecular weight of 310 or more and 1000 or less is 0.1 mass % or more and 1.5 mass % or less, and the content of compounds having a molecular weight of less than 310 is 0.1 mass % or less. Hereinafter, in this specification, such a polyamide resin may be referred to as "polyamide resin (A)".

[0011] In the polyamide resin (A), 70 mol % or more of the diamine-derived structural units are derived from xylylenediamine, preferably 80 mol % or more, more preferably 90 mol % or more, even more preferably 95 mol % or more, and even more preferably 99 mol % or more, with the upper limit being 100 mol %.

[0012] The xylylenediamine preferably contains 10 to 100 mol% metaxylylenediamine and 90 to 0 mol% paraxylylenediamine (however, the total of metaxylylenediamine and paraxylylenediamine does not exceed 100 mol%), more preferably 30 to 100 mol% metaxylylenediamine and 70 to 0 mol% paraxylylenediamine, and even more preferably 50 to 100 mol% metaxylylenediamine and 0 to 50 mol% paraxylylenediamine. Furthermore, in the xylylenediamine, the total of metaxylylenediamine and paraxylylenediamine preferably accounts for 95 mol% or more, more preferably 99 mol% or more, and even more preferably 100 mol%.

[0013] Diamine components other than xylylenediamine include aliphatic diamines such as tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine; 1,3-bis(aminomethyl)cyclohexane; 1,4-bis(aminomethyl)cyclohexane; Examples of the diamine include alicyclic diamines such as bis(4-aminophenyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminomethyl)decalin, and bis(aminomethyl)tricyclodecane; and diamines having an aromatic ring such as bis(4-aminophenyl)ether, paraphenylenediamine, and bis(aminomethyl)naphthalene. These diamines may be used alone or in combination of two or more.

[0014] In the polyamide resin (A), 70 mol % or more of the dicarboxylic acid-derived structural units are derived from α,ω-straight-chain aliphatic dicarboxylic acids having 11 to 14 carbon atoms (preferably α,ω-straight-chain aliphatic dicarboxylic acids having 12 to 14 carbon atoms, more preferably 1,12-dodecanedioic acid). The proportion of α,ω-straight-chain aliphatic dicarboxylic acids having 11 to 14 carbon atoms in the dicarboxylic acid-derived structural units is preferably 80 mol % or more, more preferably 90 mol % or more, even more preferably 95 mol % or more, and even more preferably 99 mol % or more. The upper limit is 100 mol %.

[0015] Examples of dicarboxylic acid components other than α,ω-linear aliphatic dicarboxylic acids having 11 to 14 carbon atoms include α,ω-linear aliphatic dicarboxylic acids having 10 or less carbon atoms, such as succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, and sebacic acid; phthalic acid compounds, such as isophthalic acid, terephthalic acid, and orthophthalic acid; and naphthalenedicarboxylic acids, such as 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. These can be used alone or in combination of two or more.

[0016] The phrase "composed of diamine-derived structural units and dicarboxylic acid-derived structural units" means that the amide bonds constituting the polyamide resin (A) are formed by bonds between dicarboxylic acids and diamines. Furthermore, the polyamide resin (A) contains other moieties, such as terminal groups, in addition to the dicarboxylic acid-derived structural units and diamine-derived structural units. Furthermore, it may contain repeating units having amide bonds not derived from bonds between dicarboxylic acids and diamines, or trace amounts of impurities. Specifically, in addition to the diamine component and dicarboxylic acid component, the polyamide resin (A) may also contain lactams such as ε-caprolactam and laurolactam, and aliphatic aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid, as copolymerization components, as long as the effects of this embodiment are not impaired. In this embodiment, preferably 90% by mass or more of the polyamide resin (A) is composed of diamine-derived structural units or dicarboxylic acid-derived structural units, more preferably 95% by mass or more, and even more preferably 98% by mass or more.

[0017] The polyamide resin (A) used in this embodiment contains a compound having a molecular weight of 310 to 1000 in an amount of 0.1 to 1.5% by mass. The inclusion of a trace amount of a compound having such a molecular weight increases the stretchability and linear strength of the filament. Furthermore, even after water absorption, the compound having a molecular weight of 310 to 1000 is less likely to come off the filament, allowing the filament to maintain high mechanical properties. The compound having a molecular weight of 310 to 1000 is not particularly limited in type, but may be, for example, a raw material monomer for polyamide resin (A) or an oligomer derived from other components added during the production of polyamide resin (A). In this embodiment, the compound having a molecular weight of 310 to 1000 preferably includes a cyclic compound formed from one molecule of xylylenediamine and one molecule of an α,ω-linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms. By including a predetermined amount of such a cyclic compound, the effects of the present invention can be more effectively achieved. In particular, when the raw material dicarboxylic acid for the polyamide resin is sebacic acid, the molecular weight of the cyclic compound formed from one molecule of xylylenediamine and one molecule of sebacic acid is small. Furthermore, since the filaments are thin to begin with, such cyclic compounds easily leach out of the filaments when immersed in water, resulting in a decrease in strength retention. In this embodiment, this problem is avoided by increasing the carbon number of the α,ω-linear aliphatic dicarboxylic acid. Furthermore, the polyamide resin (A) preferably contains at least a compound having a molecular weight of 310 to 700, more preferably at least a compound having a molecular weight of 310 to 500, as the compound having a molecular weight of 310 to 1000. Furthermore, the content of compounds having a molecular weight of 310 or more and 1000 or less in the polyamide resin (A) is preferably 0.3 mass% or more, more preferably 0.5 mass% or more, and even more preferably 0.6 mass% or more, and more preferably 1.2 mass% or less, and even more preferably 1.0 mass% or less. The polyamide resin (A) may contain only one kind or two or more kinds of compounds having a molecular weight of 310 or more and 1000 or less. When two or more kinds are contained, the total amount is preferably in the above range.

[0018] The polyamide resin (A) used in this embodiment also has a content of compounds with a molecular weight of less than 310 of 0.1% by mass or less. This configuration effectively prevents the elution of low-molecular-weight components when immersed in water. In particular, when the filament of this embodiment is used as a filter for filtering an aqueous solution, the low-molecular-weight components contained in the filament are likely to leak out when immersed in water, which may cause problems with the filter's performance. In this embodiment, the content of compounds with a molecular weight of less than 310 is 0.1% by mass or less, thereby effectively preventing the leakage of such low-molecular-weight components. The lower limit of the content of compounds with a molecular weight of less than 310 is ideally 0% by mass, and the detection limit would be the practical lower limit.

[0019] The polyamide resin (A) used in the present embodiment preferably has a number average molecular weight (Mn) of 6,000 to 50,000, more preferably 8,000 to 48,000, and even more preferably 9,000 to 46,000. Within such a range, the molding processability is improved.

[0020] The number average molecular weight (Mn) referred to here can be determined from a value converted into standard polymethyl methacrylate (PMMA) by gel permeation chromatography (GPC) measurement.

[0021] The polyamide resin (A) used in this embodiment may or may not have a melting point. If it has a melting point, the melting point is preferably 170 to 280° C., more preferably 170 to 250° C. By adjusting the melting point to be within this range, filaments having excellent moldability into structures and excellent heat resistance can be obtained. The melting point in the present invention refers to the peak-top temperature of the endothermic peak observed during heating by DSC (differential scanning calorimetry). Specifically, the melting point refers to the peak-top temperature of the endothermic peak observed when a 1 mg sample is heated and melted from room temperature (25°C) to a temperature equal to or higher than the expected melting point at a temperature rising rate of 10°C / min using a DSC apparatus with nitrogen as the atmospheric gas at a flow rate of 30 mL / min, and the molten polyamide resin is then rapidly cooled with dry ice and heated again at a rate of 10°C / min to a temperature equal to or higher than the melting point.

[0022] Furthermore, in the filament of this embodiment, the polyamide resin (A) preferably accounts for 70 mass% or more of the mass of the filament, more preferably 80 mass% or more, even more preferably 90 mass% or more, even more preferably 95 mass% or more, and even more preferably 98 mass% or more. The filament of the present embodiment may contain only one type of polyamide resin (A), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0023] <Other ingredients> The filament of this embodiment may contain polyamide resins other than the polyamide resin (A), thermoplastic resins other than polyamide resins, resin additives, etc., within a range that does not significantly deviate from the effects of this embodiment.

[0024] Examples of polyamide resins other than the polyamide resin (A) include polyamide 4, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 6 / 66, polyamide 610, polyamide 612, polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyamide 66 / 6T, polyamide 9T, polyamide 9MT, polyamide 6I / 6T, polyamide XD6 (polyxylylene azide), Examples of suitable polyamide resins include polyamide XD10 (polyxylylene sebacamide), polyamide 10T, 1,3-BAC10I (a polyamide resin composed of 1,3-bisaminomethylcyclohexane, sebacic acid, and isophthalic acid), and 1,4-BAC10I (a polyamide resin composed of 1,4-bisaminomethylcyclohexane, sebacic acid, and isophthalic acid), and polyamide 6, polyamide 66, polyamide 666, polyamide 610, and polyamide 612 are preferred. The filament of the present embodiment may contain only one kind of polyamide resin other than the polyamide resin (A), or may contain two or more kinds of polyamide resins. When two or more kinds are contained, the total amount is preferably within the above range. Examples of thermoplastic resins other than the polyamide resin include one or more of polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate resins, polyoxymethylene resins, polyether ketones, polyether sulfones, and thermoplastic polyether imides. Furthermore, the filament of this embodiment may be configured to be substantially free of thermoplastic resins other than the polyamide resin (A). "Substantially free" means, for example, that the content of thermoplastic resins other than the polyamide resin (A) in the filament of this embodiment is 5% by mass or less of the content of the polyamide resin (A), preferably 3% by mass or less, and more preferably 1% by mass or less.

[0025] The filaments of this embodiment may contain additives such as antioxidants, heat stabilizers, hydrolysis resistance improvers, weathering stabilizers, delustering agents, UV absorbers, nucleating agents, plasticizers, dispersants, flame retardants, antistatic agents, coloring inhibitors, antigelling agents, colorants, release agents, surface activators, dyes, etc. For details of these additives, please refer to paragraphs

[0130] to

[0155] of Japanese Patent No. 4894982, paragraph

[0021] of Japanese Unexamined Patent Publication No. 2010-281027, and paragraph

[0036] of Japanese Unexamined Patent Publication No. 2016-223037, the contents of which are incorporated herein by reference. The filament of this embodiment may contain no plasticizer, or the content of the plasticizer may be less than 0.5 parts by mass, preferably 0.4 parts by mass or less, per 100 parts by mass of the polyamide resin. In this embodiment, such a configuration is possible because a compound having a molecular weight of 310 or more and 1000 or less serves as a plasticizer. The filament of this embodiment is adjusted so that the total of the polyamide resin (A), the compound having a molecular weight of 310 or more and 1000 or less, and other components (thermoplastic resin, additives, etc.) blended as necessary, is 100 mass %.

[0026] <Filament morphology and properties> The filament of this embodiment may be a monofilament or a multifilament, but is preferably a multifilament, which makes it easier to process into a structure. When the filament of this embodiment is a multifilament, the number of filaments constituting one multifilament is preferably 10 or more, more preferably 20 or more, and may be 30 or more. The upper limit of the number of filaments constituting one multifilament is preferably 100 or less, more preferably 60 or less, and even more preferably 55 or less. By setting the number within such a range, unevenness in the single filament fineness during spinning can be suppressed, and fusion between the single filaments during spinning can be prevented. The cross section of the filament in this embodiment is usually circular. Here, circular means not only a circular shape in a geometric sense but also a shape that is generally considered to be circular in the technical field of this embodiment. Furthermore, the cross section of the filament in this embodiment may be a shape other than circular, for example, a flat shape such as an ellipse or an oval.

[0027] The filament of this embodiment has a single yarn fineness of 2.0 × 10 -5 It is preferable that the single fiber fineness is 8.0×10 to 50 dtex. By making the single fiber fineness equal to or greater than the lower limit, stable spinning is possible, and when processed into a structure, the structure can have sufficient strength. Furthermore, by making the single fiber fineness equal to or less than the upper limit, the pore size when the structure is formed can be made small, and not only can the dust collection performance be improved, but also pressure loss can be effectively suppressed. The lower limit of the single fiber fineness is 8.0×10 to 50 dtex. -5 dtex or more is preferable, and 9.0 × 10 -3 dtex or more is more preferable, and 1.0 × 10 -2 dtex or more, more preferably 0.5 dtex or more, and even more preferably 1 dtex or more. The upper limit of the single yarn fineness is preferably 40 dtex or less, more preferably 30 dtex or less, even more preferably 25 dtex or less, even more preferably 20 dtex or less, and even more preferably 18 dtex or less. Furthermore, when the filament of this embodiment is a multifilament, the fineness is preferably 10 to 1,000 dtex. By setting the fineness at or above the lower limit, stable spinning is possible, and when processed into a structure, the structure can be provided with sufficient strength. By setting the fineness at or below the upper limit, the pore size when the structure is formed can be reduced, thereby not only improving dust collection performance but also effectively suppressing pressure loss. The lower limit of the fineness of the multifilament is preferably 40 dtex or more, more preferably 60 dtex or more, and even more preferably 100 dtex or more. The upper limit of the fineness of the multifilament is preferably 800 dtex or less, more preferably 600 dtex or less, and even more preferably 400 dtex or less. The fineness is measured according to the method described in the examples below.

[0028] The filament length (mass average length) in this embodiment is not particularly limited, but is preferably 5 mm or more, more preferably 0.1 m or more, even more preferably 1 m or more, and even more preferably 100 m or more. The upper limit of the filament length (mass average length) is preferably 20,000 m or less, more preferably 1,000 m or less, and even more preferably 100 m or less.

[0029] The filament of this embodiment may or may not be drawn, but is preferably drawn. By being drawn, a filament with superior mechanical strength can be obtained. The drawing is preferably in the longitudinal direction of the filament (filament length direction). The draw ratio is preferably 2.0 times or more, more preferably 2.5 times or more, even more preferably 3.0 times or more, and even more preferably 3.5 times or more. The upper limit of the draw ratio is preferably 6.5 times or less, more preferably 6.0 times or less, even more preferably 5.5 times or less, and even more preferably 5.0 times or less.

[0030] The filament of this embodiment preferably has excellent strength. Specifically, in accordance with JIS L 1013: 2010, the linear strength of the filament is preferably 4.25 cN / dtex or more, more preferably 4.30 cN / dtex or more, and even more preferably 4.35 cN / dtex or more. There is no particular upper limit to the linear strength, but a practical upper limit is 6.50 cN / dtex or less.

[0031] The filaments of the present embodiment preferably have excellent water absorption properties. Specifically, the tensile strength retention rate when the filament is dried at 80°C for 24 hours and then immersed in water at 23°C for one week is preferably 85% or more, and more preferably 90% or more. The ideal upper limit of the retention rate is 100%, but 99.9% or less is practical.

[0032] The filament of this embodiment also preferably has excellent chemical resistance. Specifically, after conditioning the filament for one week in an environment of 23°C and 50% relative humidity, the filament retains preferably 90% or more, and more preferably 91% or more, of the tensile strength before immersion in 10% by mass hydrochloric acid for one week. The ideal upper limit of the retention is 100%, but 99.9% or less is practical. Furthermore, after conditioning the filament for one week in an environment of 23°C and 50% relative humidity, the filament preferably retains 90% or more, and more preferably 91% or more, of the tensile strength before immersion in a 10% by mass aqueous sodium hydroxide solution for one week. The ideal upper limit of the retention rate is 100%, but 99.9% or less is practical. In this embodiment, it is sufficient if either the retention rate after immersion in hydrochloric acid or the retention rate after immersion in a sodium hydroxide aqueous solution is satisfied, but it is preferable that both are satisfied.Furthermore, it is preferable that the retention rate after water absorption is also satisfied.

[0033] <Filament manufacturing method> Next, a method for producing the filament of this embodiment will be described. The filament in this embodiment is obtained by molding the resin composition. The molding method may be any, and the filament may be molded into a desired shape by any conventionally known molding method. For example, see paragraphs 0051 to 0058 of International Publication No. 2017 / 010389, the contents of which are incorporated herein by reference. In this embodiment, it is particularly preferable that the filaments be produced by melt spinning or electrospinning. Melt spinning is a method in which a resin is extruded from a multi-hole die by an extruder and stretched through a roll. Electrospinning is a method in which a resin is dissolved in a solvent and the resulting resin solution is discharged from a thin nozzle. An electric field is generated at the end of the resin solution, charging the resin solution itself, and the solvent is volatilized while being stretched by the potential difference.

[0034] <Structure> The structure of this embodiment includes the filament of this embodiment. The structure of this embodiment includes the filament of this embodiment retaining its filament shape. Here, "retaining" means that the filament shape is generally maintained, and also includes a case in which a portion of the filament (for example, 10% by volume or less) is melted and bonded to other filaments or other constituent materials that may be included in the structure (other fibers, substrates, etc.). The structure of this embodiment may be a filamentary material such as a mixed yarn, braid, twisted cord, spun yarn, or yarn having a core-sheath structure containing the filament of this embodiment. When a mixed yarn or the like is used, it is preferable to combine it with other thermoplastic resin filaments, or reinforcing fibers (filaments) such as carbon fiber or glass fiber. The structure of this embodiment is preferably a filament, nonwoven fabric, adsorbent, filter cloth, filter paper, or filter containing the filament of this embodiment. The filament, nonwoven fabric, adsorbent, filter cloth, filter paper, or filter of this embodiment is intended to include filaments, nonwoven fabrics, adsorbents, filter cloth, filter paper, or filters such as mixed yarns, braided cords, and twisted cords using the filament of this embodiment.

[0035] An example of the structure of this embodiment is a flat plate-shaped structure consisting of only a layer primarily composed of the filaments of this embodiment. Another example of the structure of this embodiment is a multilayer body consisting of a layer primarily composed of the filaments of this embodiment and a substrate. The structure of this embodiment may also be a multilayer body consisting of a layer primarily composed of the filaments of this embodiment and another nonwoven fabric, filter, or the like. A layer primarily composed of the filaments of this embodiment means that the filaments of this embodiment are the component with the highest content among the constituent structures of the layer. Examples of other nonwoven fabrics, filters, and the like include nonwoven fabrics and filters made of polyolefin (preferably polypropylene).

[0036] When the structure of this embodiment is used as a filter, the target substances are not particularly specified, but examples include slime, gel, protein in water treatment, and the polysaccharide substance LPS, which needs to be removed in seawater recycling. When the structure of this embodiment is used as a filter, the density is 1.10 to 1.25 g / cm 3 The pore size of the filter is preferably 0.001 to 500 μm. Examples of methods for producing the filter include an air blowing method and a melt blowing method. The air blowing method is a method in which filaments are extruded from a multi-hole die, melted, solidified, and then blown onto a substrate in the form of a mesh by air blowing. The melt blowing method is a method in which a resin composition is extruded in a molten state and then blown onto a substrate in the form of a mesh.

[0037] <Resin composition> Next, the resin composition of this embodiment will be described. The resin composition of this embodiment includes a polyamide resin and a compound having a molecular weight of 310 to 1000, wherein the polyamide resin is composed of diamine-derived structural units and dicarboxylic acid-derived structural units, wherein 70 mol % or more of the diamine-derived structural units are derived from xylylenediamine, and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from an α,ω-linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms, and wherein the content of the compound having a molecular weight of 310 to 1000 is 0.1 mass % to 1.5 mass %, and further, the content of the compound having a molecular weight of less than 310 is 0.1 mass % or less. Such a resin composition is preferably used for producing the filament of this embodiment, a nonwoven fabric, an adsorbent, a filter cloth, a filter paper, or a filter. The details of the polyamide resin (A) in the resin composition of this embodiment and other details are the same as those of the filament of this embodiment described above, and the preferred ranges are also the same. [Example]

[0038] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or the like, measurements can be made using other instruments with equivalent performance.

[0039] Example 1 <Synthesis of Polyamide MP12> A precisely weighed 60.00 mol of 1,12-dodecanedioic acid was placed in a jacketed reactor equipped with a stirrer, partial condenser, condenser, thermometer, dropping tank, and nitrogen gas inlet tube. The mixture was thoroughly purged with nitrogen and heated to 180°C under a small nitrogen stream to dissolve the 1,12-dodecanedioic acid and achieve a homogeneous fluid state. 60 mol of para- / meta-xylylenediamine (30 mol% of the diamine component was para-xylylenediamine and 70 mol% was meta-xylylenediamine) was added dropwise over 160 minutes with stirring. During this time, the internal pressure of the reaction system was maintained at atmospheric pressure, and the internal temperature was continuously raised to 250°C. Water distilled during the dropwise addition of para- / meta-xylylenediamine was removed from the system via the partial condenser and condenser. After the dropwise addition of para- / meta-xylylenediamine was completed, the liquid temperature was maintained at 250°C and the reaction was continued for 10 minutes. The pressure inside the reaction system was then continuously reduced to 600 Torr over 10 minutes, and the reaction was continued for 30 minutes to adjust the amount of components with a molecular weight of 1,000 or less. During this time, the reaction temperature was continuously increased to 260°C. After the reaction was completed, the reactor was pressurized with nitrogen gas at 0.3 MPa, and the polymer was removed as a strand from a nozzle at the bottom of the polymerization vessel. After water cooling, the polymer was cut into pellets to obtain pellets of the melt-polymerized product. The resulting pellets were placed at room temperature in a tumbler (rotary vacuum vessel) equipped with a heat medium heating jacket. While rotating the tumbler, the vessel was reduced in pressure (0.5 to 10 Torr), and the flowing heat medium was heated to 150°C. The pellet temperature was then raised to 130°C and maintained at that temperature for 3 hours. Nitrogen was then introduced again to return to normal pressure, and cooling was initiated. When the pellet temperature reached 70°C or below, the pellets were removed from the vessel, yielding a solid-state polymerized product. The melting point of the resulting polyamide resin (MP12) was 206°C.

[0040] <Production of polyamide filaments> The polyamide resins shown in Table 1 were melted using a single-screw extruder and spun at a spinning temperature of 290°C through a spinneret (the number of holes is shown in Table 1). After passing through a hot zone and a cooling zone, the spun polyamide filaments (hereinafter sometimes referred to as "pre-stretched filaments"), which had cooled to approximately room temperature, were immersed in a sizing agent (Takemoto Yushi Co., Ltd., Delion PP-807) to form a bundle. The unstretched filaments taken up by roll 1 were heated by passing them through roller 2 heated to 80°C, and then passed through rollers 2, 3, and 4 heated to 170°C before being wound up by a winder. The stretching was performed by setting a speed ratio between roller 2 and roller 3, and the speed ratio was adjusted to achieve the stretch ratio shown in Table 1. The speed ratio between roller 3 and roller 4 was also set to relax the stretching, with roller 4's rotation speed set 4% slower than roller 3's.

[0041] <Measurement of oligomer content> The amounts of oligomers with a molecular weight of less than 310 and oligomers with a molecular weight of 310 to 1000 were determined as follows from values ​​converted into standard polymethyl methacrylate (PMMA) by gel permeation chromatography (GPC). Two columns packed with a styrene polymer were used as the packing material. The solvent was hexafluoroisopropanol (HFIP) with a sodium trifluoroacetate concentration of 2 mmol / L. The resin concentration was 0.02% by mass, the column temperature was 40°C, the flow rate was 0.3 mL / min, and measurements were performed using a refractive index detector (RI). A calibration curve was also created by dissolving six levels of PMMA in HFIP. The amounts of oligomers with molecular weights less than 310 and oligomers with molecular weights between 310 and 1000 were expressed as mass% relative to the total amount of polyamide resin with a molecular weight greater than 1000. The components obtained by GPC were expressed as area %, but because area % can be considered equivalent to mass %, these values ​​are reported as mass %. The gel permeation chromatography apparatus used in this example was "HLC-8320GPC" manufactured by Tosoh Corporation, and the measurement column was "TSKgel SuperHM-H."

[0042] <Fineness> The filament fineness (single yarn fineness, multifilament fineness) was measured in dtex in accordance with the provisions of JIS L 1013:2010.

[0043] <Continuous spinning> After spinning, the degree of contamination on the nozzle was checked, and the adhesion of components with a molecular weight of 330 or less to the nozzle was evaluated as follows. The evaluation was carried out by five experts and was based on a majority vote. A: No or almost no adhesion. B: Other than A above, for example, there was adhesion that affected continuous spinning.

[0044] <Straight line strength> The linear strength of the filament was measured according to JIS L 1013:2010. The unit is cN / dtex.

[0045] <Water absorption resistance> The filaments were dried in a vacuum dryer at 80°C for 24 hours, then immersed in water at 23°C for one week, and evaluated based on the retention of tensile strength before immersion. Tensile strength was measured according to JIS L 1013:2010. Tensile strength retention rate = [(tensile strength before water immersion - tensile strength after water immersion) / tensile strength before water immersion] x 100 (unit: %) The unit is shown as %.

[0046] <Chemical resistance> The filaments were conditioned at 23°C and 50% relative humidity for one week, then immersed in a chemical solution (a 10% by mass aqueous solution of hydrochloric acid or a 10% by mass aqueous solution of sodium hydroxide) for one week, and the tensile strength was evaluated based on the retention of the tensile strength before immersion in the chemical solution. The tensile strength was measured according to JIS L 1013:2010. Tensile strength retention rate = [(tensile strength before immersion in chemical solution - tensile strength after immersion in chemical solution) / tensile strength before immersion in chemical solution] x 100 The unit is shown as %.

[0047] Example 2 The same procedure was carried out as in Example 1, except that the polyamide resin was changed to polyamide MXD12, the synthesis example of which is shown below. <Synthesis of Polyamide MXD12> A precisely weighed 60.00 mol of 1,12-dodecanedioic acid was placed in a jacketed reactor equipped with a stirrer, partial condenser, condenser, thermometer, dropping tank, and nitrogen gas inlet tube. The mixture was thoroughly purged with nitrogen and heated to 180°C under a small nitrogen stream to dissolve the 1,12-dodecanedioic acid and achieve a uniform flow. 60 mol of meta-xylylenediamine was then added dropwise to the mixture over 160 minutes with stirring. During this time, the internal pressure of the reaction system was maintained at atmospheric pressure, and the internal temperature was continuously raised to 250°C. Water distilled during the dropwise addition of meta-xylylenediamine was removed from the system via the partial condenser and condenser. After the dropwise addition of meta-xylylenediamine, the liquid temperature was maintained at 250°C and the reaction was continued for 10 minutes. The internal pressure of the reaction system was then continuously reduced to 600 Torr over 10 minutes, and the reaction was continued for another 30 minutes to adjust the amount of components with molecular weights of 1,000 or less. During this time, the reaction temperature was continuously increased to 260°C. After the reaction was completed, the reactor was pressurized with nitrogen gas at 0.3 MPa, and the polymer was removed as a strand from a nozzle at the bottom of the polymerization vessel. After water cooling, the polymer was cut into pellets to obtain pellets of the melt-polymerized product. The resulting pellets were placed at room temperature in a tumbler (rotary vacuum vessel) equipped with a heat medium heating jacket. While the tumbler was rotating, the vessel was evacuated (0.5 to 10 Torr), and the circulating heat medium was heated to 150°C. The pellet temperature was increased to 130°C and maintained at that temperature for 3 hours. Nitrogen was then introduced again to return to normal pressure, and cooling was initiated. When the pellet temperature reached 70°C or below, the pellets were removed from the vessel, yielding a solid-state polymerized product. The melting point of the resulting polyamide resin (MXD12) was 190°C.

[0048] Comparative Example 1 The same procedure was carried out as in Example 1, except that the polyamide resin was changed to polyamide MP10, the synthesis example of which is shown below. <Synthesis example of polyamide MP10 (M / P ratio = 7:3)> Sebacic acid was placed in a jacketed reactor equipped with a stirrer, partial condenser, condenser, thermometer, dropping tank, and nitrogen gas inlet tube. After heating and dissolving under a nitrogen atmosphere, a mixed diamine (manufactured by Mitsubishi Gas Chemical Co., Inc.) consisting of metaxylylenediamine and paraxylylenediamine in a molar ratio of 7:3 was gradually added dropwise under pressure (0.35 MPa) to achieve a molar ratio of diamine to sebacic acid of approximately 1:1. The temperature was raised to 235°C. After the addition was complete, the reaction was continued for 60 minutes to adjust the amount of components with a molecular weight of 1,000 or less. After the reaction was complete, the contents were removed in the form of strands and pelletized using a pelletizer to obtain a polyamide resin (MP10, M / P = 7:3). The melting point of the resulting polyamide resin (MP10) was 215°C.

[0049] Comparative Example 2 The same procedure was carried out as in Example 1, except that the polyamide resin was changed to PA66 (nylon 66, manufactured by Toray Industries, Inc., Amilan CM3001, melting point 265°C).

[0050] Comparative Example 3 The same procedure was carried out as in Example 1, except that the polyamide resin was changed to polyamide MP12, the synthesis example of which is shown below. <Synthesis of Polyamide MP12> A 3 L stainless steel separable flask was charged with 1 kg of polyamide resin (MP12) obtained by the same synthesis method as that described in Example 1, and 1.5 L of methanol was added. The contents were stirred while being heated with a mantle heater until the methanol temperature reached 60°C. After heating for 5 hours from the point when the methanol temperature reached 60°C, the contents were cooled to room temperature and then passed through a 40-mesh wire screen to separate the methanol phase and pellets. The above procedure was repeated three times for the separated pellets, and then the pellets were dried in a vacuum dryer at 120°C for 5 hours to obtain the resin used in Comparative Example 3.

[0051] Comparative Example 4 The same procedure was carried out as in Example 1, except that the polyamide resin was changed to polyamide MP12, the synthesis example of which is shown below. <Synthesis of Polyamide MP12> To a polyamide resin (MP12) obtained by the same synthesis method as that described in Example 1, 1% by mass of an oligomer having a molecular weight of 310 to 1000 was added and dry-blended to obtain the resin used in Comparative Example 4. The oligomer having a molecular weight of 310 to 1000 was obtained by evaporating and drying the methanol phase after the treatment described in Comparative Example 3.

[0052] [Table 1]

[0053] In the above table, "<0.1" means less than 0.1% by mass. As is clear from the above results, the filaments of the present invention were excellent in linear strength and had a high retention rate of tensile strength after absorbing water (Examples 1 and 2).Furthermore, they were also excellent in continuous productivity and chemical resistance. On the other hand, when a polyamide resin composed of xylylenediamine and sebacic acid (a C10 α,ω-linear aliphatic dicarboxylic acid) was used (Comparative Example 1), both the linear strength and the retention of tensile strength after water absorption were poor.Furthermore, continuous productivity was also poor. When polyamide 66 was used (Comparative Example 2), the linear strength was excellent, but the retention rate of tensile strength after water absorption was significantly poor, and the chemical resistance (resistance to hydrochloric acid) was also significantly poor. When a polyamide resin containing less than 0.1% by mass of compounds with a molecular weight of 310 or more and 1000 or less was used (Comparative Example 3), and when a polyamide resin containing more than 1.5% by mass of compounds with a molecular weight of 310 or more and 1000 or less was used (Comparative Example 4), the linear strength was poor.

Claims

1. Contains polyamide resin, the polyamide resin is composed of diamine-derived structural units and dicarboxylic acid-derived structural units, 70 mol % or more of the diamine-derived structural units are derived from xylylenediamine, and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from an α,ω-linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms; the content of compounds having a molecular weight of 310 or more and 1000 or less is 0.5% by mass or more and 1.5% by mass or less, the content of compounds with a molecular weight of less than 310 is 0.1% by mass or less, the compound having a molecular weight of 310 or more and 1000 or less includes a cyclic compound formed from one molecule of xylylenediamine and one molecule of an α,ω-linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms; filament.

2. The filament of claim 1 which is drawn.

3. 3. The filament according to claim 1, wherein 30 to 100 mol % of the diamine-derived structural units are derived from metaxylylenediamine, and 0 to 70 mol % are derived from paraxylylenediamine.

4. The filament according to any one of claims 1 to 3, wherein 70 mol% or more of the structural units derived from the dicarboxylic acid are 1,12-dodecanedioic acid.

5. The filament according to any one of claims 1 to 4, wherein the filament is immersed in a 10% by mass concentration hydrochloric acid for one week after conditioning the humidity in an environment of 23°C and 50% relative humidity, and the retention of tensile strength from before immersion in the chemical solution is 90% or more when the filament is immersed in a 10% by mass concentration aqueous sodium hydroxide solution for one week after conditioning the humidity in an environment of 23°C and 50% relative humidity for one week.

6. Single yarn fineness is 2.0 x 10 －５ The filament according to any one of claims 1 to 5, which has a fineness of up to 50 dtex.

7. The filament according to any one of claims 1 to 6, which is a multifilament.

8. A structure comprising the filaments of any one of claims 1 to 7.

9. The structure according to claim 8, wherein the structure is a nonwoven fabric, an adsorbent, a filter fabric, a filter paper, or a filter.

10. A resin composition comprising a polyamide resin and a compound having a molecular weight of 310 or more and 1000 or less, the polyamide resin is composed of diamine-derived structural units and dicarboxylic acid-derived structural units, 70 mol % or more of the diamine-derived structural units are derived from xylylenediamine, and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from an α,ω-linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms; the content of the compound having a molecular weight of 310 or more and 1000 or less is 0.5% by mass or more and 1.5% by mass or less, Furthermore, the content of compounds having a molecular weight of less than 310 is 0.1% by mass or less, the compound having a molecular weight of 310 or more and 1000 or less includes a cyclic compound formed from one molecule of xylylenediamine and one molecule of an α,ω-linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms, A resin composition for use in filaments, nonwoven fabrics, adsorbents, filter cloths, filter papers, or filters.

11. A method for producing the filament according to any one of claims 1 to 7, comprising spinning the resin composition according to claim 10 by melt spinning or electrospinning.

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