Filaments, materials and methods of manufacturing materials

Abstract

Provided are filaments containing a disperse dye, which have excellent dyeing fastness without impairing the strength originally possessed by the filaments, and materials using the filaments and a method for manufacturing the materials. A filament containing a polyamide resin having an aromatic ring and / or a heterocyclic ring, and a disperse dye having an aromatic ring and / or a heterocyclic ring.

Description

Technical Field

[0001] This invention relates to filaments, materials, and methods for manufacturing materials. In particular, it relates to filaments comprising polyamide resins and dyes. Background Technology

[0002] Filaments made primarily of polyamide resin have long been used for various applications. Filaments made primarily of polyamide resin have high strength, and therefore high utility.

[0003] On the other hand, when dyeing filaments made primarily of polyamide resin, it is known to use acid dyes (Patent Document 1).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 48-63050 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] When dyeing filaments with polyamide resin as the main raw material, it is known that, as described in Patent Document 1, the color fastness is good when using acid dyes. However, in cases where filaments are mixed with those dyed only with disperse dyes, disperse dyes are sometimes required when dyeing filaments with polyamide resin as the main raw material.

[0009] On the other hand, it is known that for filaments using polyamide resin as the main raw material, the color fastness is typically low when using disperse dyes. Therefore, if disperse dyes are used, color transfer problems may occur when dyeing blended fabrics with other thermoplastic filaments such as polyester to form final products such as clothing and bags.

[0010] The object of the present invention is to solve the above-mentioned problems, and to provide: a filament that does not impair the original strength of the filament and contains disperse dyes and has excellent color fastness, as well as a material using the aforementioned filament and a method for manufacturing the material.

[0011] Solution for solving the problem

[0012] Based on the above-mentioned issues, the inventors conducted research and solved the above-mentioned issues by means of the following methods.

[0013] <1> A filament comprising: a polyamide resin having aromatic rings and / or heterocyclic rings, and a disperse dye having aromatic rings and / or heterocyclic rings.

[0014] <2> according to <1> The filament wherein the disperse dye comprises at least one selected from aromatic cyclic azo compounds, heterocyclic azo compounds, and anthraquinone compounds.

[0015] <3> according to <1> The filament wherein the aforementioned disperse dye has a skeleton as shown in formula (C1) or formula (C2).

[0016] Formula (C1)

[0017] Ar 1 -N=N-Ar 2

[0018] (In formula (C1), Ar) 1 and Ar 2 Each can independently represent an aryl group with 6 to 40 carbon atoms or a heteroaryl group with 5 to 40 carbon atoms.

[0019] Formula (C2)

[0020]

[0021] <4> according to <1> ~ <3> The filament in any one of the following examples, wherein the single filament fineness is 2.0 × 10⁻⁶. -5 ~50 dtex.

[0022] <5> according to <1> ~ <4> The filament in any one of the following examples has an elongation of 30% or more as measured in accordance with JIS L 1013:2010.

[0023] <6> according to <1> ~ <5> The filament in any one of the following embodiments, wherein the aforementioned polyamide resin comprises a polyamide resin consisting of structural units derived from diamine and structural units derived from dicarboxylic acids, wherein more than 70 mol% of the aforementioned structural units derived from diamine are derived from phenylenediamine, and more than 70 mol% of the aforementioned structural units derived from dicarboxylic acids are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

[0024] <7> according to <6> The filament wherein the aforementioned phenylenediamine comprises 30-100 mol% m-phenylenediamine and 0-70 mol% p-phenylenediamine.

[0025] <8> according to <6> or <7> The filaments wherein the aforementioned dicarboxylic acid comprises α,ω-linear aliphatic dicarboxylic acids having 11 to 14 carbon atoms.

[0026] <9> according to <6> or <7> The filament wherein the aforementioned dicarboxylic acid comprises 1,12-dodecanoic acid.

[0027] <10> according to <1> ~ <9> The filament in any one of the following examples has a length of 5 mm or more.

[0028] <11> according to <1> ~ <10> The filament in any one of the following examples, wherein the aforementioned polyamide resin is a crystalline polyamide resin.

[0029] <12> according to <1> ~ <11> The filament in any one of the following examples is a multifilament.

[0030] <13> according to <1> ~ <12> The filament in any one of the following embodiments, wherein 20 to 80 mol% of all structural units constituting the aforementioned polyamide resin are structural units having aromatic rings and / or heterocyclic rings.

[0031] <14> A material comprising filaments, wherein the filaments comprise: a polyamide resin having aromatic rings and / or heterocyclic rings, and a disperse dye having aromatic rings and / or heterocyclic rings.

[0032] <15> according to <14> The aforementioned material, wherein the filament is <1> ~ <13> The filament as described in any one of the following.

[0033] <16> according to <14> or <15> The aforementioned material is a knitted or woven fabric.

[0034] <17> according to <14> ~ <16> The material described in any one of the above statements has a color fastness of 3 or higher; here, color fastness refers to the degree of coloration of the white cotton cloth when the aforementioned material is fixed on a table and a 1kg cylindrical weight fully covered by cotton No. 3-1 as specified in JIS L 0803:2011 is placed on it, and the weight is oscillated 100 times, according to the gray scale of the staining grade in accordance with JIS L 0805:2011.

[0035] <18> A sort of <1> ~ <13> The method for manufacturing the filament according to any one of the following steps includes applying a polyamide filament containing a polyamide resin having aromatic rings and / or heterocyclic rings to a liquid containing a disperse dye having aromatic rings and / or heterocyclic rings and water.

[0036] <19> A method for manufacturing a material includes the following steps: applying a woven fabric formed from polyamide filaments containing a polyamide resin having aromatic rings and / or heterocyclic rings, or a knitted fabric formed from polyamide filaments containing a polyamide resin having aromatic rings and / or heterocyclic rings, to a liquid containing a disperse dye having aromatic rings and / or heterocyclic rings and water.

[0037] The effects of the invention

[0038] According to the present invention, a filament containing disperse dye and exhibiting excellent color fastness without compromising the original strength of the filament, as well as a material using the aforementioned filament and a method for manufacturing the material, can be provided. Detailed Implementation

[0039] Hereinafter, a method for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. It should be noted that the following embodiment is an example for illustrating the present invention, and the present invention is not limited to this embodiment.

[0040] It should be noted that in this specification, "~" is used to encompass the values ​​described before and after it as the lower limit and upper limit values.

[0041] In this specification, the descriptions of groups (atomic groups) that do not specify substitution or non-substitution include both groups (atomic groups) that do not have substituents and groups (atomic groups) that do have substituents. For example, the term "alkyl" includes not only alkyl groups that do not have substituents (unsubstituted alkyl) but also alkyl groups that have substituents (substituted alkyl). In this specification, the descriptions of unsubstituent and non-substitution are preferably those that are non-substituent.

[0042] Unless otherwise specified, all physical properties and characteristic values ​​in this manual are those taken at 23°C.

[0043] The filament of this embodiment is characterized by comprising: a polyamide resin having aromatic rings and / or heterocyclic rings, and a disperse dye having aromatic rings and / or heterocyclic rings. This filament does not compromise the original strength of the polyamide filament and, containing a disperse dye, exhibits excellent colorfastness. The reason for this is speculative, but it is speculated that the aromatic rings and / or heterocyclic rings of the polyamide resin interact with the aromatic rings and / or heterocyclic rings of the disperse dye, effectively introducing them into the polyamide filament. In contrast, the acid dye described in Patent Document 1 bonds to the terminal amino ions of the polyamide resin and is introduced into the polyamide filament.

[0044] It should be noted that in this specification, the state of the filament before dyeing in this embodiment is sometimes referred to as "polyamide filament". That is, polyamide filament generally does not contain disperse dyes having aromatic rings and / or heterocyclic rings.

[0045] <Polyamide resins with aromatic rings and / or heterocyclic rings>

[0046] The filament of this embodiment comprises a polyamide resin having aromatic rings and / or heterocyclic rings. By using this polyamide resin, the polyamide filament can be dyed using disperse dyes having aromatic rings and / or heterocyclic rings.

[0047] The type of polyamide resin containing aromatic rings and / or heterocyclic rings is not particularly limited. Preferably, 20-80 mol% of all structural units constituting the polyamide resin containing aromatic rings and / or heterocyclic rings are aromatic ring and / or heterocyclic structural units; more preferably, 30-70 mol% are aromatic ring and / or heterocyclic structural units; and even more preferably, 40-60 mol% are aromatic ring and / or heterocyclic structural units. By forming this configuration, in addition to solution spinning, melt spinning and other methods can be used as spinning methods. Furthermore, even when using solution spinning, strong acids such as concentrated sulfuric acid are not required as solvents, which tends to improve manufacturability.

[0048] The polyamide resin with aromatic rings and / or heterocyclic rings used in this embodiment preferably has aromatic rings.

[0049] Furthermore, the structural unit having an aromatic ring and / or a heterocyclic ring is preferably a structural unit derived from a diamine having an aromatic ring and / or a heterocyclic ring.

[0050] Examples of polyamide resins having aromatic rings and / or heterocyclic rings used in this embodiment include nylon 6T, nylon 6 / 6T, nylon 66 / 6T, nylon 6I, nylon 66 / 6I / 6, nylon 66 / 6I, nylon 6T / 6I, nylon 6T / 12, nylon 66 / 6T / 6I, nylon 9T, nylon 9I, nylon 9T, 9I, nylon 10T, 1,3-BAC10I (a polyamide resin composed of 1,3-diaminomethylcyclohexane, sebacic acid, and isophthalic acid), 1,4-BAC10I (a polyamide resin composed of 1,4-diaminomethylcyclohexane, sebacic acid, and isophthalic acid), and diphenylamine-based polyamide resins described in detail later, with diphenylamine-based polyamide resins being preferred.

[0051] In this embodiment, the polyamide resin preferably comprises a polyamide resin (hereinafter, in this specification, sometimes referred to as "phenylene dimethylamine-based polyamide resin") composed of structural units derived from diamine and structural units derived from dicarboxylic acids, wherein at least 70 mol% of the structural units derived from diamine are derived from phenylene dimethylamine, and at least 70 mol% of the structural units derived from dicarboxylic acids are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms. By using a phenylene dimethylamine-based polyamide resin, filaments with excellent colorfastness when containing the aforementioned disperse dyes can be obtained, as well as filaments with high Young's modulus. In addition, the water absorption rate is low, therefore, the mechanical properties such as Young's modulus and strength change little over time, resulting in fiber products with tensile strength and rigidity.

[0052] In the aforementioned diphenylene diamine-based polyamide resin, the structural units derived from diamine are derived from diphenylene diamine in a manner that is at least 70 mol%, preferably at least 80 mol%, more preferably at least 90 mol%, further preferably at least 95 mol%, and even more preferably at least 99 mol%. The upper limit may also be 100 mol%.

[0053] Phenylenediamine preferably comprises 30-100 mol% m-phenylenediamine and 0-70 mol% p-phenylenediamine, more preferably 50-100 mol% m-phenylenediamine and 0-50 mol% p-phenylenediamine. Furthermore, the total percentage of m-phenylenediamine and p-phenylenediamine in the phenylenediamine preferably is 95 mol% or more, more preferably 99 mol% or more, and even more preferably 100 mol%.

[0054] Examples of diamines other than phenylenediamine include aliphatic diamines such as tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine; alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminomethyl)decahydronaphthalene, and bis(aminomethyl)tricyclodecane; and diamines with aromatic rings such as bis(4-aminophenyl)ether, p-phenylenediamine, and bis(aminomethyl)naphthalene. One or more of these diamines can be used.

[0055] In the aforementioned diphenylene diamine-based polyamide resin, at least 70 mol% of the dicarboxylic acid structural units are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms, preferably at least 80 mol%, more preferably at least 90 mol%, further preferably at least 95 mol%, and even more preferably at least 99 mol%. The upper limit may also be 100 mol%.

[0056] The aforementioned α,ω-linear aliphatic dicarboxylic acids with 4 to 20 carbon atoms preferably have 6 or more carbon atoms, more preferably 9 or more, and even more preferably 11 or more carbon atoms. Furthermore, the aforementioned α,ω-linear aliphatic dicarboxylic acids with 4 to 20 carbon atoms preferably have 16 or fewer carbon atoms, more preferably 14 or fewer. The aforementioned α,ω-linear aliphatic dicarboxylic acids with 4 to 20 carbon atoms are further preferably 12 or fewer carbon atoms, and even more preferably 12.

[0057] By setting the carbon number to 4 or higher, the water absorption rate of the diphenylene diamine-based polyamide resin is reduced. When applying polyamide filaments to liquids containing disperse dyes and water, it is less likely to degrade the physical properties during dyeing. Furthermore, by setting the carbon number to 20 or lower, a practically sufficient melting point can be achieved for polyamide filaments, making them easy to use as fiber products through various processing methods. In particular, the high melting point increases resistance to heating during dyeing processes, drying after dyeing, and heating with irons, etc. Furthermore, a suitable Young's modulus can be achieved, resulting in tensile and rigid filaments.

[0058] Specific examples of the aforementioned α,ω-linear aliphatic dicarboxylic acids with 4 to 20 carbon atoms include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, 1,11-undecanoic acid, and 1,12-dodecanoic acid. Adipic acid, sebacic acid, and 1,12-dodecanoic acid are preferred, sebacic acid and 1,12-dodecanoic acid are more preferred, and 1,12-dodecanoic acid is even more preferred. The aforementioned effects are particularly pronounced when the α,ω-linear aliphatic dicarboxylic acid with 4 to 20 carbon atoms is 1,12-dodecanoic acid.

[0059] As a dicarboxylic acid component other than α,ω-linear aliphatic dicarboxylic acids with 4 to 20 carbon atoms, examples include phthalic acid compounds such as isophthalic acid, terephthalic acid, and phthalic acid, and naphthic acid 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. One type or a mixture of two or more types can be used.

[0060] It should be noted that "composed of structural units derived from diamines and structural units derived from dicarboxylic acids" means that the amide bonds constituting the phenylenediamine-based polyamide resin are formed through the bonding of dicarboxylic acids and diamines. In addition to structural units derived from dicarboxylic acids and diamines, the phenylenediamine-based polyamide resin also includes terminal groups and other sites. Furthermore, it may sometimes contain repeating units with amide bonds not derived from the bonding of dicarboxylic acids and diamines, trace amounts of impurities, etc. Specifically, in addition to diamine and dicarboxylic acid components, the phenylenediamine-based polyamide resin may also use lactams such as ε-caprolactam and laurolactam, and aliphatic aminocarboxylic acids such as aminohexanoic acid and aminoundecanoic acid as copolymerizing components, without impairing the effects of the present invention. In the present invention, preferably 90% or more, more preferably 95% or more, and even more preferably 98% or more of the phenylenediamine-based polyamide resin are structural units derived from diamines or dicarboxylic acids.

[0061] In addition, for the aforementioned nylon 6T and the like, besides being composed only of hexamethylenediamine and terephthalic acid, structural units derived from other monomers may of course be included without impairing the effects of the present invention.

[0062] The number-average molecular weight (Mn) of the polyamide resin having aromatic rings and / or heterocyclic rings used in this embodiment is preferably 6,000 to 50,000, more preferably 8,000 to 48,000, and even more preferably 9,000 to 46,000. If it is within this range, the molding processability becomes better.

[0063] It should be noted that the number-average molecular weight (Mn) mentioned here can be obtained from the conversion value of standard polymethyl methacrylate (PMMA) determined by gel permeation chromatography (GPC).

[0064] The aforementioned polyamide resin having aromatic rings and / or heterocyclic rings can be a crystalline polyamide resin with a defined melting point or an amorphous polyamide resin without a defined melting point, but is preferably a crystalline polyamide resin. By using a crystalline polyamide resin, it is more difficult to remove the disperse dye from the filament of this embodiment. In particular, when forming blended filaments with dyes that are easily dyed by disperse dyes, such as polyester filaments, color transfer can easily occur if the disperse dye easily removes from the filament of this embodiment, but this can be effectively avoided in this embodiment.

[0065] It should be noted that in this specification, amorphous resin refers to resin with a crystalline melting enthalpy ΔHm of less than 5 J / g, and crystalline resin refers to resin with a crystalline melting enthalpy ΔHm of more than 5 J / g.

[0066] When the aforementioned polyamide resin having aromatic rings and / or heterocyclic rings has a melting point, its melting point is preferably 170–250°C. By setting it to this range, molded articles with better processability and better heat resistance can be obtained.

[0067] It should be noted that the melting point in this invention refers to the temperature at the peak of the endothermic peak observed by DSC (Differential Scanning Calorimetry) during heating. Specifically, it refers to the following temperature: using a DSC device, with a sample volume of 1 mg, nitrogen gas as the atmosphere flowing at 30 mL / min, the sample is heated from room temperature (25 °C) to a temperature above the expected melting point at a heating rate of 10 °C / min until it melts; then, the molten polyamide resin is quenched in dry ice and heated again at a rate of 10 °C / min to a temperature above the melting point, at which point the temperature at the peak of the endothermic peak is observed.

[0068] Furthermore, in the filament of this embodiment, the polyamide resin having aromatic rings and / or heterocyclic rings preferably accounts for 70% or more by mass of the filament, more preferably 80% or more by mass, even more preferably 90% or more by mass, and may also be 95% or more by mass. The upper limit is, for example, 99.9% or less by mass.

[0069] The filaments in this embodiment may contain only one type, or they may contain two or more types of polyamide resins having aromatic rings and / or heterocyclic rings. When two or more types are contained, the total amount is preferably within the range described above.

[0070] Disperse dyes having aromatic rings and / or heterocyclic rings

[0071] The filament of this embodiment comprises a disperse dye having aromatic rings and / or heterocyclic rings. By using a dye having aromatic rings and / or heterocyclic rings, it interacts with the aromatic rings and / or heterocyclic rings of the polyamide resin, thus easily introducing the dye into the polyamide filament. Furthermore, the use of disperse dyes is also preferable for cases where blended filaments are formed with filaments dyed only by disperse dyes.

[0072] The disperse dyes used in this embodiment are not particularly limited as long as they have an aromatic ring and / or a heterocyclic ring. Widely known disperse dyes can be used, including aromatic ring azo compounds, heterocyclic azo compounds, anthraquinone compounds, quinoline compounds, quinoline ketone compounds, benzodifuranone compounds, coumarin compounds, etc. Preferably, they contain at least one selected from aromatic ring azo compounds, heterocyclic azo compounds, and anthraquinone compounds; more preferably, they contain at least one selected from aromatic ring azo compounds and anthraquinone compounds. By using such compounds, there is a tendency to further improve color fastness. Here, aromatic ring azo compounds refer to compounds containing an aromatic ring (preferably a benzene ring) and an azo structure (-N=N-). Heterocyclic azo compounds refer to compounds containing a heterocyclic ring and an azo structure (-N=N-). Anthraquinone compounds refer to compounds containing an anthraquinone ring. Quinoline compounds refer to compounds containing a quinoline ring. Quinoline ketone compounds refer to compounds containing a quinoline ketone ring. Benzodifuranone compounds refer to compounds containing a benzodifuranone ring. Coumarin compounds refer to compounds containing a coumarin ring. The molecular weight of these compounds is preferably 300 to 1000. By using compounds with this molecular weight, there is a tendency to effectively introduce disperse dyes into polyamide filaments.

[0073] The disperse dyes used in this embodiment preferably have a backbone as shown in formula (C1) or formula (C2). By using such compounds, there is a tendency to further improve colorfastness. Here, a compound having a backbone refers to a compound containing the structure shown in formula (C1) or formula (C2), or a compound in which the hydrogen atoms contained in the structure shown in formula (C1) or formula (C2) are replaced by substituents (e.g., substituent T, described later).

[0074] Formula (C1)

[0075] Ar 1 -N=N-Ar 2

[0076] (In formula (C1), Ar) 1 and Ar 2 Each can independently represent an aryl group with 6 to 40 carbon atoms or a heteroaryl group with 5 to 40 carbon atoms.

[0077] In formula (C1), examples of aryl groups having 6 to 40 carbon atoms (preferably 6 to 20 carbon atoms) are phenyl and naphthyl, with phenyl being more preferred. Examples of heteroaryl groups having 5 to 40 carbon atoms (preferably 5 to 20 carbon atoms) are pyrroleyl, pyrazolyl, trifluoromethylpyridine (a pyridalyl group), benzimidazolyl, oxadiazolyl, thiadiazolyl, tetrahydroquinolinyl, dihydrobenzoxazolyl, tetrahydroisoquinolinyl, thienyl, thiazolyl, isothiazolyl, benzothiazolyl, and benzoisothiazolyl.

[0078] The hydrogen atoms contained in formula (C1) (including Ar atoms) 1 and Ar 2 The hydrogen atoms contained therein can be replaced by substituents, such as substituent T described later. The aforementioned substituents can then be replaced by substituents.

[0079] Examples of substituents T include alkyl (preferably 1-24 carbons, more preferably 1-12, even more preferably 1-6), cycloalkyl (preferably 3-24 carbons, more preferably 3-12, even more preferably 3-6), aralkyl (preferably 7-21 carbons, more preferably 7-15, even more preferably 7-11), alkenyl (preferably 2-24 carbons, more preferably 2-12, even more preferably 2-6), cycloalkenyl (preferably 3-24 carbons, more preferably 3-12, even more preferably 3-6), hydroxyl, amino (preferably 0-24 carbons, more preferably 0-12, even more preferably 0-6), mercapto, carboxyl, aryl (preferably 6-22 carbons, more preferably 6-18, even more preferably 6-10), acyl (preferably 2-12 carbons, more preferably 2-6, even more preferably 2-3), acyloxy (preferably 2-12 carbons, more preferably 2-6, even more preferably 2-3), and aromatic... Acyl group (preferably 7-23 carbons, more preferably 7-19, even more preferably 7-11), aryloxy group (preferably 7-23 carbons, more preferably 7-19, even more preferably 7-11), carbamoyl group (preferably 1-12 carbons, more preferably 1-6, even more preferably 1-3), aminosulfonyl group (preferably 0-12 carbons, more preferably 0-6, even more preferably 0-3), sulfonyl group, alkylsulfonyl group (preferably 1-12 carbons, more preferably 1-6, even more preferably 1-3), arylsulfonyl group (preferably 6-22 carbons, more preferably 6-18, even more preferably 6-10), heterocyclic group (preferably 1-12 carbons, more preferably 1-8, even more preferably 2-5, preferably containing a 5-membered or 6-membered ring), (meth)acryloyl group, (meth)acryloyloxy group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), oxygen group (=O), imino group (=NR) N ), alkylidene (=C(R) N )2) etc. R N Preferably, a hydrogen atom or an alkyl group is used, more preferably a hydrogen atom. The alkyl and alkenyl sites in each substituent can be straight-chain or branched, and can be chain-like or cyclic. If the substituent T is a substituent group, it may further include a substituent T. For example, the alkyl group can be a haloalkyl group, (meth)acryloyloxyalkyl group, aminoalkyl group, or carboxylalkyl group. If the substituent is a group capable of forming a salt of a carboxyl group, amino group, etc., then that group can form a salt.

[0080] Formula (C2)

[0081]

[0082] The hydrogen atom contained in formula (C2) can be replaced by a substituent, such as substituent T described later. The aforementioned substituent can further be replaced by another substituent.

[0083] Examples of disperse dyes having the skeleton shown in formula (C1) are the following compounds.

[0084]

[0085] Examples of disperse dyes having the skeleton shown in formula (C2) are the following compounds.

[0086]

[0087] In addition to the above, as disperse dyes having aromatic rings and / or heterocyclic rings, those described in paragraphs 0040 to 0043 of Japanese Patent Application Publication No. 2019-182780 and paragraphs 0027 to 0045 of Japanese Patent Application Publication No. 2018-168486 may also be used, and these contents are incorporated into this specification.

[0088] The content of disperse dyes having aromatic rings and / or heterocyclic rings in the filament of this embodiment is preferably 0.1% by mass or more, more preferably 0.4% by mass or more, and even more preferably 0.5% by mass or more. By setting it to the aforementioned lower limit or above, the target hue can be effectively represented. Furthermore, the content of disperse dyes having aromatic rings and / or heterocyclic rings in the filament of this embodiment is preferably 5% by mass or less, more preferably 3.5% by mass or less, and even more preferably 3% by mass or less. By setting it to the aforementioned upper limit or less, differences from the target hue can be prevented, and color transfer during use as a fiber product can be more effectively suppressed.

[0089] The filaments of this embodiment may contain only one type, or they may contain two or more disperse dyes having aromatic rings and / or heterocyclic rings. When two or more types are contained, the total amount is preferably within the range described above.

[0090] <Other Ingredients>

[0091] The filaments of this embodiment may contain polyamide resins having aromatic rings and / or heterocyclic rings, and other components other than disperse dyes having aromatic rings and / or heterocyclic rings.

[0092] The filaments in this embodiment may comprise polyamide resins other than polyamide resins having aromatic rings and / or heterocyclic rings, or thermoplastic resins other than polyamide resins.

[0093] Examples of polyamide resins other than those having aromatic rings and / or heterocyclic rings include aliphatic polyamide resins such as polyamide 4, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 6 / 66, polyamide 610, and polyamide 612.

[0094] Other examples of thermoplastic resins besides polyamide resins include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate resins, polyoxymethylene resins, polyetherketone, polyethersulfone, and thermoplastic polyetherimide.

[0095] The content of polyamide resins other than polyamide resins having aromatic rings and / or heterocyclic rings and thermoplastic resins other than polyamide resins, when including these resins, is preferably 1 to 10 by mass of the filament in this embodiment.

[0096] The filament of this embodiment may further include, without impairing the purpose / effect of the present invention, additives such as antioxidants, heat stabilizers, hydrolysis resistance modifiers, weather stabilizers, matting agents, ultraviolet absorbers, nucleating agents, plasticizers, flame retardants, antistatic agents, antigelling agents, release agents, and surfactants. Details of these additives can be found in paragraphs 0130 to 0155 of Japanese Patent No. 4894982, paragraph 0021 of Japanese Unexamined Patent Application Publication No. 2010-281027, and paragraph 0036 of Japanese Unexamined Patent Application Publication No. 2016-223037, the contents of which are incorporated herein by reference. Regarding the content of these components, when these components are included, it is preferably 0.001 to 5% by mass of the filament of this embodiment.

[0097] The filaments in this embodiment are adjusted such that the total of the polyamide resin having aromatic rings and / or heterocyclic rings, the disperse dye having aromatic rings and / or heterocyclic rings, and other components (resins, additives, etc.) that are to be blended as needed is 100% by mass.

[0098] <Morphology and Properties of Filaments>

[0099] The filament in this embodiment can be a monofilament or a multifilament, but multifilament is preferred. By forming multifilaments, it becomes easier to process them into various fiber forms such as woven fabrics, knitted fabrics, ropes, and nonwoven fabrics.

[0100] In this embodiment, when the filament is a multifilament, the number of filaments constituting one multifilament is preferably 10 or more, more preferably 20 or more, and may also be 30 or more. Furthermore, 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 this range, unevenness in the fineness of the monofilaments during spinning can be suppressed, and furthermore, welding between monofilaments during spinning can be prevented.

[0101] The cross-section of the filament in this embodiment is typically circular. Here, "circular" refers not only to a circle in a geometric sense, but also to anything considered approximately circular within the technical field of this embodiment. However, the cross-section of the filament in this embodiment can be other shapes than a circle, such as an ellipse, oblong, or other flat shapes.

[0102] In this embodiment, the preferred single filament fineness of the filament is 2.0 × 10⁻⁶. -5 ~50 dtex. By setting it to a value above the aforementioned lower limit, stable spinning can be achieved, and when processed into various fiber product forms, the fiber products can have sufficient strength. Furthermore, by setting it to a value below the aforementioned upper limit, dyes can easily penetrate into the fiber interior, allowing for more vibrant dyeing. The aforementioned lower limit for monofilament fineness is preferably 8.0 × 10⁻⁶ dtex. -5 dtex or higher, preferably 9.0 × 10 dtex -3 dtex or higher, preferably 1.0 × 10⁻⁶ -2 The fineness is dtex or more, more preferably 0.5 dtex or more, and even more preferably 1 dtex or more. In addition, the upper limit of the aforementioned monofilament 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, even more preferably 18 dtex or less, and even more preferably 10 dtex or less.

[0103] Furthermore, in this embodiment, the fineness of the multifilament is preferably 10 to 1000 dtex. By setting it to the aforementioned lower limit or above, stable molding can be performed, and when processed into various fiber products, the fiber products can have sufficient strength. Furthermore, by setting it to the aforementioned upper limit or below, dye can easily penetrate into the fiber interior, allowing for more vibrant dyeing. 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. Furthermore, 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 500 dtex or less.

[0104] Fineness was determined according to the method described in the examples described later.

[0105] The filament length (weight-average length) in this embodiment is not particularly limited, but is preferably 5 mm or more, more preferably 0.1 m or more, further preferably 1 m or more, and even more preferably 100 m or more. Furthermore, as an upper limit for the filament length (weight-average length), it is preferably 20,000 m or less, more preferably 1,000 m or less, and even more preferably 100 m or less.

[0106] The elongation of the filament in this embodiment, measured according to JIS L 1013:2010, is preferably 30% or more. By ensuring an elongation of 30% or more, filament breakage during processing can be effectively suppressed. The aforementioned elongation is preferably 35% or more, more preferably 40% or more. The upper limit of the aforementioned elongation is preferably 70% or less, more preferably 60% or less. By setting it to the aforementioned upper limit or less, there is a tendency to further improve processability when processing into various fiber forms such as woven fabrics, knitted fabrics, ropes, and nonwoven fabrics.

[0107] The dye fastness of the filaments in this embodiment is preferably high. Specifically, when forming a material containing filaments as described in detail below, the dye fastness is preferably 3 or higher. The upper limit is preferably 5 or lower. Dye fastness refers to the degree of coloration of white cotton fabric when the aforementioned material is fixed on a table and a 1kg cylindrical weight fully covered by cotton 3-1 as specified in JIS L 0803:2011 is placed on it, and the weight is oscillated 100 times. This is determined using the grayscale level of staining according to JIS L 0805:2011.

[0108] <Materials>

[0109] The material in this embodiment is a material containing filaments, wherein the filaments comprise: a polyamide resin having aromatic rings and / or heterocyclic rings, and a disperse dye having aromatic rings and / or heterocyclic rings. Materials containing such filaments have excellent design flexibility and are therefore preferred for various applications. The aforementioned filaments are preferably the filaments of this embodiment.

[0110] The filaments of this embodiment can be used directly or processed into materials such as blended filaments, ropes, braids, short fiber yarns, and filaments with core-sheath structures. When forming blended filaments, it is preferable to combine them with reinforcing fibers (filaments) such as thermoplastic resin filaments, carbon fibers, and glass fibers.

[0111] The material in this embodiment can be a woven fabric, knitted fabric, or nonwoven fabric made of the filaments of this embodiment. Furthermore, by dyeing the woven fabric, knitted fabric, or nonwoven fabric made of polyamide filaments, the filaments in this embodiment contain polyamide resin having aromatic rings and / or heterocyclic rings, and disperse dyes having aromatic rings and / or heterocyclic rings. The woven fabric, knitted fabric, or nonwoven fabric in this embodiment also includes blended yarns, cords, braids, etc., using the filaments of this embodiment described above. The material in this embodiment is preferably a knitted fabric or a woven fabric.

[0112] Woven fabrics can be made using any weave pattern, such as plain weave, twill weave, satin weave, or gauze weave. Examples of knitted fabrics include plain knit.

[0113] The density of the material in this embodiment is preferably 1.10 to 1.25 g / cm³. 3 .

[0114] The material used in this embodiment preferably has high color fastness. Specifically, it is preferably 3 or higher. The upper limit is preferably 5 or lower. Here, color fastness refers to the degree of colorfastness of the white cotton cloth after the aforementioned material is fixed on a table and a 1kg cylindrical weight fully covered by cotton No. 3-1 as specified in JIS L 0803:2011 is placed on it, and the degree of colorfastness is determined by the gray scale of the stain according to JIS L 0805:2011 when the weight is rubbed back and forth 100 times.

[0115] The material in this embodiment refers to the filament that retains the shape of a filament. Here, "retaining" means maintaining the approximate shape of a filament, and also includes filaments formed by melting a portion (e.g., less than 10% by volume) of the filament and combining it with other filaments, reinforcing fibers, etc.

[0116] <Manufacturing Method>

[0117] The filament in this embodiment is obtained by molding a composition comprising a polyamide resin having aromatic rings and / or heterocyclic rings. The molding method is arbitrary and can be shaped into the desired shape using any conventionally known molding method such as melt spinning. For example, reference can be made to paragraphs 0051 to 0058 of International Publication No. 2017 / 010389, the contents of which are incorporated herein by reference.

[0118] In this embodiment, the polyamide filament is preferably manufactured by melt spinning or electrospinning. Melt spinning refers to a method in which a composition containing a polyamide resin having aromatic rings and / or heterocyclic rings is extruded from a porous die using an extruder and stretched by rollers. Electrospinning, on the other hand, involves dissolving a composition containing a polyamide resin having aromatic rings and / or heterocyclic rings in a solvent, and when the dissolved resin solution is discharged from a fine nozzle, an electric field is created at the outlet, causing the resin solution itself to become charged, stretching is achieved through a potential difference, and solvent is dispersed.

[0119] Furthermore, in this embodiment, the filament is generally preferably formed by impregnating the interior with disperse dye after forming a polyamide filament from a composition containing a polyamide resin having aromatic rings and / or heterocyclic rings. Specifically, in this embodiment, it is preferable to dye the polyamide filament by applying (preferably impregnating) the polyamide filament containing a polyamide resin having aromatic rings and / or heterocyclic rings to a liquid containing a disperse dye having aromatic rings and / or heterocyclic rings and water.

[0120] In this embodiment, when applying polyamide filament to a liquid containing a disperse dye having aromatic rings and / or heterocyclic rings and water, it is preferable to heat the liquid containing the disperse dye having aromatic rings and / or heterocyclic rings and water. The heating temperature is preferably 60°C or higher, more preferably 100°C or higher, and further preferably 120°C or higher, more preferably 125°C or higher. The upper limit of the aforementioned heating temperature is preferably 180°C or lower, more preferably 160°C or lower, further preferably 155°C or lower, and even more preferably 150°C or lower. By setting the temperature to the lower limit or higher, not only is dyeability improved, but the dye fastness of the dyed polyamide filament is also increased. By setting the temperature to the upper limit or lower, hydrolysis during dyeing is suppressed, and the reduction in tensile strength can be more effectively suppressed.

[0121] Furthermore, the filament in this embodiment is preferably stretched. Stretching can be performed either before or after applying the polyamide filament to a liquid containing a disperse dye having aromatic rings and / or heterocyclic rings and water, but stretching is preferred before application. The stretching ratio is preferably 1.5 to 6.0 times, more preferably 2.0 to 5.5 times. By stretching, the molecular chains are unidirectionally oriented, which further improves the tensile strength of the filament.

[0122] The preferred application time for the aforementioned liquid containing disperse dye and water is 10 to 100 minutes.

[0123] Furthermore, when the filaments of this embodiment are formed into knitted or woven fabrics, the polyamide filaments can be dyed and then processed into knitted or woven fabrics, or the polyamide filaments can be processed into knitted or woven fabrics and then dyed. By processing the polyamide filaments into knitted or woven fabrics and then dyeing them, processing costs can be reduced, and it becomes easier to handle small-batch, multi-variety production.

[0124] As a method of dyeing, it is preferable to apply polyamide filaments or knitted or woven fabrics formed from polyamide filaments to a liquid containing disperse dyes having aromatic rings and / or heterocyclic rings and water.

[0125] The term "disperse dye with aromatic rings and / or heterocycles" in a liquid containing disperse dyes with aromatic rings and / or heterocycles has the same meaning as the aforementioned disperse dyes with aromatic rings and / or heterocycles. For the aforementioned liquid containing disperse dyes and water, the disperse dye preferably accounts for 0.01 to 1% by mass of the liquid, and the water preferably accounts for 0.05 to 0.7% by mass of the liquid. Furthermore, the aforementioned liquid containing disperse dyes and water may contain components other than disperse dyes and water, or it may not contain any of them. Examples of components other than disperse dyes and water include anionic or nonionic / anionic surfactants, acetic acid, biphenyl, trichlorobenzene, methylnaphthalene, o-benzylphenol, p-benzylphenol, o-phenylphenol, propyl benzoate, butyl benzoate, 2-hydroxy-4-methoxybenzophenone, butyl p-hydroxybenzoate, methyl salicylate, vanillin, etc. The aforementioned liquid containing disperse dyes and water may contain only one type or two or more disperse dyes. When two or more types are contained, the total amount preferably falls within the range described above.

[0126] <Uses>

[0127] The filaments in this embodiment are preferably used in handbags, socks, clothing, carpets, fishing lines, fishing nets, industrial materials, racket strings, etc.

[0128] Furthermore, the filaments and materials of this embodiment are widely used in automobile and other transport aircraft parts, general mechanical parts, precision mechanical parts, electronic / electrical equipment parts, OA equipment parts, building materials / residential construction related parts, medical devices, leisure and sports products (e.g., fishing lines), game toys, medical products, food packaging films, clothing and other daily necessities, defense and aerospace products, etc.

[0129] In this embodiment, the filaments can be wound onto the core material. That is, a wound body having a core material and filaments wound onto the core material can also be formed.

[0130] Example

[0131] The following examples further illustrate the present invention. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0132] If the measuring equipment used in the examples is difficult to obtain due to production stoppages or other reasons, other equipment with equivalent performance can be used for measurement.

[0133] 1. Raw materials

[0134] <Synthesis of Polyamide MP12>

[0135] In a jacketed reactor equipped with a stirrer, condenser, condenser, thermometer, dropping tank, and nitrogen inlet pipe, 60.00 mol of precisely weighed 1,12-dodecanoic acid was added. The reactor was then thoroughly purged with nitrogen. Further, under a small nitrogen flow, the temperature was raised to 180°C to dissolve the 1,12-dodecanoic acid and create a homogeneous flow. Then, under stirring, 60 mol of p / m-phenylenediamine (30 mol% p-phenylenediamine and 70 mol% m-phenylenediamine) was added dropwise over 160 minutes. During this process, the reaction system was kept at atmospheric pressure, and the internal temperature was continuously raised to 250°C. Simultaneously, the distilled water was discharged from the system through the condenser and condenser during the dropwise addition of p / m-phenylenediamine. After the addition of p / m-phenylenediamine 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, followed by a 20-minute reaction. During this period, the reaction temperature was continuously increased to 260°C. After the reaction, a pressure of 0.3 MPa was applied using nitrogen gas inside the reactor, and the polymer was extracted from the nozzle at the bottom of the polymerization tank as a wire. After water cooling, it was cut into granules to obtain granules of the molten polymer. At room temperature, the obtained granules were fed into a rotating vacuum tank with a jacket heated by a hot medium. While rotating the tank, a reduced pressure (0.5–10 Torr) was created inside, and the circulating hot medium was heated to 150°C, raising the granule temperature to 130°C and maintaining this temperature for 3 hours. Then, nitrogen gas was introduced again to create atmospheric pressure, and cooling began. When the granule temperature dropped below 70°C, the granules were removed from the tank, yielding the solid-phase polymer.

[0136] The obtained polyamide resin (MP12) has a melting point of 206℃.

[0137] <Synthesis of Polyamide MXD12>

[0138] In a jacketed reactor equipped with a stirrer, condenser, condenser, thermometer, dropping tank, and nitrogen inlet pipe, 60.00 mol of precisely weighed 1,12-dodecanoic acid was added. The reactor was then fully purged with nitrogen. The temperature was further increased to 180°C under a small nitrogen flow to dissolve the 1,12-dodecanoic acid and create a homogeneous flow. Then, 60 mol of m-phenylenediamine was added dropwise over 160 minutes with stirring. During this time, the reaction system was kept at atmospheric pressure, and the internal temperature was continuously raised to 250°C. Water distilled off during the dropwise addition of m-phenylenediamine was discharged outside the system through the condenser and condenser. After the addition of m-phenylenediamine was completed, the liquid temperature was maintained at 250°C for 10 minutes. Afterward, the internal pressure was continuously reduced to 600 Torr over 10 minutes, and the reaction was continued for 20 minutes. During this time, the reaction temperature was continuously raised to 260°C. After the reaction, a pressure of 0.3 MPa is applied using nitrogen gas inside the reactor to extract the polymer as a thread from a nozzle at the bottom of the polymerization tank. After water cooling, the polymer is cut into granules to obtain granules of the molten polymer. At room temperature, the obtained granules are fed into a rotating vacuum tank with a jacket heated by a hot medium. While rotating the tank, a reduced pressure (0.5–10 Torr) is created inside, and the flowing hot medium is heated to 150°C, raising the granule temperature to 130°C and maintaining this temperature for 3 hours. Then, nitrogen gas is introduced again to create atmospheric pressure, and cooling begins. When the granule temperature drops below 70°C, the granules are removed from the tank to obtain the solid-phase polymer.

[0139] The resulting polyamide resin (MXD12) has a melting point of 190℃.

[0140] <Example of synthesis of polyamide MP10 (M / P ratio = 7:3)>

[0141] In a jacketed reactor equipped with a stirrer, condenser, condenser, thermometer, dropping tank, and nitrogen inlet pipe, sebacic acid was added and heated to dissolve under a nitrogen atmosphere. While stirring the contents, a mixed diamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) with a molar ratio of m-phenylenediamine to p-phenylenediamine of approximately 7:3 was slowly added dropwise under pressure (0.35 MPa) at a diamine to sebacic acid molar ratio of approximately 1:1, raising the temperature to 235°C. After the addition was complete, the reaction was continued for 60 minutes, adjusting the amount of components with a molecular weight below 1000. After the reaction was complete, the contents were removed in a thread and granulated in a granulator to obtain polyamide resin (MP10, M / P = 7:3).

[0142] The resulting polyamide resin (MP10) has a melting point of 215℃.

[0143] <Synthesis of Polyamide 1,3-BAC10I>

[0144] In a 50L pressure-resistant reaction vessel equipped with a stirrer, partial condenser, total condenser, pressure regulator, thermometer, drip tray, pump, suction device, nitrogen inlet pipe, bottom drain valve, and wire die, precisely weighed sebacic acid (made by Itoh Oil Chemicals Co., Ltd.), phthalic acid (made by Itoh Oil Chemicals Co., Ltd.), calcium hypophosphite (made by Kanto Chemical Co., Ltd.), and sodium acetate (made by Kanto Chemical Co., Ltd.) were placed in the vessel. After thorough nitrogen purging, the reaction vessel was sealed, and the pressure inside the vessel was maintained at 0.4MPa while the temperature was raised to 200°C with stirring. After reaching 200°C, 9847 g (69.22 mol) of 1,3-bis(aminomethyl)cyclohexane (1,3-BAC, isomer molar ratio: cis / trans = 75 / 25) (manufactured by Mitsubishi Gas Chemical Co., Ltd.) stored in the dropping tank was added dropwise to the raw materials in the reaction vessel. While maintaining the pressure in the vessel at 0.4 MPa, the generated condensation water was drained out of the system, and the temperature in the reaction vessel was raised to 295°C. After the addition of 1,3-BAC was completed, the pressure in the reaction vessel was slowly restored to atmospheric pressure, and then the pressure in the reaction vessel was reduced to 80 kPa using a suction device to remove the condensation water. The stirring torque of the stirrer was observed during the depressurization process. Stirring was stopped when the specified torque was reached, the reaction vessel was pressurized with nitrogen, the bottom drain valve was opened, the polymer was extracted from the wire die and wired, cooled, and then granulated using a granulator to obtain polyamide resin (1,3-BAC10I). According to JIS K7121, the enthalpy of crystal melting ΔHm(X) of the polyamide resin during the heating process was measured, and the result was 0 J / g, indicating that it is an amorphous polyamide resin.

[0145] PA6: Manufactured by Toray Industries, Inc., Amilan CM1017, melting point 225℃

[0146] PA66: Manufactured by Toray Industries, Inc., Amilan CM3001, melting point 265℃

[0147] Aromatic cyclic azo compounds: Disperse Blue 14, manufactured by Tokyo Chemical Industry Co., Ltd.

[0148] Anthraquinone compounds: Disperse Diazo Black 3BF, manufactured by Tokyo Chemical Industry Co., Ltd.

[0149] Examples 1-6, Comparative Examples 1 and 2

[0150] <Manufacturing of Polyamide Filaments>

[0151] The polyamide resin shown in Table 1 was melted using a single-screw extruder, and the spinning temperature was set to 290°C. The spun polyamide filaments were then spun through a spinneret (the number of orifices is shown in Table 1). After passing through a heating and cooling zone, the polyamide filaments, which were then brought to approximately room temperature (hereinafter sometimes referred to as "pre-drawing filaments"), were impregnated with a bundling agent (DELION PP-807, manufactured by Takemoto Oils & Fats Co., Ltd.) to form a bundle. This bundle was then collected using an unheated roller 1 and continuously drawn without being wound. The pre-drawing filaments collected using roller 1 were then heated by passing through roller 2, which was heated to 80°C. After passing through rollers 2, 3, and 4, which were heated to 170°C, the filaments were wound using a winding machine. At this time, a speed ratio was set between rollers 2 and 3 to achieve the desired drawing ratio, which was adjusted to a drawing ratio of 2 to 4. Additionally, a speed ratio was set between rollers 3 and 4 to allow for relaxation, and the rotational speed of roller 4 was set to be 4% slower than that of roller 3.

[0152] <Skin Fiber>

[0153] According to JIS L 1013:2010, the fineness of the filaments (positive fineness of multifilaments and fineness of monofilaments) shall be measured separately. The unit is expressed in dtex.

[0154] <Tensile Strength>

[0155] According to JIS L 1013:2010, after humidity adjustment at 23℃ and 50%RH, the filament was measured under the conditions of chuck spacing of 50cm and stretching speed of 50cm / min. The load at which the filament breaks was calculated by dividing the fineness (positive fineness) of the filament.

[0156] The unit is expressed in cN / dtex.

[0157] <Elongation>

[0158] According to JIS L 1013:2010, after humidity adjustment at 23℃ and 50%RH, the elongation was measured at a chuck spacing of 50cm and a stretching speed of 50cm / min. The elongation was calculated from the chuck spacing at the time of filament breakage using the following formula.

[0159] Elongation = {[(chuck spacing at fracture) - (chuck spacing before test)] / (chuck spacing before test)} × 100

[0160] The unit is expressed as %.

[0161] <Adsorption>

[0162] Using the filaments obtained above, the adsorption properties of the dye are evaluated according to the following method.

[0163] Using polyamide filaments, tubular knitted fabrics with 30 warp loops / 2.54 cm and 30 weft loops / 2.54 cm were made. These fabrics were then immersed in an aqueous solution containing either an azo compound (dye concentration: 0.5% by mass) or an anthraquinone compound (dye concentration: 0.5% by mass). While immersed, the fabrics were heated at 130°C for 30 minutes and then cooled to room temperature (25°C). The tubular knitted fabrics were removed from the solution and then immersed in aqueous solutions containing sodium hydroxide (Tokyo Chemical Industries), hyposulfite (Tokyo Chemical Industries), and Bisnol SK (LION SPECIALTY CHEMICALS) at concentrations of 1 g / L. While immersed, the fabrics were heated at 80°C for 10 minutes and then cooled to room temperature (25°C). The tubular knitted fabrics were removed from the solution, rinsed with water, and then wiped dry.

[0164] After allowing the tubular knitted fabric to air dry, it was fixed on a table, and a cylindrical weight covered with cotton 3-1 as specified in JIS L0803:2011 was placed on it. The evaluation of the fabric's absorbency was based on the presence or absence of color transfer after the weight was rubbed back and forth 100 times. The evaluation was conducted by five experts, and the judgment was made by majority vote.

[0165] A: No color transfer to white cotton fabric was observed. Or, color transfer to white cotton fabric is practically undetectable.

[0166] B: In addition to A above, for example, there is a clear color transfer on white cotton fabric.

[0167] <Dye fastness>

[0168] Fix the material on the table and place a 1kg cylindrical weight fully covered by cotton No. 3-1 as specified in JIS L 0803:2011. Determine which level of gray scale for pollution according to JIS L 0805:2011 corresponds to the degree of coloration of the white cotton cloth after the weight is rubbed back and forth 100 times.

[0169] <Ease of dye removal>

[0170] A tubular knitted fabric, prepared and dyed using the same method as described in the adsorption evaluation, was fixed on a table. A 5cm square piece of white cotton fabric (Cotton No. 3-1 as specified in JIS L 0803:2011) was placed on top of the fabric. An electric iron heated to 120–130°C was placed above the fabric, ensuring contact with approximately the center of the bottom surface. After 3 minutes, the tubular knitted fabric and the white cotton fabric were removed. The ease of dye removal was evaluated based on the presence or absence of color transfer to the white cotton fabric. The evaluation was conducted by five experts, with judgment made by majority vote.

[0171] A: No color transfer was observed on the white cotton fabric. Or, it is basically impossible to confirm.

[0172] B: In addition to A above, for example, there is a clear color transfer on white cotton fabric.

[0173] [Table 1]

[0174]

[0175] The above results demonstrate that the filaments of the present invention exhibit excellent strength and high color fastness (Examples 1-6). In contrast, the filaments of the comparative examples have low color fastness (Comparative Examples 1 and 2).

Claims

1. A filament comprising: a polyamide resin having aromatic rings and / or heterocyclic rings, and a disperse dye having aromatic rings and / or heterocyclic rings, wherein the polyamide resin comprises more than 90% by mass of the filament, and the polyamide resin comprises a polyamide resin consisting of structural units derived from diamines and structural units derived from dicarboxylic acids, wherein more than 70 mol% of the structural units derived from diamines are derived from phenylenediamine, and more than 70 mol% of the structural units derived from dicarboxylic acids are derived from α,ω-linear aliphatic dicarboxylic acids having 10 to 14 carbon atoms.

2. The filament according to claim 1, wherein, The disperse dye comprises at least one selected from aromatic cyclic azo compounds, heterocyclic azo compounds, and anthraquinone compounds.

3. The filament according to claim 1, wherein, The disperse dye has a skeleton as shown in formula (C1) or formula (C2). Formula (C1) Ar 1 -N=N-On 2 In formula (C1), Ar 1 and Ar 2 Each can independently represent an aryl group with 6 to 40 carbon atoms or a heteroaryl group with 5 to 40 carbon atoms. Formula (C2) 4. The filament according to any one of claims 1 to 3, wherein, The single filament fineness is 2.0 × 10⁻⁶. -5 ~50 dtex.

5. The filament according to any one of claims 1 to 3, wherein the elongation measured in accordance with JIS L 1013:2010 is 30% or more.

6. The filament according to claim 1, wherein, The phenylenediamine comprises 30 to 100 mol% m-phenylenediamine and 0 to 70 mol% p-phenylenediamine.

7. The filament according to claim 1 or 6, wherein, The dicarboxylic acid comprises α,ω-linear aliphatic dicarboxylic acids with 11 to 14 carbon atoms.

8. The filament according to claim 1 or 6, wherein, The dicarboxylic acid comprises 1,12-dodecanoic acid.

9. The filament according to any one of claims 1 to 3, wherein the filament length is 5 mm or more.

10. The filament according to any one of claims 1 to 3, wherein, The polyamide resin is a crystalline polyamide resin.

11. The filament according to any one of claims 1 to 3, wherein, The filament is a multifilament.

12. The filament according to any one of claims 1 to 3, wherein, Of all the structural units constituting the polyamide resin, 20 to 80 mol% are structural units having aromatic rings and / or heterocyclic rings.

13. A material comprising filaments, wherein the filaments comprise: a polyamide resin having aromatic rings and / or heterocyclic rings, and a disperse dye having aromatic rings and / or heterocyclic rings, wherein the filaments are any one of claims 1 to 12.

14. The material according to claim 13, wherein, The material is a knitted or woven fabric.

15. The material according to claim 13 or 14, wherein the color fastness is 3 or higher; here, the color fastness refers to the degree of coloration of the white cotton cloth when the material is fixed on a table and a 1kg cylindrical weight fully covered by cotton No. 3-1 as specified in JIS L 0803:2011 is placed on it and the weight is rubbed back and forth 100 times, as determined by the gray scale of the staining according to JIS L 0805:2011.

16. A method for manufacturing a filament according to any one of claims 1 to 12, comprising the step of applying a polyamide filament containing a polyamide resin having aromatic rings and / or heterocyclic rings to a liquid containing a disperse dye having aromatic rings and / or heterocyclic rings and water.

17. A method of manufacturing a material, comprising the steps of: applying a woven fabric formed from a polyamide filament comprising a polyamide resin having aromatic rings and / or heterocyclic rings, or a knitted fabric formed from a polyamide filament comprising a polyamide resin having aromatic rings and / or heterocyclic rings, to a liquid comprising a disperse dye having aromatic rings and / or heterocyclic rings and water. The polyamide resin accounts for more than 90% by mass of the polyamide filament, and the polyamide resin comprises the following polyamide resin: it is composed of structural units derived from diamine and structural units derived from dicarboxylic acid, wherein more than 70 mol% of the structural units derived from diamine are derived from phenylenediamine, and more than 70 mol% of the structural units derived from dicarboxylic acid are derived from α,ω-linear aliphatic dicarboxylic acids having 10 to 14 carbon atoms.

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