JP6654439B2 - Fabric, method for producing the same, and fiber product - Google Patents

Description

  The present invention relates to a fabric containing meta-type wholly aromatic polyamide fibers, having flame retardancy and washing durability, and having antifouling properties, a method for producing the same, and a fiber product.

Conventionally, fabrics containing meta-type wholly aromatic polyamide fibers have been used as protective clothing such as work clothes and firefighting suits because of their excellent flame retardancy (for example, Patent Document 1).
However, a fabric containing a meta-type wholly aromatic polyamide fiber, having flame retardancy and washing durability and having an antifouling property has not been proposed so far.

JP 2005-273093 A

  The present invention has been made in view of the above background, and an object of the present invention is to provide a fabric containing a meta-type wholly aromatic polyamide fiber, having flame retardancy and washing durability, having an antifouling property, a method for producing the same, and a fiber product. Is to provide.

  The present inventors have conducted intensive studies to achieve the above object, and as a result, when a water-repellent agent is applied to a fabric containing a meta-type wholly aromatic polyamide fiber using a specific crosslinking agent, flame retardancy and washing durability are improved. The present inventors have found that a cloth having a certain antifouling property can be obtained, and have made extensive studies to complete the present invention.

Thus, according to the present invention, "a fabric containing a meta-type wholly aromatic polyamide fiber, which is subjected to 10 washes according to JIS L0217-1998, 103 methods, and then specified by JIS L1919-2012 B methods. fabric antifouling of Ri der quaternary or higher, and is a crosslinking agent and a water-repellent agent having an oxazoline group, characterized in that it comprises a binder containing an acrylic resin and / or urethane resins. "is provided You.

In this case, it is preferable that the meta-type wholly aromatic polyamide fiber contains an organic dye, an organic pigment, or an inorganic pigment. Preferably, the fabric further contains polyester fibers. Further, the fabric further comprises para-type wholly aromatic polyamide fiber, wholly aromatic polyester fiber, polybenzoxazole (PBO) fiber, polybenzimidazole (PBI) fiber, polybenzthiazole (PBTZ) fiber, polyimide (PI) fiber, Consists of polysulfonamide (PSA) fiber, polyetheretherketone (PEEK) fiber, polyetherimide (PEI) fiber, polyarylate (PAr) fiber, melamine fiber, phenol fiber, fluorine-based fiber, and polyphenylene sulfide (PPS) fiber It is preferable to include at least one selected from the group. In addition, the fabric is further selected from the group consisting of cellulose fibers, polyolefin fibers, acrylic fibers, rayon fibers, cotton fibers, animal hair fibers, polyurethane fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, acetate fibers and polycarbonate fibers. It is preferable to include at least one of them. Further, it is preferable that any fiber constituting the fabric contains a flame retardant . Also, it is preferable crystallinity of the meta-type wholly aromatic polyamide fibers is in the range of 15-25%. The meta-type wholly aromatic polyamide fiber preferably has a residual solvent amount of 0.1% by mass or less. The meta-type wholly aromatic polyamide forming the meta-type wholly aromatic polyamide fiber is a main structural unit having a repeating structure in an aromatic polyamide skeleton containing a repeating structural unit represented by the following formula (1). It is preferable to use an aromatic polyamide obtained by copolymerizing different aromatic diamine components or aromatic dicarboxylic acid halide components as the third component so as to be 1 to 10 mol% with respect to the total amount of the repeating structural units of the aromatic polyamide. .
-(NH-Ar1-NH-CO-Ar1-CO)-... Formula (1)
Here, Ar1 is a divalent aromatic group having a binding group other than the meta-coordination or parallel axis direction.
In this case, the aromatic diamine serving as the third component is preferably represented by Formulas (2) and (3), or the aromatic dicarboxylic acid halide is preferably represented by Formulas (4) and (5).
H ₂ N—Ar ₂ —NH ₂ Formula (2)
_{H 2 N-Ar2-Y-} Ar2-NH 2 ··· formula (3)
XOC-Ar3-COX Formula (4)
XOC-Ar3-Y-Ar3-COX Formula (5)
Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group. Or X is a functional group, and X represents a halogen atom.

Further, the fabric preferably contains an ultraviolet absorber and / or a reflector. Further, it is preferable that the afterflame is 2.0 seconds or less in the flammability measurement specified in JIS L1091-1992 A-4 method.
Further, according to the present invention, there is provided the method for producing a fabric as described above, wherein a cross-linking agent having an oxazoline group, a water repellent , an acrylic resin and / or a urethane-based fabric are added to a fabric containing meta-type wholly aromatic polyamide fibers. A method for producing a fabric, characterized by providing a binder containing a resin .
According to the present invention, any of the above-mentioned cloths is used and selected from the group consisting of protective clothing, fire and fire protection clothing, fire fighting clothing, rescue clothing, workwear, police uniform, SDF clothing, and military clothing. Are provided.

  ADVANTAGE OF THE INVENTION According to this invention, the fabric which contains meta type wholly aromatic polyamide fiber, has flame retardancy and washing durability, and has antifouling property, its manufacturing method, and a fiber product are obtained.

Hereinafter, embodiments of the present invention will be described in detail.
First, the meta-type wholly aromatic polyamide fiber used in the present invention is a fiber comprising a polymer in which 85 mol% or more of the repeating unit is m-phenylene isophthalamide. Such a meta-type wholly aromatic polyamide may be a copolymer containing the third component in a range of less than 15 mol%.

  Such a meta-type wholly aromatic polyamide can be produced by a conventionally known interfacial polymerization method, and the polymerization degree of the polymer is 0.5 g / 100 ml in N-methyl-2-pyrrolidone solution. Those having a measured intrinsic viscosity (IV) in the range of 1.3 to 1.9 dl / g are preferably used.

  The meta-type wholly aromatic polyamide may contain an alkylbenzenesulfonic acid onium salt. Examples of the alkylbenzenesulfonic acid onium salts include hexylbenzenesulfonic acid tetrabutylphosphonium salt, hexylbenzenesulfonic acid tributylbenzylphosphonium salt, dodecylbenzenesulfonic acid tetraphenylphosphonium salt, and dodecylbenzenesulfonic acid tributyltetradecylphosphonate. Compounds such as a sodium salt, tetrabutylphosphonium dodecylbenzenesulfonate, and tributylbenzylammonium dodecylbenzenesulfonate are preferably exemplified. Above all, tetrabutylphosphonium dodecylbenzenesulfonate or tributylbenzylammonium dodecylbenzenesulfonate is easily available, has good thermal stability, and has high solubility in N-methyl-2-pyrrolidone. It is preferably exemplified.

  The content ratio of the above-mentioned alkylbenzenesulfonic acid onium salt is at least 2.5 mol%, preferably 3.0 to 7.0 mol, based on poly-m-phenyleneisophthalamide in order to obtain a sufficient effect of improving dyeability. % Is preferred.

  As a method of mixing poly-m-phenylene isophthalamide and onium salt of alkylbenzenesulfonic acid, a method of mixing and dissolving poly-m-phenyleneisophthalamide in a solvent and dissolving the onium salt of alkylbenzenesulfonic acid therein is used. Etc. are used, and any of them may be used. The dope thus obtained is formed into fibers by a conventionally known method.

The polymer used for the meta-type wholly aromatic polyamide fiber has a repeating structure in an aromatic polyamide skeleton containing a repeating structural unit represented by the following formula (2) for the purpose of improving dyeing properties and resistance to discoloration. It is also possible to copolymerize an aromatic diamine component or an aromatic dicarboxylic acid halide component different from the main constituent unit of the above as a third component so as to be 1 to 10 mol% with respect to the total amount of the repeating structural units of the aromatic polyamide. It is.
-(NH-Ar1-NH-CO-Ar1-CO)-... Formula (1)
Here, Ar1 is a divalent aromatic group having a binding group other than the meta-coordination or parallel axis direction.

It is also possible to copolymerize as the third component. Specific examples of the aromatic diamine represented by the formulas (2) and (3) include, for example, p-phenylenediamine, chlorophenylenediamine, methylphenylenediamine, Acetylphenylenediamine, aminoanisidine, benzidine, bis (aminophenyl) ether, bis (aminophenyl) sulfone, diaminobenzanilide, diaminoazobenzene and the like can be mentioned. Specific examples of the aromatic dicarboxylic acid dichloride represented by the formulas (4) and (5) include, for example, terephthalic acid chloride, 1,4-naphthalenedicarboxylic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4 '-Biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, bis (chlorocarbonylphenyl) ether and the like.
H ₂ N—Ar ₂ —NH ₂ Formula (2)
_{H 2 N-Ar2-Y-} Ar2-NH 2 ··· formula (3)
XOC-Ar3-COX Formula (4)
XOC-Ar3-Y-Ar3-COX Formula (5)
Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group. Or X is a functional group, and X represents a halogen atom.

The crystallinity of the meta-type wholly aromatic polyamide fiber is 5 to 35% in that the dye has good exhaustion properties and is easily adjusted to a target color even with a smaller amount of dye or weak dyeing conditions. Preferably, there is. Further, the content is more preferably 15 to 25% from the viewpoint that the uneven distribution of the dye surface hardly occurs, the discoloration resistance is high, and the dimensional stability required for practical use can be secured.
Further, the residual solvent amount of the meta-type wholly aromatic polyamide fiber is 0 in that the excellent flame-retardant performance of the meta-type wholly aromatic polyamide fiber is not impaired and that the dye is less likely to be unevenly distributed on the surface and the discoloration resistance is high. 0.1% by weight or less.

The meta-type wholly aromatic polyamide fiber can be produced by the following method, and in particular, the crystallinity and the amount of the remaining solvent can be adjusted to the above ranges by the method described later.
The method of polymerizing the meta-type wholly aromatic polyamide polymer is not particularly limited. For example, the solution weight described in Japanese Patent Publication No. 35-14399, U.S. Pat. No. 3,360,595, and Japanese Patent Publication No. 47-10863 may be used. A legal method or an interfacial polymerization method may be used.

The spinning solution is not particularly limited, but an amide-based solvent solution containing an aromatic copolyamide polymer obtained by the above solution polymerization or interfacial polymerization may be used, or the polymer may be converted from the polymerization solution. It may be used after isolation and dissolution in an amide solvent.
Examples of the amide-based solvent used herein include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, and the like. In particular, N, N-dimethylacetamide Is preferred.

The copolymerized aromatic polyamide polymer solution obtained as described above is further stabilized by containing an alkali metal salt or an alkaline earth metal salt, and can be used at a higher concentration and at a lower temperature, which is preferable. Preferably, the alkali metal salt and alkaline earth metal salt are at most 1% by weight, more preferably at most 0.1% by weight, based on the total weight of the polymer solution.
In the spinning / coagulation step, the spinning solution (meta-type wholly aromatic polyamide polymer solution) obtained above is spun into a coagulation solution and coagulated.

The spinning device is not particularly limited, and a conventionally known wet spinning device can be used. Further, as long as the spinning can be performed stably, the number of spinning holes, arrangement state, hole shape, etc. of the spinneret need not be particularly limited. For example, the number of spinning holes is 1,000 to 30,000, and the spinning hole diameter is 0.05. You may use a multi-hole spinneret or the like for a soup of up to 0.2 mm.
The temperature of the spinning solution (meta-type wholly aromatic polyamide polymer solution) when spinning from the spinneret is suitably in the range of 20 to 90 ° C.

  As a coagulation bath used for obtaining the fiber, an aqueous solution of an amide-based solvent, preferably having an NMP concentration of 45 to 60% by mass, containing substantially no inorganic salt, is used at a bath solution temperature of 10 to 50 ° C. Used. If the concentration of the amide solvent (preferably NMP) is less than 45% by mass, the skin has a thick structure, the washing efficiency in the washing step is reduced, and it becomes difficult to reduce the residual solvent amount of the fiber. On the other hand, when the concentration of the amide-based solvent (preferably NMP) exceeds 60% by mass, uniform coagulation cannot be performed even to the inside of the fiber. Becomes difficult. The time for immersing the fibers in the coagulation bath is suitably in the range of 0.1 to 30 seconds.

Subsequently, an amide-based solvent, preferably an aqueous solution having an NMP concentration of 45 to 60% by mass, in a plastic stretching bath in which the temperature of the bath solution is in the range of 10 to 50 ° C., at a stretching ratio of 3 to 4 times. Perform stretching. After the stretching, washing is sufficiently performed through an aqueous solution having an NMP concentration of 20 to 40% by mass at 10 to 30 ° C, and subsequently to a warm water bath at 50 to 70 ° C.
The washed fiber is subjected to a dry heat treatment at a temperature of 270 to 290 ° C. to obtain a meta-type wholly aromatic aramid fiber satisfying the above ranges of crystallinity and residual solvent amount.
In the meta-type wholly aromatic aramid fiber, the fiber may be a long fiber (multifilament) or a short fiber. In particular, short fibers having a fiber length of 25 to 200 mm are preferable for blending with other fibers. The single fiber fineness is preferably in the range of 1 to 5 dtex.

  In the present invention, the fabric may be composed of only the meta-type wholly aromatic aramid fiber, but preferably further contains polyester fiber. If the fabric contains polyester fibers, the SP value (dissolution parameter) of a binder comprising an oxazoline group or an acrylic resin and / or a urethane resin as described later is close to that of the polyester fibers and the polyester fibers have Since it is easy to adhere, it is preferable because the washing durability of the antifouling property can be improved. At this time, the weight of the polyester fiber contained in the fabric is preferably in the range of 2 to 20% by weight based on the weight of the fabric. If the weight of the polyester fiber is larger than the above range, the flame retardancy may be reduced. Conversely, if the weight of the polyester fiber is smaller than the above range, the washing durability of the antifouling property may decrease.

Further, a para-type wholly aromatic polyamide fiber, a wholly aromatic polyester fiber, a polybenzoxazole (PBO) fiber, a polybenzimidazole (PBI) fiber, a polybenzthiazole (PBTZ) fiber, a polyimide (PI) fiber, Difficulty of polysulfonamide (PSA) fiber, polyetheretherketone (PEEK) fiber, polyetherimide (PEI) fiber, polyarylate (PAr) fiber, melamine fiber, phenol fiber, fluorine-based fiber, polyphenylene sulfide (PPS) fiber, etc. It is preferable that fuel fibers are included.
At that time, it is preferable that the limit oxygen index (LOI) of the flame-retardant fiber is 20 or more.

Further, the fabric further contains cellulose fiber, polyolefin fiber, acrylic fiber, rayon fiber, cotton fiber, animal hair fiber, polyurethane fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, acetate fiber, polycarbonate fiber and the like. , Water absorption, dyeability, wearing comfort and the like are added, which is preferable.
Here, it is preferable that these fibers are blended. At that time, in order to exhibit excellent heat resistance and flame retardancy of the meta-type wholly aromatic polyamide fiber, it is preferable that the meta-type wholly aromatic polyamide fiber is 50% by mass or more. As a more specific example, the meta-type wholly aromatic polyamide fiber is 50 to 98% by mass, the polyester fiber is 2 to 20% by mass, and the cellulose-based mass fiber is 0 to 50%. It is also possible to improve both the dyeing properties and the comfort. Further, the fibers constituting the fabric may contain a flame retardant, an ultraviolet absorber, a reflector and the like.

In the present invention, the method for producing the fabric is not particularly limited, and any known method can be used. For example, it is preferable that a spun yarn is obtained by blending a spun yarn of the above-mentioned fibers, and then a single yarn or a twin yarn is woven into a twill weave, a plain weave or the like using a rapier loom or the like.
In the present invention, the cloth specified by the JIS L1919-2012 B method has the antifouling property of class 4 or higher after washing 10 times according to the JIS L0217-1998, 103 method.

The cloth having such antifouling properties can be produced, for example, by the following production method. That is, a treatment liquid containing a crosslinking agent having an oxazoline group, a water repellent, and a binder may be applied to the fabric containing the meta-type wholly aromatic polyamide fiber.
Here, examples of the water repellent include a fluorine-based water repellent, a silicone-based water repellent, and a hydrocarbon-based water repellent as described in JP-A-2006-291372. A fluorine-based water repellent having a total concentration of perfluorooctanoic acid and perfluorooctanesulfonic acid of 0 to 5 ng / g may be used. Examples of such a fluorine-based water repellent include “Asahigard AG-E061” manufactured by Asahi Glass Co., Ltd.

  Among them, a fluorine-based water repellent having a hydrophilic segment is preferable for obtaining excellent antifouling properties. In particular, a fluorine-based water repellent having a hydrophilic segment as described in JP-A-2013-72165 is preferable. That is, the fluorinated water repellent having a hydrophilic segment includes a copolymer obtained by copolymerizing a hydrophilic segment and a fluorinated hydrophobic segment.

The hydrophilic segment is used to modify ethylenically unsaturated substances such as acrylates, methacrylates, vinyl acetate, and vinyl chloride, and to react with hydrophilic groups such as ethylene oxide, hydroxyl groups, carboxyl groups, and sulfonic acid groups. Is introduced. Among them, a hydrophilic segment obtained by reacting hydrogen sulfide with polyethylene glycol dimethacrylate is preferred from the viewpoint of improving the stain removal property and excellent stain resistance.
Further, as the fluorinated hydrophobic segment, a fluoroalkyl acrylate containing a perfluoroalkyl group is preferable from the viewpoint of preventing adhesion of dirt and excellent antifouling properties. As such a fluorine-based water repellent, a commercially available product can be suitably used, and specific examples thereof include "Asahigard AG-E100" manufactured by Asahi Glass Co., Ltd.

As the binder, those having a contact angle with the fiber of 90 ° or less (preferably 70 ° or less, more preferably 50 ° or less) are suitable. Since the smaller the contact angle, the better the wettability, the binder is uniformly coated on the surface of the single fiber. As a result, not only the durability of the antifouling property (water repellency) is improved, but also the soft texture of the fabric is not impaired. Examples of the binder resin having a contact angle with the fiber of 90 degrees or less include a melamine resin, an epoxy resin, a urethane resin, and an acrylic resin. Particularly, those containing an acrylic resin and / or a urethane resin are preferable.
Further, the water repellent and the binder resin should be added to the processing liquid so that the amount of adhesion to the cloth is 0.001 to 5% by weight based on the total weight of the target cloth, based on the weight of the resin solids. Is preferred.

  The crosslinking agent having an oxazoline group refers to a general organic compound or a compound having an oxazoline group (preferably a 2-oxazoline group) at a terminal or a side chain of a substance having a main skeleton of an organic polymer or oligomer. By using a cross-linking agent having an oxazoline group, the water-repellent agent easily permeates between the single fibers, and antifouling properties with higher washing durability can be obtained. The oxazoline group can have one or more oxazoline groups in its skeleton, but it is more preferable to have many oxazoline groups that are reactive functional groups in order to improve adhesion performance. As the skeleton of the main chain of the oxazoline group-containing substance, hydrocarbon chains, ethylene glycol chains, bisphenols such as bisphenol A, and prepolymers such as phenolic resins, novolak resins, and resole resins are used. Among them, a substance containing an aromatic ring or a hetero ring is also used. Further, a substance containing an oxazoline group at a terminal or a side chain of a main component monomer and / or a polymer or oligomer comprising the same is also useful. As these monomers, styrene, styrene derivatives, acrylonitrile, methacrylic acid ester, methacrylic acid, ethylene, butadiene, acrylamide and the like are used, and these are used as a single polymer and / or oligomer and further as a copolymer material. . Further, they can also be used as a mixture thereof.

  The oxazoline group-containing substance may be in the form of a liquid, a melt, a solid, a solution in water or an organic solvent capable of dissolving them, or a suspension dispersed in water (emulsion particles, latex particles, etc.). used. For example, a compound obtained by dissolving such a compound as it is or, if necessary, in a small amount of a solvent is used with a known emulsifier, for example, sodium alkylbenzenesulfonate, sodium salt of dioctylsulfosuccinate, nonylphenol-ethylene oxide adduct, or the like. Alternatively, a method of emulsification or dissolution may be used.

  As a method of applying the treatment liquid to the cloth, the treatment liquid may be prepared and treated by means such as immersion, coating, spraying and the like. At this time, the treatment liquid adhesion amount is preferably 0.01 to 10% by weight (more preferably 0.03 to 5% by weight) based on the weight of the fabric. If the treatment liquid adhesion amount is smaller than the above range, the antifouling property may be reduced. Conversely, if the treatment liquid adhesion amount is larger than the above range, the antifouling property will not be further improved, and the properties of the fiber product may be rather deteriorated. As a processing method, a method (padding method) of heating and drying after squeezing so as to maintain a predetermined amount of the processing liquid is preferable.

In addition, before and / or after the treatment liquid is applied to the fabric, a water absorbing process (a hydrophilizing agent is applied) or a dyeing process may be performed.
Here, the hydrophilic agent is preferably polyethylene glycol diacrylate, a derivative of polyethylene glycol diacrylate, a polyethylene terephthalate-polyethylene glycol copolymer, a water-soluble polyurethane or a polyethylene glycol-amino silicone copolymer.

The amount of the hydrophilic agent attached to the fabric is preferably 0.1 to 2.0% by weight (more preferably 0.1 to 0.7% by weight) based on the weight of the fabric. The amount of the hydrophilic agent attached can be calculated by the following equation.
Amount of hydrophilic agent attached (%) = ((weight of fabric after hydrophilic agent attached) − (weight of fabric before hydrophilic agent attached)) / (weight of fabric before hydrophilic agent attached) ) × 100
However, the weight of the fabric after the attachment of the hydrophilizing agent is the weight after drying.

Examples of a method for imparting a hydrophilic agent to a fabric include a method of performing padding treatment, a method of performing treatment in a same bath with a dyeing liquid during dyeing processing, and the like.
Furthermore, various other processes that provide flame retardants, heat storage agents, ultraviolet shielding agents, antistatic agents, antibacterial agents, deodorants, insect repellents, mosquito repellents, luminous storage agents, retroreflective agents, etc. are additionally applied. Is also good.

In the thus obtained fabric, the basis weight is preferably 130 to 360 g / m ² (more preferably, 140 to 260 g / m ² ).
Since such a cloth uses the cross-linking agent having an oxazoline group as described above, the antifouling agent easily permeates between the single fibers, and the antifouling property with higher washing durability can be obtained. Also, since it contains meta-type wholly aromatic polyamide fibers, it has excellent flame retardancy.
Here, as the flame retardancy, it is preferable that the after-flame is 2.0 seconds or less in the flammability measurement specified in JIS L1091-1992 A-4 method.

  Next, the textile product of the present invention is any one selected from the group consisting of protective clothing, fire and fire protection clothing, fire fighting clothing, rescue clothing, workwear, police uniform, SDF clothing, and military uniform using the above-mentioned cloth. It is a textile product. Since such a fiber product uses the above-mentioned cloth, it has flame retardancy and anti-fouling properties with washing durability.

  Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In addition, each physical property in an Example is measured by the following method.

(1) Antifouling property of cloth The cloth was washed 10 times according to JIS L0217-1998, 103 method, and then the antifouling property was measured according to JIS L1919-2012 B method.

(2) Flame retardancy of fabric (vertical combustion test)
The afterflame time was measured according to JIS L1091-1992 A-4 method.

(3) Amount of Residual Solvent About 8.0 g of the raw fiber was collected, dried at 105 ° C. for 120 minutes, and then allowed to cool in a desiccator, and the fiber mass (M1) was weighed. Subsequently, the fiber was subjected to reflux extraction in methanol for 1.5 hours using a Soxhlet extractor to extract an amide-based solvent contained in the fiber. The fiber after the extraction was taken out, vacuum-dried at 150 ° C. for 60 minutes, allowed to cool in a desiccator, and weighed (M2). The amount of the solvent remaining in the fiber (the mass of the amide-based solvent) was calculated by the following equation using the obtained M1 and M2.
Residual solvent amount (%) = [(M1-M2) / M1] × 100

(4) Crystallinity Using an X-ray diffractometer (RINT TTRIII, manufactured by Rigaku Corporation), the raw fibers were arranged in a bundle of fibers having a diameter of about 1 mm, mounted on a fiber sample table, and the diffraction profile was measured. The measurement conditions were a Cu-Kα radiation source (50 kV, 300 mA), a scanning angle range of 10 to 35 °, continuous measurement of 0.1 ° width, and scanning at 1 ° / min. Air scattering and incoherent scattering were corrected by linear approximation from the measured diffraction profile to obtain a total scattering profile. Next, the crystal scattering profile was obtained by subtracting the amorphous scattering profile from the total scattering profile. The crystallinity was determined from the area intensity of the crystal scattering profile (crystal scattering intensity) and the area intensity of the total scattering profile (total scattering intensity) according to the following equation.
Crystallinity (%) = [crystal scattering intensity / total scattering intensity] × 100

(5) Fabric weight Measured according to JIS L 1096.
[Production of meta-type wholly aromatic aramid fiber]
The meta-type wholly aromatic aramid fiber was produced by the following method.
20.0 parts by mass of a polymetaphenylene isophthalamide powder having an intrinsic viscosity (IV) of 1.9, produced by an interfacial polymerization method according to the method described in JP-B-47-10863, at -10 ° C. The suspension was suspended in 80.0 parts by mass of cooled N-methyl-2-pyrrolidone (NMP) to form a slurry. Subsequently, the suspension was heated to 60 ° C. and dissolved to obtain a transparent polymer solution. To the polymer solution was added 3.0% by mass of 2- [2H-benzotriazol-2-yl] -4-6-bis (1-methyl-1-phenylethyl) phenol powder (solubility in water: 0% by mass relative to the polymer). .01 mg / L), and the mixture was dissolved under reduced pressure to obtain a spinning solution (spinning dope).
[Spinning / coagulation process]
The above spinning dope was discharged from a spinneret having a hole diameter of 0.07 mm and a number of holes of 500 into a coagulation bath at a bath temperature of 30 ° C and spun. The composition of the coagulation solution was water / NMP = 45/55 (parts by mass), and the coagulation liquid was spun at a yarn speed of 7 m / min into a coagulation bath.
[Plastic stretching bath stretching step]
Subsequently, the film was stretched at a draw ratio of 3.7 times in a plastic stretching bath having a composition of water / NMP = 45/55 at a temperature of 40 ° C.
[Washing process]
After stretching, the film was washed with a 20 ° C. water / NMP = 70/30 bath (immersion length 1.8 m), followed by a 20 ° C. water bath (immersion length 3.6 m), and further washed with a 60 ° C. warm water bath (immersion length 5 m). .4m) to sufficiently wash.
[Dry heat treatment process]
The washed fiber was subjected to dry heat treatment with a hot roller having a surface temperature of 280 ° C. to obtain a meta-type wholly aromatic aramid fiber.
[Properties of fibrils]
Physical properties of the obtained meta-type wholly aromatic aramid fiber were a fineness of 1.7 dtex, a residual solvent amount of 0.08% by mass, and a crystallinity of 19%. The obtained raw fiber was crimped and cut to obtain a staple fiber (raw cotton) having a length of 51 mm.
Other raw cotton fibers used were as follows.
Polyester fiber; polyethylene terephthalate fiber made by Teijin Fiber Flame-retardant rayon fiber; "LenzingFR (registered trademark)" manufactured by Lenzing
Para-type wholly aromatic polyamide fiber; "Twaron (registered trademark)" manufactured by Teijin Aramid Co., Ltd.
Conductive thread (nylon): "NO SHOCK (registered trademark)" manufactured by Sorcia

(Nylon conductive yarn kneaded with conductive carbon fine particles)
[Method of dyeing fabric]
The staining method was performed under the following conditions.
(Staining conditions)
Cationic dye: manufactured by Nippon Kayaku Co., Ltd., trade name: Kayacryl Red GL-ED
The obtained dyed product was washed in the following reducing bath (pH 5.5).
Bath ratio; 1:20
Temperature × time; 120 ° C. × 30 minutes Reduction bath composition and washing conditions:
Reduction bath; thiourea dioxide 1 g / liter bath ratio; 1:20
Temperature x time; 70 ° C x 15 minutes Then, after drying at a temperature of 110 ° C for 10 minutes, a dry heat setting at a temperature of 130 ° C for 2 minutes was performed.
[Anti-fouling processing conditions]
100 g / L of a fluorinated water repellent having a hydrophilic segment (Asahigard AG-E100, manufactured by Asahi Glass Co., Ltd.), 100 g / L of an acrylic urethane binder DYF-30, and a crosslinking agent (Epocross WS having an oxazoline group) -500) was immersed in a mixed solution of 50 g / L, squeezed (pickup ratio: 100%), dried (105 ° C. × 3 minutes), and cured (160 ° C. × 1 minute).

[Example 1]
Meta-type wholly aromatic aramid fiber (MA) (length 51 mm), para-type wholly aromatic polyamide fiber (PA) (length 51 mm), polyester fiber (length 51 mm) (PE), flame-retardant rayon (Ry) ( Each staple fiber having a length of 51 mm) was made into a spun yarn 36-count / twist blended at a ratio of MA / PA / PE / RY = 65/5/15/15, and the weaving density was 100 yarns / 25.4 mm, the weft. The yarn was woven at 56 yarns / 25.4 mm to obtain a twill woven fabric having a basis weight of 230 g / m ² . Using this, it dyed by the above-mentioned method, and performed antifouling processing. Table 1 shows the results.

[Examples 2 and 3]
Except that the spun yarn was changed to a spun yarn obtained by blending a meta-type wholly aromatic polyamide fiber (MA), a para-type wholly aromatic polyamide fiber (PA), and a nylon conductive yarn (AS) at a blending ratio shown in Table 1. The same operation as in Example 1 was performed. Table 1 shows the results.

[Example 4]
Example 1 Except that the spun yarn was changed to a spun yarn obtained by blending a meta-type wholly aromatic polyamide fiber (MA), a para-type wholly aromatic polyamide fiber (PA), and a polyester fiber (PE) at a blending ratio shown in Table 1. The same operation as described above was performed. Table 1 shows the results.

[Example 5]
Except that the spun yarn was changed to a spun yarn obtained by blending a meta-type wholly aromatic polyamide fiber (MA), a para-type wholly aromatic polyamide fiber (PA), and a flame-retardant rayon fiber (RY) with the blend ratio shown in Table 1. The same operation as in Example 1 was performed. Table 1 shows the results.

[Comparative Examples 1 to 5]
The same operation as in Example 1 was performed except that the amount of the used crosslinking agent was reduced from 50 g / L to 30 g / L. Table 1 shows the results.

[Comparative Examples 6, 7]
The same operation as in Example 1 was performed, except that the crosslinking agent was changed to a glyoxal-based fixer (manufactured by Hayashi Chemical), and the material was changed to a spun yarn blended at the blending ratio shown in Table 1. Table 1 shows the results.

  According to the present invention, a fabric containing a meta-type wholly aromatic polyamide fiber, having flame retardancy and washing durability and having antifouling properties, a method for producing the same, and a fiber product are provided, and the industrial value thereof is extremely large. is there.

Claims (14)

A cloth containing a meta-type wholly aromatic polyamide fiber, wherein after performing 10 washes according to JIS L0217-1998, 103 method, the antifouling property of the cloth specified by JIS L1919-2012 B method is 4 or more. der is, and fabric of the crosslinking agent and the water-repellent agent having an oxazoline group, characterized in that it comprises a binder containing an acrylic resin and / or urethane resins.   The fabric according to claim 1, wherein the meta-type wholly aromatic polyamide fiber contains an organic dye, an organic pigment, or an inorganic pigment.   3. The fabric according to claim 1 or claim 2, wherein the fabric further comprises polyester fibers.   The fabric further comprises para-type wholly aromatic polyamide fiber, wholly aromatic polyester fiber, polybenzoxazole (PBO) fiber, polybenzimidazole (PBI) fiber, polybenzthiazole (PBTZ) fiber, polyimide (PI) fiber, polysulfonamide (PSA) fiber, polyetheretherketone (PEEK) fiber, polyetherimide (PEI) fiber, polyarylate (PAr) fiber, melamine fiber, phenol fiber, fluorine-based fiber, and polyphenylene sulfide (PPS) fiber. The fabric according to any one of claims 1 to 3, comprising at least one selected from the group consisting of:   Any one of the fabrics further selected from the group consisting of cellulose fibers, polyolefin fibers, acrylic fibers, rayon fibers, cotton fibers, animal hair fibers, polyurethane fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, acetate fibers and polycarbonate fibers. The fabric according to any one of claims 1 to 4, comprising at least one kind.   The fabric according to any one of claims 1 to 5, wherein one of fibers constituting the fabric contains a flame retardant. The fabric according to any one of claims 1 to 6 , wherein the crystallinity of the meta-type wholly aromatic polyamide fiber is in the range of 15 to 25%. The fabric according to any one of claims 1 to 7 , wherein the meta-type wholly aromatic polyamide fiber has a residual solvent amount of 0.1% by mass or less. The meta-type wholly aromatic polyamide forming the meta-type wholly aromatic polyamide fiber has a different aromatic structure from the main structural unit of the repeating structure in the aromatic polyamide skeleton containing the repeating structural unit represented by the following formula (1). An aromatic polyamide obtained by copolymerizing an aromatic diamine component or an aromatic dicarboxylic acid halide component as a third component in an amount of 1 to 10 mol% with respect to the total amount of the repeating structural units of the aromatic polyamide. 8. The fabric according to any one of 8 above.
-(NH-Ar1-NH-CO-Ar1-CO)-... Formula (1)
Here, Ar1 is a divalent aromatic group having a binding group other than the meta-coordination or parallel axis direction. The fabric according to claim 9 , wherein the aromatic diamine serving as the third component is represented by Formulas (2) and (3), or the aromatic dicarboxylic acid halide is represented by Formulas (4) and (5).
H ₂ N—Ar ₂ —NH ₂ Formula (2)
_{H 2 N-Ar2-Y-} Ar2-NH 2 ··· formula (3)
XOC-Ar3-COX Formula (4)
XOC-Ar3-Y-Ar3-COX Formula (5)
Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group. Or X is a functional group, and X represents a halogen atom. The fabric according to any one of claims 1 to 10 , wherein the fabric comprises an ultraviolet absorber and / or a reflector. The fabric according to any one of claims 1 to 11 , wherein the afterflame is 2.0 seconds or less in a flammability measurement defined in JIS L1091-1992 A-4 method. The method for producing a fabric according to claim 1, wherein a binder containing a crosslinker having an oxazoline group, a water repellent, and an acrylic resin and / or a urethane resin is added to a fabric containing meta-type wholly aromatic polyamide fibers. And a method for producing a fabric. It is made of the cloth according to any one of claims 1 to 12 , and is selected from the group consisting of protective clothing, fire and fire protection clothing, fire fighting clothing, rescue clothing, workwear, police uniform, SDF clothing, and military clothing. Any textile products.