WO2016035638A1

WO2016035638A1 - Fabric and fiber product

Info

Publication number: WO2016035638A1
Application number: PCT/JP2015/074013
Authority: WO
Inventors: 憲二岩下
Original assignee: 帝人株式会社
Priority date: 2014-09-03
Filing date: 2015-08-26
Publication date: 2016-03-10
Also published as: RU2017110597A; BR112017003977B1; TWI675137B; JPWO2016035638A1; BR112017003977A2; EP3192908A1; EP3192908B1; RU2671648C2; CA2960129A1; EP3192908A4; CA2960129C; CN106661783A; AU2015313044A1; US20170292210A1; KR20170047241A; TW201629286A; CN106661783B; ES2703347T3; JP6388659B2; RU2017110597A3

Abstract

In order to provide a fabric and a fiber product, which have hygroscopicity and durability as well as flame retardancy, a hydrophilizing agent is added to a fabric containing aramid fibers.

Description

Fabrics and textile products

The present invention relates to a fabric and a textile product having not only flame retardancy but also durable water absorption.

Conventionally, fabrics containing aramid fibers are excellent in flame retardancy and are used for fire fighting clothes and work clothes. In addition, fire fighters and workers have many opportunities to work in high temperature and humidity environments, and there is a problem of sweating. However, priority has been given to protecting firefighters and workers from flames and the like, and the wearing comfort of the fabric has not been considered so far.

On the other hand, a fabric that efficiently absorbs generated sweat has been proposed as a fabric that enhances wearing comfort during sweating (see, for example, Patent Document 1).

However, a fabric having not only flame retardancy but also durable water absorption has not been proposed so far.

JP 2011-94285 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 and a textile product having not only flame retardancy but also durable water absorption.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have obtained a fabric having not only flame retardancy but also durable water absorption by adding a hydrophilizing agent to the fabric containing aramid fibers. As a result, the present invention has been completed.

Thus, according to the present invention, there is provided “a fabric including an aramid fiber and characterized by being provided with a hydrophilizing agent”.

In that case, it is preferable that the aramid fiber contains 30 to 97% by weight of meta-aramid fiber and 3 to 70% by weight of para-aramid fiber.

Further, it is preferable that the crystallinity of the meta-type wholly aromatic polyamide fiber is in the range of 15 to 25%. In addition, the meta type wholly aromatic polyamide forming the meta type wholly aromatic polyamide fiber is an aromatic polyamide skeleton including a repeating structural unit represented by the following formula (1): A meta-type wholly aromatic polyamide obtained by copolymerizing different aromatic diamine components or aromatic dicarboxylic acid halide components as a third component so as to be 1 to 10 mol% based on the total amount of repeating structural units of the aromatic polyamide. It is preferable.

— (NH—Ar 1 —NH—CO—Ar 1 —CO) — (1)
Here, Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.

In that case, it is preferable that the aromatic diamine as the third component is the formula (2), (3), or the aromatic dicarboxylic acid halide is the formula (4), (5).

H ₂ N—Ar ₂ —NH ₂ Formula (2)
H ₂ N—Ar ₂ —Y—Ar ₂ —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 it is a functional group and X represents a halogen atom.

Moreover, it is preferable that the residual solvent amount of the said meta type | mold aromatic polyamide fiber is 0.1 weight% or less. Moreover, it is preferable that a fabric contains a conductive fiber further. Moreover, it is preferable that a fabric contains a polyester fiber further. Moreover, it is preferable that the said polyester fiber is a polyester fiber containing a flame retardant. Moreover, it is preferable that the aramid fiber and / or the conductive fiber and / or the polyester fiber are contained in the fabric as spun yarn. Moreover, it is preferable that the said aramid fiber and the said polyester fiber are contained in a fabric as a blended yarn. The fabric preferably has a double woven structure. The hydrophilizing agent is preferably polyethylene glycol diacrylate, a polyethylene glycol diacrylate derivative, a polyethylene terephthalate-polyethylene glycol copolymer, or a water-soluble polyurethane. The fabric weight is preferably within the range of 130 to 260 g / m ² . Moreover, it is preferable that the fabric is dyed. In addition, the afterflame is preferably 2.0 seconds or less in the flammability measurement specified in JIS L1091-1992 A-4 method. Moreover, it is preferable that the water absorption performance prescribed | regulated by AATCC79 is 10 seconds or less. Further, after 20 washings specified by ISO 6339; 2012 (6N-F), the water absorption performance specified by AATCC 79 is preferably 30 seconds or less.

Further, according to the present invention, any one selected from the group consisting of protective clothing, fire-fighting clothing, fire-fighting clothing, rescue clothing, workwear, police uniforms, self-defense clothing, and military clothing, using the fabric described above. Textile products are provided.

According to the present invention, it is possible to obtain a fabric and a textile product having not only flame retardancy but also durable water absorption.

6 is a woven structure diagram used in Example 3. FIG.

Hereinafter, embodiments of the present invention will be described in detail.

First, the fabric of the present invention includes an aramid fiber (fully aromatic polyamide fiber). When the aramid fiber is not included in the fabric, it is not preferable because sufficient flame retardancy cannot be obtained.

Such aramid fibers may be meta-aramid fibers or para-aramid fibers.

The meta-aramid fiber may be either an original type or a dyed type. A flame retardant type containing a flame retardant may also be used. Furthermore, the smaller the residual solvent of the meta-aramid fiber, the better. Since the self-extinguishing property of the fiber itself is higher when the residual solvent is smaller, it is preferably 1% by weight or less (more preferably 0.3% by weight or less).

Such meta-aramid fibers are those in which the aromatic ring constituting the main skeleton is bonded to meta by an amide bond, and 85 mol% or more of all repeating units of the polymer are metaphenylene isophthalamide units. To do. In particular, polymetaphenylene isophthalamide homopolymer is preferable. Examples of the third component that can be copolymerized at 15 mol% or less (preferably 5 mol% or less) of all repeating units include those described below. For example, as a diamine component, paraphenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, paraxylylenediamine, biphenylenediamine, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine And aromatic diamines such as 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, and 1,5-naphthalenediamine. Examples of the acid component include aromatic dicarboxylic acids such as terephthalic acid, naphthalene-2,6-dicarboxylic acid, and naphthalene-2,7-dicarboxylic acid. In these aromatic diamines and aromatic dicarboxylic acids, part of the hydrogen atoms of the aromatic ring may be substituted with an alkyl group such as a halogen atom or a methyl group. When 20% or more of all terminals of the polymer are blocked with a monovalent diamine such as aniline or a monovalent carboxylic acid component, the decrease in fiber strength is reduced even when kept at a high temperature for a long time. Therefore, it is preferable. Such meta-aramid fibers may contain a pigment such as carbon black, and a flame retardant, an ultraviolet absorber, and other functional agents in order to maintain functional characteristics. As such meta-aramid fibers, commercially available products include Conex (registered trademark) and Nomex (registered trademark).

Such a meta-type wholly aromatic polyamide can be produced by a conventionally known interfacial polymerization method. The polymerization degree of the polymer is N-methyl-2-pyrrolidone solution having a concentration of 0.5 g / 100 ml. 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 alkylbenzene sulfonic acid onium salt. Examples of the onium salt of alkylbenzene sulfonate include tetrabutyl phosphonium salt of hexyl benzene sulfonate, tributyl benzyl phosphonium salt of hexyl benzene sulfonate, tetraphenyl phosphonium salt of dodecyl benzene sulfonate, tributyl tetradecyl phosphonate of dodecyl benzene sulfonate. Preferred examples include compounds such as a nium salt, tetrabutylphosphonium salt of dodecylbenzenesulfonate, and tributylbenzylammonium salt of dodecylbenzenesulfonate. Among them, dodecylbenzenesulfonic acid tetrabutylphosphonium salt or dodecylbenzenesulfonic acid tributylbenzylammonium salt is particularly easy to obtain and has good thermal stability and high solubility in N-methyl-2-pyrrolidone. Preferably exemplified.

The content ratio of the alkylbenzenesulfonic acid onium salt is 2.5 mol% or more, preferably 3.0 to 7.0 mol, relative to poly-m-phenyleneisophthalamide in order to obtain a sufficient dyeing effect. Those in the range of% are preferred.

As a method of mixing poly-m-phenylene isophthalamide and alkylbenzene sulfonic acid onium salt, poly-m-phenylene isophthalamide is mixed and dissolved in a solvent, and alkylbenzene sulfonic acid onium salt is dissolved in the solvent. Any of these 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 is used in the aromatic polyamide skeleton containing a repeating structural unit represented by the following formula (1) for the purpose of improving dyeability and resistance to discoloration. An aromatic diamine component or an aromatic dicarboxylic acid halide component different from the main structural unit of the structure may be copolymerized so as to be 1 to 10 mol% based on the total amount of the repeating structural units of the aromatic polyamide as the third component. Is possible.

It is also possible to copolymerize as the third component. Specific examples of the aromatic diamines represented by the formulas (2) and (3) include, for example, p-phenylenediamine, chlorophenylenediamine, methylphenylenediamine, acetylphenylenediamine, aminoanisidine, benzidine, and bis (aminophenyl). Examples include ether, bis (aminophenyl) sulfone, diaminobenzanilide, diaminoazobenzene and the like. 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 Examples include '-biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, bis (chlorocarbonylphenyl) ether, and the like.

The crystallinity of the meta-type wholly aromatic polyamide fiber is 5 to 35% in terms of good exhaustibility of the dye and easy adjustment to the target color even with less dye or weak dyeing conditions. Preferably there is. Further, it is more preferably 15 to 25% in that the surface uneven distribution of the dye hardly occurs, the discoloration resistance is high, and the dimensional stability necessary for practical use can be secured.

Further, the residual solvent amount of the meta-type wholly aromatic polyamide fiber is 0 in that it does not impair the excellent flame retardant performance of the meta-type wholly aromatic polyamide fiber, and the surface unevenness of the dye hardly occurs, and the discoloration resistance is high. .1% by weight or less is preferable.

The meta-type wholly aromatic polyamide fiber can be produced by the following method, and in particular, the crystallinity and the residual solvent amount can be within the above ranges by the method described later.

The polymerization method of the meta-type wholly aromatic polyamide polymer is not particularly limited. For example, the solution weight described in Japanese Patent Publication No. 35-14399, US Pat. No. 3,360,595, Japanese Patent Publication No. 47-10863, etc. A combination method or an interfacial polymerization method may be used.

The spinning solution is not particularly limited, but an amide solvent solution containing an aromatic copolyamide polymer obtained by the above solution polymerization or interfacial polymerization may be used, or the polymer may be removed from the polymerization solution. You may use what was isolated and melt | dissolved in the amide-type solvent.

Examples of the amide solvent used here include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP), and dimethyl sulfoxide. N-dimethylacetamide is preferred.

The copolymerized aromatic polyamide polymer solution obtained as described above is preferably stabilized by containing an alkali metal salt or an alkaline earth metal salt, and can be used at a higher concentration and lower temperature. Preferably, the alkali metal salt and alkaline earth metal salt are 1% by weight or less (more preferably 0.1% by weight or less) 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 coagulating solution and coagulated.

The spinning apparatus is not particularly limited, and a conventionally known wet spinning apparatus can be used. In addition, the number of spinning holes, the arrangement state, the hole shape, etc. of the spinneret need not be particularly limited as long as they can be stably wet-spun. For example, the number of holes is 1,000 to 30,000, and the spinning hole diameter is 0.05. A multi-hole spinneret for ˜0.2 mm sufu may be used.

The temperature of the spinning solution (meta-type wholly aromatic polyamide polymer solution) when spinning from the spinneret is preferably in the range of 20 to 90 ° C.

As a coagulation bath used to obtain fibers, an amide solvent, preferably an aqueous solution containing 45 to 60% by weight of NMP, which is substantially free of inorganic salts, is used at a bath temperature of 10 to 50 ° C. Use. If the concentration of the amide solvent (preferably NMP) is less than 45% by weight, the skin has a thick structure, and the washing efficiency in the washing step may be lowered, making it difficult to reduce the amount of residual solvent in the fiber. . On the other hand, when the concentration of the amide solvent (preferably NMP) exceeds 60% by weight, uniform coagulation cannot be performed up to the inside of the fiber, and therefore, the residual solvent amount of the fiber can be reduced. May become difficult. The fiber immersion time in the coagulation bath is preferably in the range of 0.1 to 30 seconds.

Subsequently, an amide solvent, preferably an aqueous solution having a concentration of NMP of 45 to 60% by weight, in a plastic stretching bath in which the temperature of the bath liquid is in the range of 10 to 50 ° C., at a stretching ratio of 3 to 4 times. Stretching is performed. After stretching, the film is thoroughly washed through an aqueous solution having an NMP concentration of 20 to 40% by weight at 10 to 30 ° C., followed by a hot 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-mentioned range of crystallinity and residual solvent amount.

Para-aramid fiber is a fiber made of polyamide having an aromatic ring in the main chain. Poly-p-phenylene terephthalamide (PPTA) or copolymer type copolyparaphenylene-3,4'oxydiphenylene terephthalamide (PPODPA) may be used. As such para-aramid fibers, commercially available products include Technora (registered trademark), Kevlar (registered trademark), and Twaron (registered trademark).

In particular, when the aramid fiber contains 30 to 97% by weight of meta-aramid fiber and 3 to 70% by weight of para-aramid fiber, the shrinkage of the fabric is reduced during combustion and the fabric is less likely to be perforated. .

The fabric of the present invention may be composed of only the aramid fibers as described above, or may contain fibers other than the aramid fibers (other fibers).

For example, it is preferable that conductive cloth is contained in the fabric because a flame due to generation of static electricity can be suppressed by a synergistic effect with the hydrophilizing agent applied to the fabric.

The conductive fiber is preferably a fiber containing at least one of carbon black, conductive titanium oxide, conductive whisker, and carbon nanotube as a conductor of the conductive portion of the conductive fiber.

The form of the conductive fiber may be a structure in which the entire fiber is made of a conductive part, or the non-conductive part and the conductive part may have a cross-sectional shape such as a core sheath, a sandwich, or an eccentricity. The resin forming the conductive part and the non-conductive part is not particularly limited as long as it has fiber-forming properties. Specific examples of nylon resins include 6 nylon, 1 1 nylon, 1 2 nylon, and 6 6 nylon. Polyester resins include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane terephthalate and their copolymers and acid components (terephthalic acid) partially replaced with isophthalic acid. Can be mentioned.

Commercially available conductive fibers include Teijin's “Metallian” (trade name), Unitika Fiber's “Meghana” (trade name), Toray's “Luana” (trade name), and Kuraray's “Kurabo”. (Product name) is exemplified.

In addition, the fabric may contain fibers such as polyester fiber, nylon fiber, acrylic fiber, acrylate fiber, flame retardant rayon fiber, and flame retardant vinylon fiber. In particular, when the fabric contains polyester fibers, the water absorption performance is further improved.

The polyester fiber is a fiber containing polyester as one component. The polyester is a polyester having terephthalic acid as a main dicarboxylic acid component and at least one glycol, preferably at least one alkylene glycol selected from ethylene glycol, trimethylene glycol, tetramethylene glycol and the like as a main glycol component. is there. In the polyester, the third component may be modified by copolymerization and / or blending as necessary. Such polyester may be material-recycled or chemical-recycled polyester or polyethylene terephthalate using a monomer component obtained using biomass, that is, a biological material as a raw material. Furthermore, it may be a polyester obtained by using a catalyst containing a specific phosphorus compound and a titanium compound as described in JP-A-2004-270097 and JP-A-2004-212268.

The polyester may contain optional additives such as a catalyst, an anti-coloring agent, a heat-resistant agent, a flame retardant, an antioxidant, and inorganic fine particles as necessary. In particular, it is preferable to add a flame retardant in the polyester polymer or on the surface of the polyester fiber because the flame retardancy of the fabric is improved.

The polyester fiber preferably has a single fiber fineness of 5.0 dtex or less (more preferably 0.0001 to 1.5 dtex) in order to increase the surface area of the fiber to obtain excellent sweat absorption.

In the polyester fiber, the cross-sectional shape (transverse cross-sectional shape) of the single fiber is preferably an irregular shape (a shape other than a round shape). The atypical cross-sectional shape is preferably a flat cross-section, a W-shape, a cross or a hollow (for example, a round hollow, a triangular hollow, a square hollow, etc.) or a triangular. Further, it may be a flat cross section having a constriction as described in Japanese Patent Application Laid-Open No. 2004-52191, or a cross section having fin portions protruding radially from a hollow core as described in Japanese Patent Application Laid-Open No. 2012-97380. . When the organic fiber has an atypical cross-sectional shape, voids are formed between the fibers, and excellent water absorption is obtained by capillary action. It also has a synergistic effect that flame retardancy is further improved by moisture absorbed by the water absorption action. Among the above-mentioned cross-sectional shapes, the W-type is particularly preferable because even a small amount of fibers can easily form voids between the fibers.

The polyester fiber may be a composite fiber in which two components are bonded side by side or in an eccentric core-sheath type. Such a composite fiber usually has fine crimps in which latent crimps are expressed, and thus has not only stretchability but also excellent water absorption due to capillary action.
At that time, the two components constituting the composite fiber were selected from the group consisting of a combination of polytrimethylene terephthalate and polytrimethylene terephthalate, a combination of polytrimethylene terephthalate and polyethylene terephthalate, and a combination of polyethylene terephthalate and polyethylene terephthalate. Any combination is preferable.

In the fabric of the present invention, the fiber form of the aramid fiber and other fibers constituting the fabric is not particularly limited, and may be a short fiber (spun yarn) or a long fiber (multifilament). In particular, a spun yarn is preferable for maintaining the hydrophilic agent with good washing durability.

At that time, the aramid fiber and other fibers may be blended at the same time, or may be used separately and knitted or woven. Among them, it is preferable that the aramid fiber and the polyester fiber are blended and included in the fabric as a blended yarn because not only excellent flame retardancy can be obtained but also the hydrophilizing agent can be retained with good washing durability.

Further, it is preferable that the spun yarn has a coil shape, which can impart stretch properties to the fabric. A spun yarn having such a coil shape can be obtained by the following method, for example.

That is, first, a spun yarn containing an aramid fiber is prepared. At that time, conductive yarn or other fiber raw cotton may be mixed with the aramid fiber. The spun yarn fineness (count) is preferably 20 to 60 cotton count (Ecc) in terms of yarn breakage resistance and strength. The number of single yarns is preferably 60 or more, and the raw cotton single yarn fineness is preferably 3.0 dtex or less (more preferably 0.001 to 3.0 dtex). The twist coefficient (primary twist coefficient) of the spun yarn is preferably in the range of 3.6 to 4.2 (more preferably 3.8 to 4.0). The larger the twist coefficient, the more the fluff converges and the pilling resistance of the fabric improves. On the other hand, the spun yarn becomes stiff, the elongation decreases, the tear strength of the fabric decreases, and the fabric may be cured. . In addition, a twist coefficient is represented by a following formula.
Twist factor = number of twists (times / 2.54cm) ^/ cotton count of spun yarn (Ecc) ^1/2
The spinning method of the spun yarn may be a normal spinning method such as innovative spinning such as ring spinning, MTS, MJS, MVS, or ring spinning. The twist direction may be either the Z direction or the S direction.

Next, the spun yarn is subjected to a twist set (vacuum steam set) as necessary, and then two or more (preferably 2 to 4, particularly preferably 2) spun yarns are aligned and combined. Twist. Examples of the twisting machine used for the twisting include twisting machines such as an up twister, a covering machine, an italic twisting machine, and a double twister.

At that time, the twisting direction of the upper twist is the additional twisting direction. For example, when the twist direction of the spun yarn is Z twist, the twist is performed in the Z direction in the same direction. The number of twists is preferably 2000 times / m or more, more preferably 2100 to 3000 times / m, and particularly preferably 2300 to 2800 times / m. When the number of twists is less than 2000 times / m, the spun yarn may not be coiled after twisting set and untwisting.

Next, a twist set (a high-pressure vacuum steam set similar to a conventional aramid twin-thread set) is applied to such a twisted yarn. When it is necessary to provide a strong twist-stop set, the number of twist-stop sets may be increased, or the twist-stop set temperature and set time may be changed. For example, the set temperature may be 115 to 125 ° C., the set time may be 20 to 40 minutes, and the number of times may be 1 to 3. The higher the set temperature and the longer the set time, the better the setability. It is possible to increase the setability by increasing the number of twist set, increasing the processing time or raising the temperature, but production management (safety of work management, quality control, etc.) and production processing Considering the cost, it is preferable to increase the processing time. Moreover, the higher the degree of vacuum, the better the quality and the better.

Next, the twisted and set twisted yarn is untwisted (twisting direction opposite to the twisted twisting direction) and heat-set as necessary. At that time, the untwisted twist number is preferably in the range of 70 to 90%. By performing untwisting with the number of twists in this range, a spun yarn having stretch properties and processed into a coil shape can be obtained. In the spun yarn processed into the coil shape, the twist number is preferably in the range of 200 to 860 turns / m in order to obtain excellent stretch properties.

The structure of the fabric is not particularly limited, and examples thereof include plain weave, twill, double weave and the like. Especially, it is preferable that the fabric structure is a double woven structure having a two-layer structure because the water absorption performance is further improved. At that time, the fibers constituting the yarns constituting the two layers are not particularly limited, but the yarns exposed to the skin side layer are mainly composed of 10% by weight or more of polyester fibers, and mainly the outside air side layer. The exposed yarn is preferably composed of polyester fibers in the range of 0 to 10% by weight. By disposing more polyester fibers with excellent water absorption performance on the yarn exposed mainly on the skin side, the water absorption performance is increased, and by reducing the polyester fiber content mainly in the yarn exposed on the outside air layer, The flame retardant performance of the entire fabric can be maintained.

The fabric of the present invention has not only flame retardancy but also durable water absorption by being provided with a hydrophilizing agent.

Here, the hydrophilizing agent is preferably polyethylene glycol diacrylate, a polyethylene glycol diacrylate derivative, a polyethylene terephthalate-polyethylene glycol copolymer, a water-soluble polyurethane, or a polyethylene glycol-aminosilicone copolymer.

The adhesion amount of the hydrophilizing agent to the fabric is preferably 0.1 to 2.0% by weight (more preferably 0.1 to 0.7% by weight) relative to the weight of the fabric. In addition, the adhesion amount of a hydrophilizing agent can be calculated by the following formula.
Adhering amount of hydrophilizing agent (%) = ((weight of fabric after attaching hydrophilizing agent) − (weight of fabric before attaching hydrophilizing agent)) / (weight of fabric before attaching hydrophilizing agent) ) × 100
However, the weight of the fabric after attaching the hydrophilizing agent is the weight after drying.

Examples of the method for imparting a hydrophilizing agent to the fabric include a padding method and a treatment method using the same bath as the dyeing solution during dyeing.

It is preferable that the fabric is dyed. In addition, various other treatments that apply water repellent, heat storage agent, ultraviolet shielding or antistatic agent, antibacterial agent, deodorant agent, insect repellent agent, mosquito repellent agent, phosphorescent agent, retroreflective agent, etc. are additionally applied. Also good.

In the fabric thus obtained, the basis weight is preferably 130 to 260 g / m ² (more preferably 140 to 220 g / m ² ).

Such a fabric contains aramid fibers as described above and is provided with a hydrophilizing agent, so that it has not only flame retardancy but also durable water absorption.

Here, it is preferable that the afterflame is 2.0 seconds or less in the flammability measurement prescribed in JIS L1091-1992 A-4 method. Further, it is preferable that the water absorption performance of the flame retardant fabric is 10 seconds or less (more preferably, 0.1 to 8 seconds at the initial stage) in the initial stage. The water absorption performance specified by AATCC 79 is preferably 30 seconds or less (more preferably 1 to 20 seconds) after 20 washings specified by ISO 6339; 2012 (6N-F).

The textile product of the present invention is any one selected from the group consisting of protective clothing, fire fighting clothing, fire fighting clothing, rescue clothing, work wear, police uniform, self-defense clothing, and military clothing. It is a textile product.

Since such a fabric uses the above-mentioned fabric, it has not only flame retardancy but also durable water absorption.

Next, although the Example and comparative example of this invention are explained in full detail, this invention is not limited by these. In addition, each physical property in an Example is measured with the following method.
(1) Residual solvent amount About 8.0 g of fibrils were collected, dried at 105 ° C. for 120 minutes, allowed to cool in a desiccator, and the fiber weight (M1) was weighed. Subsequently, this fiber was subjected to reflux extraction using a Soxhlet extractor in methanol for 1.5 hours to extract an amide solvent contained in the fiber. The extracted fiber was taken out, vacuum-dried at 150 ° C. for 60 minutes, allowed to cool in a desiccator, and the fiber weight (M2) was weighed. The amount of solvent remaining in the fiber (amide solvent weight) was calculated by the following formula using M1 and M2 obtained.
Residual solvent amount (%) = [(M1-M2) / M1] × 100
The obtained fiber was crimped and cut to obtain a staple fiber (raw cotton) having a length of 51 mm.
(2) Crystallinity Using an X-ray diffractometer (RINT TTRIII, manufactured by Rigaku Corporation), the fibrils were aligned on a fiber bundle having a diameter of about 1 mm and mounted on a fiber sample table to measure a diffraction profile. The measurement conditions were Cu—Kα radiation source (50 kV, 300 mA), scanning angle range 10 to 35 °, continuous measurement 0.1 ° width measurement, 1 ° / min scanning. From the measured diffraction profile, air scattering and incoherent scattering were corrected by linear approximation to obtain a total scattering profile. Next, a crystal scattering profile was obtained by subtracting the amorphous scattering profile from the total scattering profile. The degree of crystallinity was determined by the following equation from the area intensity of the crystal scattering profile (crystal scattering intensity) and the area intensity of the total scattering profile (total scattering intensity).
Crystallinity (%) = [crystal scattering intensity / total scattering intensity] × 100
[Example 1]
Meta-type wholly aromatic polyamide fiber (MA) made of Conex (registered trademark), para-type wholly aromatic polyamide fiber (PA) made of Twaron (registered trademark), "NO SHOCK (registered trademark)" manufactured by Solcia Each staple fiber of conductive nylon fiber (NY) (each fiber length is 51 mm) is made into a spun yarn of 40 yarns / twist yarn blended at a weight ratio of MA / PA / NY = 93/5/2. After weaving a plain woven fabric at 56 / 25.4mm and weft 48 / 25.4mm, carrying out hair burning and refining under the usual processing conditions, a polyethylene terephthalate-polyethylene glycol copolymer was prepared by a padding method. the hydrophilizing agent to impart containing, resulting then heat set was performed at 180 ° C., mass per unit area of 150 g / ^{m 2,} a plain weave fabric of hydrophilizing agent adhesion amount 0.2-0.5 wt% .
In the obtained woven fabric, the sweat absorption performance specified by AATCC 79 is 2.0 seconds at the beginning and 25 seconds after 20 washings specified by ISO 6339; 2012 (6N-F). It was what had. Further, in the flammability measurement stipulated in JIS L1091-1992 A-4 method, the after flame was 2.0 seconds or less, and there was no problem. When working clothes were sewed and worn using such a fabric, they sweated when sweating and had excellent comfort.

[Example 2]
Meta-type wholly aromatic polyamide fiber (MA), para-type wholly aromatic polyamide fiber (PA), conductive nylon fiber (NY), and flame-retardant polyester fiber (PE) staple fibers (each fiber length is 51 mm) Was made in the same manner as in Example 1 except that the spun yarn was 40 yarn / twist yarn blended at a weight ratio of MA / PA / NY / PE = 73/5/2/20.

In the obtained woven fabric, the water absorption performance specified by AATCC 79 is 0.9 seconds at the beginning, and 11 seconds after 20 washings specified by ISO 6339; 2012 (6N-F). It was what had. Further, in the flammability measurement specified in JIS L1091-1992 A-4 method, the afterflame was 2.0 seconds or less, and there was no problem. When working clothes were sewed and worn using such a fabric, they sweated when sweating and had excellent comfort.

[Example 3]
Example 2 was carried out in the same manner as Example 2 except that a double woven fabric was woven according to the woven structure diagram shown in FIG. 1 at a weaving density of 56 yarns / 25.4 mm and 60 wefts / 25.4 mm.

In the obtained woven fabric, the water absorption performance specified by AATCC 79 is 0.6 seconds at the initial stage and 9.0 seconds after 20 washings specified by ISO 6339; 2012 (6N-F). It had water absorption. Further, in the flammability measurement specified in JIS L1091-1992 A-4 method, the afterflame was 2.0 seconds or less, and there was no problem. When the work clothes were sewn and worn using such a woven fabric, the sweat was absorbed when sweating, and the work clothes and the skin did not adhere to each other, and the clothes had excellent comfort.

[Comparative Example 1]
Example 1 was carried out in the same manner as Example 1 except that the hydrophilizing agent was not added. The resulting fabric has a water absorption performance specified by AATCC 79 of 58 seconds at the beginning and 48.0 seconds after 20 washings specified by ISO 6339; 2012 (6N-F). It was not. Further, in the flammability measurement stipulated in JIS L1091-1992 A-4 method, the after flame was 2.0 seconds or less, and there was no problem. When working clothes were sewn and worn using such a fabric, they were uncomfortable because they did not absorb sweat when perspiration.

[Example 4]
Meta-type wholly aromatic polyamide fiber (MA), para-type wholly aromatic polyamide fiber (PA), polyester fiber (PE) whose cross-sectional shape is W-type, and conductive nylon fiber (NY) staple fibers (all fibers) The length is 51 mm), and the spun yarn is 40 count / twist yarn blended at a weight ratio of MA / PA / PE / NY = 78/5/15/2, and the weaving density is 56 warps / 25.4 mm, 48 wefts / After weaving a plain woven fabric at 25.4 mm and carrying out hair firing and refining under ordinary processing conditions, a sweat absorbing agent containing a polyethylene terephthalate-polyethylene glycol copolymer is processed by padding, and then 180 ° C. Then, heat setting was performed to obtain a plain fabric with a basis weight of 150 g / m ² .

In the obtained woven fabric, the water absorption performance defined by AATCC 79 is 0.5 seconds at the beginning and 8.0 seconds after 20 washings defined by ISO 6339; 2012 (6N-F). It had sweat absorbency. Further, in the flammability measurement specified in JIS L1091-1992 A-4 method, the afterflame was 2.0 seconds or less, and there was no problem. When working clothes were sewed and worn using such a fabric, they sweated when sweating and had excellent comfort.

[Example 5]
Meta-type wholly aromatic polyamide fiber (MA), para-type wholly aromatic polyamide fiber (PA), flame-retardant polyester fiber (NPE) whose cross-sectional shape is W-type, and conductive nylon fiber (NY) staple fiber (any The fiber length was 51 mm), and the same procedure as in Example 4 was conducted except that the spun yarn was 40 yarn / twist yarn blended at a weight ratio of MA / PA / NPE / NY = 78/5/15/2. .

The obtained woven fabric also had no problem because the afterflame was 2.0 seconds or less in the flammability measurement prescribed in JIS L1091-1992 A-4 method. In addition, the water absorption performance specified by AATCC 79 is 1.1 seconds at the initial stage and 13 seconds after 20 washings specified by ISO 6339; 2012 (6N-F). When the clothes were sewn and worn, they sweated when sweating and had excellent comfort.

[Example 6]
Meta-type wholly aromatic polyamide fiber (MA), para-type wholly aromatic polyamide fiber (PA), polyester fiber (PE) having a round cross-sectional shape, and conductive nylon fiber (NY) staple fibers (all fibers) The length was 51 mm), and the same procedure as in Example 4 was performed except that the spun yarn was 40 yarn / twist yarn blended at a weight ratio of MA / PA / PE / NY = 78/5/15/2.

The obtained woven fabric was satisfactory because the afterflame was 2.0 seconds or less in the flammability measurement specified in JIS L1091-1992 A-4 method. In addition, the water absorption performance specified by AATCC 79 is 1.2 seconds at the beginning, and 12 seconds after 20 washings specified by ISO 6339; 2012 (6N-F). When the clothes were sewn and worn, they sweated when sweating and had excellent comfort.

[Example 7]
Meta-type wholly aromatic polyamide fiber (MA), para-type wholly aromatic polyamide fiber (PA), conductive nylon fiber (NY) staple fibers (each fiber length is 51 mm), MA / PA / PE / NY A composite fiber composed of 40 spun yarn / twist yarn blended at a weight ratio of 93/5/2 as a warp yarn, and 40 spun yarn / twist yarn and polyethylene terephthalate / polytrimethylene terephthalate ( A total weave of 84 dtex / 24 filament) was used as a weft to make a weft, and the same procedure as in Example 4 was performed except that a plain weave was woven at a weaving density of warp 56 / 25.4 mm and weft 43 / 25.4 mm. .

The obtained woven fabric was satisfactory because the afterflame was 2.0 seconds or less in the flammability measurement specified in JIS L1091-1992 A-4 method. In addition, the water absorption performance specified by AATCC 79 is 1.0 seconds at the initial stage and 14 seconds after 20 washings specified by ISO 6339; 2012 (6N-F). When the clothes were sewn and worn, they sweated when sweating and had excellent comfort. Further, it was stretchable in the lateral direction and easily moved.

[Example 8]
Meta-type wholly aromatic aramid fibers were produced by the following method.

20.0 parts by weight of polymetaphenylene isophthalamide powder produced by an interfacial polymerization method according to the method described in Japanese Patent Publication No. 47-10863 and having an intrinsic viscosity (IV) of 1.9 is placed at −10 ° C. It was suspended in 80.0 parts by weight 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, 3.0% by weight of 2- [2H-benzotriazol-2-yl] -4-6-bis (1-methyl-1-phenylethyl) phenol powder (solubility in water: 0) .01 mg / L) was mixed and dissolved, and depressurized under reduced pressure to obtain a spinning solution (spinning dope).
[Spinning and coagulation process]
The spinning dope was spun from a spinning nozzle having a hole diameter of 0.07 mm and a hole number of 500 into a coagulation bath having a bath temperature of 30 ° C. The composition of the coagulation liquid was water / NMP = 45/55 (parts by weight), and was spun by discharging into the coagulation bath at a yarn speed of 7 m / min.
[Plastic stretching bath stretching process]
Subsequently, the film was stretched at a stretching 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 then a 60 ° C. hot water bath (immersion length 5). 4m) and thoroughly washed.
[Dry heat treatment process]
The washed fiber was subjected to a dry heat treatment with a heat roller having a surface temperature of 280 ° C. to obtain a meta-type wholly aromatic aramid fiber.
[Physical properties of fibrils]
The 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 weight, and a crystallinity of 19%. The following thing was used for the other fiber raw cotton.
Polyester fiber; Teijin's polyethylene terephthalate fiber Flame-retardant rayon fiber; Lenzing's "LenzingFR (registered trademark)"
Para-type aramid fiber; “Twaron (registered trademark)” manufactured by Teijin Aramid
Conductive yarn (nylon): “NO SHOCK (registered trademark)” manufactured by Solcia (nylon conductive yarn kneaded with conductive carbon fine particles)
Next, meta-type wholly aromatic aramid fiber (MA) (length: 51 mm), para-type wholly aromatic polyamide (PA) (length: 50 mm), polyester fiber (length: 38 mm) (PE), flame retardant rayon (Ry) Each staple fiber (length: 51 mm) is a 40 / twisted spun yarn obtained by blending at a weight ratio of MA / PA / PE / RY = 55/5/15/25 and has a weaving density of 67 yarns / 25.4 mm. Weaving was performed at 56 weft / 25.4 mm, and a twill woven fabric having a basis weight of 170 g / m ² was obtained. After using this for dyeing and finishing by a conventional method, the following perspiration treatment was applied.
[Cloth sweat absorption]
The test cloth was immersed in a sweat processing agent polyethylene glycol-aminosilicone copolymer (50 g / L), pressed, dried, and then subjected to a dry heat setting at 180 ° C. for 2 minutes.
In the obtained woven fabric, afterflame was 2.0 seconds or less in the flammability measurement specified in JIS L1091-1992 A-4 method, and there was no problem. Further, the water absorption performance defined by AATCC 79 was 0.9 seconds at the initial stage, and 9.0 seconds after 20 washings defined by ISO 6339; 2012 (6N-F). When the work clothes were sewn and worn using such a woven fabric, the sweat was absorbed when sweating, and the work clothes and the skin did not adhere to each other, and the clothes had excellent comfort.

According to the present invention, there are provided fabrics and fiber products that have not only flame retardancy but also durable water absorption properties, and their industrial value is extremely large.

Claims

A fabric containing an aramid fiber, which is provided with a hydrophilizing agent.
The fabric according to claim 1, wherein the aramid fibers contain 30 to 97% by weight of meta-aramid fibers and 3 to 70% by weight of para-aramid fibers.
The fabric according to claim 2, wherein the crystallinity of the meta-type wholly aromatic polyamide fiber is in the range of 15 to 25%.
The meta-type wholly aromatic polyamide forming the meta-type wholly aromatic polyamide fiber has an aromatic different from the main constituent unit of the repeating structure in the aromatic polyamide skeleton containing the repeating structural unit represented by the following formula (1). A meta-type wholly aromatic polyamide obtained by copolymerizing an aromatic diamine component or an aromatic dicarboxylic acid halide component as a third component so as to be 1 to 10 mol% based on the total amount of repeating structural units of the aromatic polyamide. Item 3. The fabric according to Item 2.
— (NH—Ar 1 —NH—CO—Ar 1 —CO) — (1)
Here, Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.
The fabric according to claim 4, wherein the aromatic diamine as the third component is represented by the formula (2) or (3), or the aromatic dicarboxylic acid halide is represented by the formula (4) or (5).
H 2 N—Ar 2 —NH 2 Formula (2)
H 2 N—Ar 2 —Y—Ar 2 —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 it is a functional group and X represents a halogen atom.
The fabric according to claim 2, wherein the amount of residual solvent of the meta-type aromatic polyamide fiber is 0.1% by weight or less.
The fabric according to claim 1, wherein the fabric further contains conductive fibers.
The fabric according to claim 1, wherein the fabric further comprises a polyester fiber.
The fabric according to claim 8, wherein the polyester fiber is a polyester fiber containing a flame retardant.
The fabric according to claim 8, wherein the polyester fiber has an atypical cross-sectional shape.
In the polyester fiber, the cross-sectional shape of the single fiber is flat or W-shaped, cross, hollow or triangular.
The fabric according to claim 8, wherein the aramid fiber and / or the conductive fiber and / or the polyester fiber is contained in a fabric as a spun yarn.
The fabric according to claim 8, wherein the aramid fiber and the polyester fiber are contained in the fabric as a blended yarn.
The fabric according to claim 1, wherein the fabric has a double woven structure.
The fabric according to claim 1, wherein the hydrophilizing agent is polyethylene glycol diacrylate or a derivative of polyethylene glycol diacrylate, a polyethylene terephthalate-polyethylene glycol copolymer, a water-soluble polyurethane, or a polyethylene glycol-aminosilicone copolymer.
The fabric according to claim 1, wherein the fabric weight is within a range of 130 to 260 g / m 2 .
The fabric according to claim 1, wherein the fabric is dyed.
The fabric according to claim 1, wherein the afterflame is 2.0 seconds or less in the flammability measurement specified in JIS L1091-1992 A-4 method.
The fabric according to claim 1, wherein the water absorption performance defined by AATCC 79 is 10 seconds or less.
The fabric according to claim 1, wherein the water absorption performance defined by AATCC 79 is 30 seconds or less after 20 washings defined by ISO 6339; 2012 (6N-F).
A textile product comprising the fabric according to claim 1 and selected from the group consisting of protective clothing, fire-fighting clothing, fire-fighting clothing, rescue clothing, workwear, police uniforms, SDF clothing, and military clothing. .