JP2020026595A - Fabric and protection product - Google Patents

Abstract

To provide a fabric and a protection product that can be made of any colors, and have activity and electrical arc protection performance.SOLUTION: The present invention provides a fabric made from spun yarn containing a meta-type aromatic polyamide fiber. The fabric has an infrared absorber fixed thereto in a range of 0.02-50 g/m. In the arc resistance test ASTM F1959-1999, it has an ATPV value of 8.0 cal/cmor more.SELECTED DRAWING: None

Description

  The present invention relates to a fabric and a protective product that can be developed in any color and have an activity and a protective performance against an electric arc.

  Persons working near electrical equipment and rescue workers responding to accidents near electrical equipment can potentially be exposed to electric arcs and flash fires. Electric arcs are very catastrophic events, typically involving thousands of volts and thousands of amps of electricity. The event is formed in the atmosphere when the potential difference (or voltage) between the two electrodes ionizes the atoms in the atmosphere and allows them to power electricity.

Fabrics using various flame-retardant fibers have been proposed for protection against such electric arcs and flash fires (for example, see Patent Documents 1 to 11).
Conventionally, in order to enhance the protection performance against electric arc and flash fire, methods of increasing the thickness of the dough, increasing the texture density of the dough, or darkening the dough have been generally performed. .

  Further, in recent years, a method of using a fiber into which carbonized fine particles are kneaded has been proposed. However, in such a method, since a hard substance is kneaded into the fiber, the original texture of the fiber is impaired, and not only infrared light but also visible light is absorbed, so that there is a problem that only a dark color product can be obtained. .

  As described above, it is difficult for the work clothes to have both the activity and the design and the protection performance against electric arc and flash fire.

International Publication No. 2011/126999 pamphlet WO 2010/141554 pamphlet JP 2011-527734 A JP-T-2009-503278 JP-T-2007-529648 JP 2007-535415 A Japanese Patent Publication No. 2007-501341 JP 2006-516306 A JP 2010-502849 A Japanese Patent No. 4,846,739 International Publication No. 2012/077681 pamphlet

  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 protective product that can be developed in any color and have an activity and a protective performance against an electric arc.

  The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have formed a fabric using a spun yarn containing a meta-type aromatic polyamide fiber, and fixed an infrared absorbent to the surface of the fabric to obtain an electrical property. The present inventors have found that the protection performance against an arc is improved, and have made extensive studies to complete the present invention.

Thus, according to the present invention, "a fabric using spun yarn containing a meta-type aromatic polyamide fiber, wherein an infrared absorbent is fixed in a range of 0.02 to 50 g / m ² , In a test ASTM F1959-1999, a fabric characterized by having an ATPV value of 8.0 cal / cm ² or more. "

In that case, it is preferable that the infrared absorber is metal oxide-based fine particles or carbon fine particles. Further, it is preferable that the infrared absorbent is fixed with a binder resin. Further, it is preferable that the compounding ratio of the infrared absorbent and the binder resin is in the range of 1: 0.1 to 1:50. Preferably, the metal oxide-based fine particles are any one selected from the group consisting of antimony-doped tin oxide, tin-doped indium oxide, tungsten-based composite oxide, and lanthanum hexaboride. Further, the visible light transmittance of the metal oxide-based fine particles is preferably 40% or more. Preferably, the carbon fine particles are fixed only to the fiber surface on the back surface of the fabric. In addition, a para-type aromatic polyamide fiber, a polyphenylene sulfide fiber, a polyimide fiber, a polybenzimidazole fiber, a polybenzoxazole fiber, a polyamideimide fiber, a polyetherimide fiber, a Pyromex (registered trademark), a carbon fiber, an acrylic fiber And at least one selected from the group consisting of cellulose fibers, and conductive fibers. Further, the basis weight is preferably in the range of 120 to 250 g / m ² . Further, the meta-type aromatic polyamide fiber is preferably dyed.

  Further, according to the present invention, any one selected from the group consisting of arc protective clothing, flame-resistant protective clothing, work clothing, activity clothing, gloves, protective apron, and protective member using the cloth described above. Protection products are provided.

  ADVANTAGE OF THE INVENTION According to this invention, any color development is possible, and the cloth and protective product which have the protection performance against an activity and an electric arc are obtained.

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

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

  The meta-type aromatic polyamide may contain an onium salt of alkylbenzenesulfonic acid. 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 aromatic polyamide fiber has a repeating structure having a repeating structure in an aromatic polyamide skeleton containing a repeating structural unit represented by the following formula (1) for the purpose of improving dyeing resistance and discoloration resistance. An aromatic diamine component or an aromatic dicarboxylic acid halide component different from the main structural unit can be copolymerized 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. is there.
-(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.

  Further, the crystallinity of the meta-type 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. Is preferred. Further, the content is more preferably from 15 to 25% from the viewpoint that the uneven distribution of the dye on the 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 aromatic polyamide fiber is 0.1% by weight or less (preferably 0.001 to 0.1% by weight) in that the excellent flame retardant performance of the meta-type aromatic polyamide fiber is not impaired. Is important.

  The meta-type aromatic polyamide fiber can be produced by the following method. In particular, the crystallinity and the amount of the remaining solvent can be set in the above ranges by the method described later.

  The method for polymerizing the meta-type aromatic polyamide polymer is not particularly limited, and for example, a solution polymerization method described in JP-B-35-14399, U.S. Pat. No. 3,360,595, JP-B-47-10863, and the like. Alternatively, 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 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.

  Further, the temperature of the spinning solution (meta-type 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 aromatic polyamide fiber satisfying the above-mentioned range of crystallinity and residual solvent amount.

  In the meta-type aromatic polyamide 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 (more preferably 30 to 150 mm) are preferred for blending with other fibers. Further, the single fiber fineness is preferably in the range of 0.5 to 5 dtex.

  In the woven or knitted fabric of the present invention, the weight ratio of the meta-type aromatic polyamide fiber is preferably in the range of 25 to 99% by weight (more preferably 50 to 95% by weight) based on the weight of the woven or knitted fabric. When the weight ratio of the meta-type aromatic polyamide fiber is smaller than the range, the flame retardancy of the woven or knitted fabric may be reduced.

  Next, in the present invention, the infrared absorbent is fixed to the fiber surface of the woven or knitted fabric with a binder resin. Here, the infrared absorbent may be fixed to both surfaces (entire surface) of the woven or knitted fabric, or may be fixed to only one surface. When fixed to only one surface, when the surface is the back surface, that is, when the woven or knitted fabric is used as clothing, the surface becomes the skin side of the human body, when the infrared absorbing agent or the binder resin is colored. Also, since these agents and resins do not appear on the surface of the woven or knitted fabric, there is no fear that a problem in appearance will occur.

  The infrared absorber is not particularly limited as long as it has an absorptance of 10% or more in an infrared region having a wavelength of 700 to 2000 nm, and examples thereof include metal oxide-based fine particles, carbon black, and an infrared absorbing dye of an organic compound. Is done. Among these infrared absorbers, those having a thermal conductivity of 10 W / m · K (27 ° C.) or more (more preferably 20 W / m · K or more) are preferable. By having such a thermal conductivity, when the woven or knitted fabric to which the infrared absorbing agent is fixed is used for clothing and an electric arc accident or a flash fire occurs, the infrared absorbing agent is used for an electric arc or a flame flash. It can absorb heat energy and suppress heat energy reaching the human body. Specifically, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), diimonium-based compounds, aminium-based compounds, anthraquinone-based compounds, polymethine-based compounds, cyanine-based compounds, phthalocyanine-based compounds, and dithiol metal complex-based compounds And metal oxide-based fine particles having an average particle diameter of 100 nm or less, such as squarylium-based compounds and naphthalocyanine-based compounds. Such metal oxide-based fine particles are also a transparent material that transmits visible light, and are also preferable in that they do not change the hue of the main body of the woven or knitted fabric. That is, the visible light transmittance of the metal oxide-based fine particles is preferably 40% or more (more preferably 50% or more). Such metal oxide-based fine particles can be obtained as an aqueous dispersion or a solvent-based dispersion such as toluene. Further, when the color of the cloth is black, navy blue, or a dark color product such as reddish color, carbon black can also be suitably used, and the particle diameter of such carbon black is about several μm. I just need. In addition, when carbon black is applied to a light-colored cloth, the surface of the cloth becomes gray, and in order to avoid discoloration in appearance, one side of the cloth (the back side, that is, the woven or knitted fabric is used for clothing). In this case, it is preferable to fix only to the skin side of the human body).

The amount of the infrared absorbent fixed to the fabric is preferably in the range of 0.02 to 50 g / m ² (more preferably 0.1 to 30 g / m ² ) with respect to the fabric. If the amount of the infrared absorbent fixed is less than the above range, the fabric cannot absorb the heat energy of the electric arc or the flame flash, and the effect of suppressing the heat energy reaching the human body may not be sufficient. On the other hand, if the amount of the infrared absorbent fixed is larger than the above range, the effect is sufficient but it is not economical.

The binder resin used in the present invention is not particularly limited, and examples thereof include a urethane resin, an acrylic resin, a polyester resin, a silicone resin, a vinyl chloride resin, and a nylon resin. Fixed amount of the binder resin, with respect to the fabric at a resin solids basis, is preferably 0.01~40g / ^{m 2} (more preferably 1 to 30 g / ^{m 2)} is in the range of. Usually, the infrared absorbent and the binder resin are applied to the fabric as a blended composition of both. At this time, such a blended composition may be composed of any of a water-based composition and a solvent-based composition, but an aqueous composition is preferred in view of the working environment of the processing step. Examples of the solvent include toluene, isopropyl alcohol, dimethylformamide, methyl ethyl ketone, and ethyl acetate. A crosslinking agent such as an epoxy-based crosslinking agent may be used in combination with the composition. Further, an appropriate additive may be further used in combination for the purpose of, for example, improving the adhesion to the fabric body.

  The mixing ratio of the infrared absorber and the binder resin (based on the resin solid content) is preferably in the range of 1: 0.1 to 1:50 (more preferably 1: 0.5 to 1:40). If the compounding ratio of the binder resin is less than the above range, the infrared absorbent tends to fall off during washing after the fabric is formed as a protective product, so that the protective performance against electric arc may be reduced. Conversely, if the mixing ratio of the binder resin is larger than the above range, the flame retardancy of the fabric may be reduced.

  As a means for applying the infrared absorbing agent and the binder resin to the fabric, first, both are formed into the above-described composition, and then the composition is subjected to a padding method, a gravure coating method, a known method such as a screen printing method. An application means can be used.

In the present invention, the spun yarn further includes para-type aromatic polyamide fiber, polyphenylene sulfide fiber, polyimide fiber, polybenzimidazole fiber, polybenzoxazole fiber, polyamideimide fiber, polyetherimide fiber, and Pyromex (registered trademark). , Carbon fiber, acrylic fiber, cellulosic fiber, and conductive fiber, when one or more selected from the group is included, retains the carbonization event characteristics of the fabric, and has the shrinkage resistance of the carbonized portion and the carbonized portion. Is preferably maintained. If these fibers are not contained in the spun yarn, the woven or knitted fabric is carbonized when exposed to an electric arc and crushed into crisp and ragged shapes, making it impossible to maintain the shape of the fabric and possibly causing holes in the carbonized woven or knitted fabric portion. There is. In particular, it is preferable that such fibers be contained in an amount of 1 to 75% by weight (more preferably 5 to 50% by weight) based on the weight of the spun yarn.
Here, the para-aramid fibers are represented by Technora (registered trademark), Kevlar (registered trademark) and Twaron (registered trademark), and are fibers made of polyamide having an aromatic ring in the main chain. And poly-p-phenylene terephthalamide (PPTA) or copolymer type copolyparaphenylene-3,4'oxydiphenylene terephthalamide (PPODPA).

The spun yarn may be obtained by blending or blending the above-mentioned fiber by a conventional method, but depending on the expected functional characteristics, a composite using a core-sheath double-layered spun yarn, a core spun yarn or a drawn yarn is used. It may be a thread. Further, a spun yarn having a coil shape obtained by the following method may be used. That is, first, the above-mentioned spun yarn is prepared. At that time, the spun yarn fineness (count) is preferably cotton count (Ecc) 20 to 60 in terms of yarn breakage resistance and strength. The number of single yarns is preferably 60 or more, and the fineness of raw cotton single fiber 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 better the pilling resistance of the fabric, but the spun yarn becomes rigid, the elongation is reduced, the tear strength of the fabric is reduced, and the fabric may be hardened. . The twist coefficient is represented by the following equation.
Twisting coefficient = number of twists (twice / 2.54 cm) ^/ cotton count of spun yarn (Ecc) ^1/2
The spinning method of the spun yarn may be a normal spinning method such as ring spinning, innovative spinning such as ring spinning, MTS, MJS, and MVS. The twist direction may be either the Z direction or the S direction.

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

  At that time, the twisting direction of the ply twist (upper twist) is the additional twist direction. For example, when the twist direction of the spun yarn is Z twist, twisting is performed in the same Z 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 2,000 turns / m, the spun yarn may not be coiled after the twist set and untwisting.

  Next, a twisting set (a high-pressure vacuum steam set similar to the conventional aramid twin yarn twisting set) is applied to such a plied yarn. When it is necessary to provide a strong twisting set, the number of twisting sets may be increased, or the twisting set temperature or the setting 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 times. The higher the set temperature and the longer the set time, the better the setability and the better. Increasing the number of twisting sets, increasing the processing time, and raising the temperature can increase the setability. However, production management (safety of work management, quality control, etc.) and production processing Considering the cost, it is preferable to increase the processing time. Also, the higher the degree of vacuum, the better the quality, which is preferable.

  Next, the twisted set twisted yarn is untwisted (twisting direction opposite to the twisting twisting direction), and heat set as necessary. In this case, the untwisting number is preferably 70 to 90%. By performing untwisting with the number of twists in this range, a coiled spun yarn having stretchability can be obtained. In such a coiled spun yarn, the number of twists is preferably in the range of 200 to 860 turns / m in order to obtain excellent stretchability.

  The raw cotton used for the spun yarn may be dyed (yarn-dyed) raw cotton or raw cotton, or the raw cotton that has been subjected to functionalization treatment (such as sweat absorption, quick drying, antifouling, flame retardancy, and ultraviolet absorption). May be. In particular, in order to obtain a woven or knitted fabric having a high-quality appearance, it is important that the meta-type aromatic polyamide fiber be dyed with a dye.

  In the present invention, the structure of the fabric is not particularly limited, and may be any of a woven fabric, a knitted fabric, and a nonwoven fabric. However, a woven fabric is preferable in terms of flame retardancy, flame resistance, strength, and the like. At that time, as the woven fabric, Mihara structure such as plain weave, oblique weave, satin weave, change structure such as change oblique weave, single double structure such as vertical double weave, weft double weave, etc. Is exemplified. The woven fabric having these woven structures can be woven by a normal method using a normal loom such as a rapier loom or an air jet loom. The number of layers is not particularly limited, and may be a single layer or a woven fabric having a multilayer structure of two or more layers. In the case of a knit, the type may be a weft knit or a new knit. Preferable examples of the weft knitting structure include sheeting, rubber knitting, double-sided knitting, pearl knitting, tack knitting, floating knitting, one-sided knitting, lace knitting, and bristle knitting. Preferred examples of the warp knitting structure include a single denby knit, a single atlas knit, a double cord knit, a half knit, a fleece knit, and a jacquard knit. The knitting can be performed by an ordinary method using an ordinary knitting machine such as a circular knitting machine, a flat knitting machine, a tricot knitting machine, a Raschel knitting machine and the like. The number of layers is not particularly limited, and may be a single layer or a knitted article having a multilayer structure of two or more layers.

  Post-processing is preferably performed subsequent to weaving and knitting, and specific post-processing steps can include, for example, steps such as scouring, drying, relaxing, hair burning, dyeing, and functionalizing treatment. The scouring or relaxing treatment may be a spreading treatment or a liquid scouring / relaxing treatment. Specifically, in the continuous scouring and continuous drying, a method of treating with a spreading non-tensioning machine is used, for example, a method using a softer scouring machine, a dry cloth, a shrink surfer, a short loop, a luciol dryer, or the like. In some cases, the scouring and relaxing steps can be omitted.

  In order to improve other properties, the composition may be sheared and / or burned, and / or a sweat absorbent, a water repellent, a heat storage agent, an ultraviolet ray shielding or antistatic agent, an antibacterial agent, a deodorant, an insect repellent, and a mosquito repellent. Various other processes for imparting functions such as a mosquito repellent, a phosphorescent agent, and a retroreflective agent may be additionally applied. Here, as the sweat absorbing agent, polyethylene glycol diacrylate, a derivative of polyethylene glycol diacrylate, a polyethylene terephthalate-polyethylene glycol copolymer, or a water-soluble polyurethane is preferable. Examples of a method of applying a sweat absorbing agent to a woven or knitted material include a method of performing padding treatment, a method of performing treatment in a same bath with a dyeing solution during dyeing.

In the present invention, the woven or knitted fabric is preferably dyed in a dye bath containing a cationic dye. At this time, a method of performing a reduction treatment and drying after preferably dyeing at 115 to 135 ° C. can be employed, but the method is not limited thereto.
The cationic dye refers to a water-soluble dye that is soluble in water and has a basic group, and is widely used for dyeing acrylic fibers, natural fibers, and cationic dyeable polyester fibers. Examples of the cationic dye include diacrylmethane, triacrylmethane, quinone imine (azine, oxazine, thiazine), xanthene, methine (polymethine, azamethine), and heterocyclic azo (thiazoleazo, triazoleazo, benzothiazole). Azo), anthraquinone type and the like. In addition, recently, there is a cationic dye which is made into a dispersion type by blocking a basic group, but both can be used. Among them, an azo type is desirable, and for example, C.I. I. Basic Blue 54, C.I. I. Basic Blue 3, C.I. I. Basic Red 29, C.I. I. Basic Yellow 67 and the like.

  In the dyeing process, it is preferable to use a carrier agent, and a dyeing treatment of a cationic dye and a carrier agent in the same bath can be employed. Further, by treating the woven or knitted fabric with a special surfactant before the cationic dyeing, it becomes possible to carry out the deep dyeing by spread dyeing.

  Here, as the carrier agent, for example, DL-β-ethylphenethyl alcohol, 2-ethoxybenzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p-isopropylbenzyl alcohol, 2-methylphenethyl alcohol, 3-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2-methoxybenzyl alcohol, 3-iodobenzyl alcohol, cinnamon alcohol, p-anisyl alcohol, benzhydrol, and cyclohexylpyrrolidone Preferably, it is at least one selected. The amount of the carrier agent is preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the meta-type wholly aromatic polyamide fiber.

In the woven or knitted fabric thus obtained, the basis weight of the woven or knitted fabric is preferably in the range of 120 to 250 g / m ² (more preferably, 150 to 230 g / m ² ). If the basis weight of the woven or knitted fabric is smaller than the range, the protection performance against an electric arc may be reduced. Conversely, if the basis weight of the woven or knitted fabric is larger than the range, the lightness and the wearing comfort may be reduced.

  Since the woven or knitted fabric of the present invention has the above-described configuration, it has a light-colored hue, has activity and wearing comfort, and has a protective performance against an electric arc, and is resistant to a flash flame.

Here, in the arc resistance test ASTM F1959-1999, it is important that the ATPV (Arc Thermal Performance Value) value is 8.0 cal / cm ² or more (preferably 8.0 to 12.0 cal / cm ² ). .

  The protective product of the present invention is any one selected from the group consisting of arc protective clothing, flame-resistant protective clothing, work clothing, activity clothing, gloves, protective apron, and protective member using the cloth described above. It is a protective product. The work clothes include work clothes for steel works and steel factories, work clothes for welding work, work clothes in explosion-proof areas, and the like. The gloves include work gloves used in the aircraft industry, information equipment industry, precision equipment industry, and the like that handle precision parts.

  Such a protective product uses the woven or knitted fabric for a protective product described above, and is not only lightweight and flame-retardant, but also has resistance to flash flame (protective force), and is excellent in comfort and safety. The resistance (protective force) to the flash flame increases as the woven or knitted fabric is laminated like a stab (quilt stitch).

Next, Examples and Comparative Examples of the present invention will be described in detail, but the present invention is not limited thereto.
(1) Weight per unit area Measured according to JIS L1096.
(2) ATPV (Arc Thermal Performance Value) The ATPV value was measured by an arc resistance test ASTM F1959-1999. A value of 8.0 cal / cm ² or more is considered acceptable (level 2 clear).

[Example 1]
Meta-type aromatic polyamide fiber (manufactured by Teijin Limited, “Teijinconex NEO” (registered trademark), single fiber fineness: 1.7 dtex, fiber length: 51 mm), para-type wholly aromatic polyamide fiber (manufactured by Teijin Aramid, “Twaron” ( (Registered trademark), single fiber fineness 1.7 dtex, fiber length 50 mm), conductive nylon fiber (single fiber fineness 4.5 dtex, fiber 51 mm, sheath: nylon 6 / core: eccentric core-sheath conductivity of white metal compound Nylon fiber) is spun yarn of 1/68 count so that the meta-type wholly aromatic polyamide fiber: 93% by weight, the para-type wholly aromatic polyamide fiber: 5% by weight, and the conductive nylon fiber: 2% by weight. Thus, a twin-ply twisted yarn was obtained. Then, a plain woven fabric having a warp density of 57 pieces / 2.54 cm and a weft density of 50 pieces / 2.54 cm was woven.

  The undyed woven fabric (raw machine) obtained is debended / bound in a conventional manner, desizing scouring, cylinder drying, and baking, and then using a normal liquid jet dyeing, a dye bath containing a cationic dye and a carrier agent. Then, the temperature was raised from room temperature to dye at 130 ° C. for 60 minutes. Thereafter, a finishing set was performed to obtain a base cloth.

Next, the following composition was prepared.
[Composition of blended composition]
・ Acrylic binder 3.0%
(Solid content 40%)
・ ATO aqueous dispersion 2.0%
(Solid content 15%, thermal conductivity of ATO 50 W / m · K, fine particle diameter of ATO 50 nm or less)
・ Water 95%
Next, the composition was applied to the entire surface of the fiber surface of the woven fabric by padding (ATO content: 0.3 g / m ² , binder resin solid content: 1.2 g / m ² ), and then dried at 160 ° C. An arc protective fabric was obtained.
The obtained arc protective fabric had a basis weight of 162 g / m ² and an ATPV value of 8.6 cal / cm ² , which was good.

[Example 2]
A dyed fabric was obtained in the same manner as in Example 1. Next, the following composition was prepared.
[Composition of blended composition]
・ Acrylic binder 60.0%
(Solid content 40%)
・ ATO aqueous dispersion 5.0%
(Solid content 15%, thermal conductivity of ATO 50 W / m · K, fine particle diameter of ATO 50 nm or less)
・ Water 35.0%
Next, the blended composition was applied to the entire surface of the fiber on the back surface of the woven fabric by a rotary screen printing machine (ATO content: 1.2 g / m ² , binder resin solid content: 24.2 g / m ² ), and then 160 ° C. To obtain an arc protective fabric.
The obtained arc protective fabric had a basis weight of 186 g / m ² and an ATPV value of 10.2 cal / cm ² , which was good.

[Comparative Example 1]
A dyed fabric was obtained in the same manner as in Example 1.
[Composition of blended composition]
・ Acrylic binder 10.0%
(Solid content 40%)
・ ATO water dispersion 0.1%
(Solid content 15%, thermal conductivity of ATO 50 W / m · K, fine particle diameter of ATO 50 nm or less)
・ Water 89.9%
Next, the composition was applied to the entire surface of the fiber surface of the woven fabric by the padding method (ATO content: 0.01 g / m ² , binder resin solid content: 4.0 g / m ² ), and then dried at 160 ° C. An arc protective fabric was obtained.
The obtained arc protective fabric had a basis weight of 159 g / m ² , but had an insufficient ATPV value of 7.4 cal / cm ² .

  According to the present invention, there is provided a fabric and a protective product which are capable of developing any color, have an activity and a protective performance against an electric arc, and their industrial value is extremely large.

Claims (11)

A fabric using a spun yarn containing a meta-type aromatic polyamide fiber, wherein an infrared absorber is fixed in a range of 0.02 to 50 g / m ² , and an ATPV is used in an arc resistance test ASTM F1959-1999. A fabric having a value of 8.0 cal / cm ² or more.   The fabric according to claim 1, wherein the infrared absorber is metal oxide-based fine particles or carbon fine particles.   3. The fabric according to claim 1, wherein the infrared absorbent is fixed with a binder resin.   The fabric according to any one of claims 1 to 3, wherein a mixing ratio of the infrared absorbent and the binder resin is in a range of 1: 0.1 to 1:50.   The metal oxide-based fine particle is any one selected from the group consisting of antimony-doped tin oxide, tin-doped indium oxide, tungsten-based composite oxide, and lanthanum hexaboride. Cloth.   The fabric according to any one of claims 1 to 5, wherein the visible light transmittance of the metal oxide-based fine particles is 40% or more.   The fabric according to any one of claims 1 to 6, wherein the carbon fine particles are fixed only to the fiber surface on the back surface of the fabric.   For fabric, para-type aromatic polyamide fiber, polyphenylene sulfide fiber, polyimide fiber, polybenzimidazole fiber, polybenzoxazole fiber, polyamideimide fiber, polyetherimide fiber, Pyromex (registered trademark), carbon fiber, acrylic fiber, cellulose The fabric according to any one of claims 1 to 7, further comprising at least one selected from the group consisting of a system fiber and a conductive fiber. Basis weight in the range of 120~250g / ^{m 2,} the fabric according to any one of claims 1 to 8.   The fabric according to any one of claims 1 to 9, wherein the meta-type aromatic polyamide fiber is dyed.   Any one selected from the group consisting of arc protective clothing, flame-resistant protective clothing, work clothing, activity clothing, gloves, protective apron, and protective member using the fabric according to any one of claims 1 to 10. Protection products.