WO2016147779A1

WO2016147779A1 - Multilayered spun yarn, heat-resistant fabric obtained using same, and heat-resistant protective garment

Info

Publication number: WO2016147779A1
Application number: PCT/JP2016/054388
Authority: WO
Inventors: 大森英城; 高橋雅信; 岡部孝之
Original assignee: 日本毛織株式会社
Priority date: 2015-03-18
Filing date: 2016-02-16
Publication date: 2016-09-22
Also published as: JP2016176149A; EP3109351A1; JP5972420B1; EP3109351A4

Abstract

This multilayered spun yarn (20) comprises a core component (21) constituted of para-based aramid fiber yarns obtained by stretch breaking spinning and a sheath component (22) including polybenzimidazole fibers, wherein the sheath component (22) has been obtained by mix spinning so as to include the polybenzimidazole fibers and meta-based aramid fibers, the polybenzimidazole fibers and the meta-based aramid fibers having at least two different colors. In the multilayered spun yarn (20), the polybenzimidazole fibers and the meta-based aramid fibers apparently differ in color tone. This heat-resistant fabric is obtained using the multilayered spun yarn, and this heat-resistant protective garment is obtained using the heat-resistant fabric. Thus, a multilayered spun yarn which renders color matching easy and has not only high laundering resistance but also high heat resistance and flame retardancy, a heat-resistant fabric obtained using the multilayered spun yarn, and a heat-resistant protective garment are provided.

Description

Multi-layer structure spun yarn, heat-resistant fabric using the same, and heat-resistant protective clothing

The present invention relates to a multi-layer structure spun yarn including polybenzimidazole fiber and para-aramid fiber, a heat-resistant fabric using the same, and a heat-resistant protective clothing.

Protective clothing is used as work clothes for fire fighters, ambulance crews, life crews, marine rescuers, military, oil-related facilities workers, chemical factory workers, and others. In recent years, fire fighting garments in the United States, Canada, Australia, and some Europe use polybenzimidazole fibers having excellent heat resistance and flame retardancy. Since this fiber has a weak strength of about 2.4 cN / decitex (decitex is abbreviated as dtex hereinafter), a woven fabric woven with para-aramid fiber is usually used. This woven fabric is composed of a warp yarn or a weft yarn, one of which is a spun yarn made of polybenzimidazole fiber, and the other of which is a filament yarn made of para-aramid fiber. As another woven fabric excellent in heat resistance and flame retardancy, the present inventors use a check spun yarn of para-aramid fiber for the core, and meta-aramid fiber, flame-retardant acrylic fiber or polyetherimide fiber for the sheath. Have been proposed (Patent Documents 1 and 2).

WO2009 / 014007 WO2012 / 137556

However, since polybenzimidazole fibers cannot be dyed, only limited-color fibers can be obtained depending on the original, and there is a problem that it is difficult to obtain yarns and fabrics of various colors. In addition, fabrics made by interweaving conventional spun yarns made of polybenzimidazole fibers and filament yarns made of para-aramid fibers are easily fibrillated by the rubbing action during washing and wearing, and whitened on the fabric surface. In addition to the problem that the phenomenon occurs and the appearance deteriorates remarkably, the para-aramid fiber is discolored by light, and the strength is easily reduced. Further, the fiber compositions proposed in Patent Documents 1 and 2 have a problem that heat resistance and flame retardancy are insufficient.

In order to solve the above-mentioned conventional problems, the present invention is a multi-layered spun yarn having a high heat resistance and flame retardancy, and a heat-resistant and flame-resistant multi-layer spun yarn that is easy to color match, does not cause poor appearance and light embrittlement due to fibrillation. A protective fabric and heat-resistant protective clothing are provided.

The multilayer structure spun yarn of the present invention is a para-aramid fiber yarn in which the core component is check spun, and the sheath component is a multilayer structure spun yarn containing polybenzimidazole fiber, wherein the sheath component is polybenzimidazole fiber And a flame retardant fiber (excluding the para-aramid fiber yarn and the polybenzimidazole fiber), and the polybenzimidazole fiber and the flame retardant fiber are different in at least two colors. The multi-layer structure spun yarn has a color tone that is apparently different from that of the polybenzimidazole fiber and the flame-retardant fiber.

The heat resistant fabric of the present invention is characterized by using the above-mentioned multilayered spun yarn. The heat-resistant protective clothing of the present invention is characterized by using the heat-resistant fabric.

The multi-layer structure spun yarn of the present invention is a para-aramid fiber yarn in which the core component is check spun, and the sheath component is a multi-layer structure spun yarn containing polybenzimidazole fiber, and the sheath component is composed of polybenzimidazole fiber and And flame retardant fibers (excluding the para-aramid fiber yarn and the polybenzimidazole fiber), and the polybenzimidazole fiber and the flame retardant fiber are at least two different colors. The multi-layer structure spun yarn apparently has a color tone different from that of the polybenzimidazole fiber and the flame retardant fiber, so that color matching is easy and resistance to appearance is not exhibited in the sense that it does not exhibit poor appearance due to fibrillation. A multilayer structure spun yarn having high washability and high heat resistance and flame retardancy, a heat resistant fabric and a heat resistant protective clothing using the same can be provided. That is, color matching is facilitated by blending different colored fibers at the same time, and a sheath component containing polybenzimidazole fiber having higher heat resistance and flame retardancy is arranged in the portion directly exposed to the flame, Cloth made by fibrillation of para aramid fiber even if it is washed repeatedly by arranging para-aramid fiber yarn spun in the core component to maintain high strength, heat resistance and flame retardancy. It can be set as the fabric in which the whitening phenomenon of a surface does not occur easily. In addition, since polybenzimidazole fiber has a high moisture content, the total heat loss (Total 大きく heat 熱 loss) is large, and the heat transfer emanating from the body is also large, so that the heat-resistant protective clothing is comfortable to wear.

FIG. 1 is a perspective view showing a main part of a ring spinning machine for producing a core-sheath structure spun yarn in one embodiment of the present invention. FIG. 2 is a schematic perspective view of a core-sheath spun yarn in one embodiment of the present invention. FIG. 3 is a woven structure diagram of a fabric in one embodiment of the present invention.

The multi-layer structure spun yarn of the present invention is a para-aramid fiber yarn in which the core component is check-spun, and the sheath component is a polybenzimidazole fiber and a flame-retardant fiber (provided that the para-aramid fiber yarn and the poly-aramide fiber yarn). It is a fiber that has been blended with (excluding benzimidazole fiber). Polybenzimidazole (hereinafter also referred to as “PBI”) fiber is, for example, a fiber made from a polymer of 2,2 ′-(m-phenylen) -5,5′-bibenzimidazole, and has a thermal decomposition temperature exceeding 600 ° C. The deflection temperature under load is 410 ° C., the glass transition point is 427 ° C., and the oxygen index (OI) value is 41 or more. This fiber has a strength retention of 95% even after being exposed to air at 230 ° C. for 2 weeks, can maintain the fiber performance up to 1000 ° C. in nitrogen, is essentially nonflammable and has high heat resistance (hereinafter “ Encyclopedia of Textiles, page 848, Maruzen, March 25, 2002). PBI fiber is a product manufactured by PBI Performance Products, Inc. in the United States. Since PBI fiber has a high equilibrium moisture content of about 14.6% by weight, the fabric containing this fiber has a total heat loss measured by ASTM F 1868 Part C of 300 W / m ² or more, Heat transfer that emanates from the body also increases, making it a comfortable heat-resistant protective clothing.

Para-aramid fiber is a homopolymerization system manufactured by DuPont in the US, trade name "Kevlar" (same product name from Toray DuPont in Japan), Teijin, trade name "Twaron" There is a product name "Technora" manufactured by Teijin Limited. These fibers have a tensile strength of 20.3 to 24.7 cN / dtex, a thermal decomposition starting temperature of about 500 ° C., and an oxygen index (OI) value of 25 to 29. Although heat resistance and flame retardancy are inferior to PBI fibers, they are higher than ordinary fibers.

In the present invention, the sheath component is blended including PBI fiber and flame retardant fiber (excluding the para-aramid fiber yarn and the PBI fiber), and the PBI fiber and the flame retardant fiber are at least two colors. The PBI fiber and the flame retardant fiber appear to have different colors. Each fiber is mixed by spinning and has a predetermined color tone, which facilitates color matching.

The PBI fibers are preferably produced or original fibers. Here, the term “generated” refers to a state in which neither the original deposition nor the staining is performed. PBI fibers are yellow in their formed state. Therefore, this yellow color is mixed. The original is colored by adding a colorant to a polymer and then fiberized. Therefore, the color tone is limited. There are the following three stages for imparting a hue to a dyeable fiber. (1) Cotton stage: There are rose dyeing for directly dyeing disjointed fiber lumps, sliver dyeing for short fiber bundles, that is, dyeing in a sliver state, and top dyeing after winding this up and dyeing. (2) Thread stage: Thread dyeing is dyed in the yarn state, but this is dyed with cocoon dye according to its shape, and then corn dyeed after being softly wound up on a special die cone tube to make it easier to pass through the dye liquor. There is. (3) Knitted fabric stage: Anti-dyeing is performed by dyeing fabric in the fabric state. It is also called post-dying because it is dyed after weaving the fabric yarn. On the other hand, the above-mentioned (1), which has already been given a hue before weaving, is called colored yarn, (2) is called dyed yarn, and both are also called pre-dyed.

The flame-retardant fiber of the multi-layer structure spun yarn is preferably colored with at least one selected from an original fiber, rose dyeing, sliver dyeing, top dyeing fiber and yarn dyeing. The flame-retardant fiber after making into a fabric may be post-dyed. As a result, the PBI fiber is a produced or original fiber, and the color tone is limited. However, a desired color tone can be expressed by blending or dyeing the flame-retardant fiber in various colors.

When the sheath component is 100% by mass, the PBI fiber is preferably 10% by mass to 90% by mass, and the flame retardant fiber is preferably 10% by mass to 90% by mass. More preferably, the PBI fiber is 20% by mass or more and 80% by mass or less, the flame retardant fiber is 20% by mass or more and 80% by mass or less, and more preferably, the PBI fiber is 30% by mass or more and 70% by mass or less. The flame retardant fiber is 30% by mass or more and 70% by mass or less. Within the above range, color matching is easy and heat resistance is high.

When the multilayer structure spun yarn is 100% by mass, the core component is 20 to 40% by mass, the sheath component is preferably 60 to 80% by mass, and more preferably the core component is 22 to 35% by mass. The component is 65 to 78% by mass. When the core component is less than 20% by mass, the check spun yarn of the core component must be made extremely fine, and it is difficult to produce the check spun yarn. On the other hand, when the core component exceeds 40% by mass, the sheath fiber coverage becomes low. Further, when the sheath component is less than 60% by mass, the covering property is not good, and when it exceeds 80% by mass, the fineness of the entire multi-layer structure spun yarn is undesirably increased.

The PBI fiber is preferably a toe-breaked check fiber, a bias-cut or square-cut fiber. A toe-breaked check fiber is a fiber similar to a check-spun para-aramid fiber yarn of the core component (both torn fibers), so the affinity between the core component and the sheath component is good and unity It becomes a good multilayer structure spun yarn. The sheath component may be bias cut or square cut. Bias cut refers to alternately repeating perpendicular cutting and oblique cutting with respect to the traveling direction of the long fiber bundle (tow). For example, in the case of a 76/102 mm bias cut, the fiber length is uniformly distributed from the shortest 76 mm to the longest 102 mm. On the other hand, the square cut repeats only a fixed length of right-angle cutting. For example, in the case of a 51 mm square cut, all the fiber lengths are uniformly 51 mm.
Further, in recent years, there are also products that have a stepwise distribution called a mix cut, such as 76 mm (33%) + 89 mm (34%) + 102 mm (33%), in which square cuts having different fiber lengths are mixed. It is in circulation. The preferred fiber length of the cut fibers is in the range of 30 to 180 mm, more preferably 45 to 150 mm, particularly preferably 50 to 125 mm. Within this range, the strength can be maintained higher. The single fiber fineness is preferably in the range of 1 to 5 dtex, more preferably in the range of 1.5 to 4 dtex.

The flame retardant fiber preferably has an oxygen index (O.I) measured by JIS K 7201-2 of 26 or more. If it is the said range, the multi-layer structure spun yarn with high heat resistance and a flame retardance will be obtained with the para-aramid fiber yarn by which the core component was spun and the PBI fiber of the sheath component. The flame retardant fiber is at least one selected from meta-aramid fiber, polyarylate fiber, polybenzoxazole fiber, polyetherimide fiber, flame retardant wool, flame retardant rayon, flame retardant cotton and flame retardant acrylic fiber. One fiber is preferred.

The sheath component fiber is processed into a coated short fiber bundle having an optimal shape and form by a spinning method according to the fineness and fiber length. French style wool spinning is a suitable method for wool with thick fineness and long fiber length. Here, the hues and different types of fibers are mixed by, for example, passing a plurality of types of fiber bundles (sliver) each having a composition of 100% through an intersecting gill box, and doubling in the subsequent comber or pre-spinning process. And leveling by the drafting action. Hereinafter, this method is referred to as “sliver blending”. This method has a good yield and is suitable for high-mix low-volume production. On the other hand, cotton spinning is a method suitable for cotton having a small fineness and a short fiber length. Here, the hue and the dissimilar fibers are mixed mainly by a card machine during the blended cotton and carding process. Hereinafter, this method is referred to as “card blending”, which is suitable for mass production of small varieties although the yield is poor.

It is preferable that the coated fiber is further blended with an antistatic fiber. When antistatic fibers are blended, it is possible to prevent ignition due to static electricity. The antistatic fiber is preferably blended in the range of 0.1 to 1% by mass.

The multi-layer structure spun yarn preferably has a metric count of 28 to 52 (fineness: 357 to 192 dtex). If it is in this range, protective work clothes with good workability can be obtained.

In the present invention, a heat-resistant fabric is produced using the above-described multilayered spun yarn. The fabric is preferably a woven fabric. In the flameproof test of EN532, the heat resistant fabric has no flame, no holes, no melt, an average flame time of 2 seconds or less, and an average dust time of 2 seconds or less. Is preferred. The heat-resistant fabric preferably has a shrinkage rate of 5% or less without melting, dropping, separating and igniting the fabric in 5 minutes at 180 ° C. in a heat resistance test of ISO 1311613-1999. With these physical properties, the heat resistance and flame retardancy are very excellent. The heat resistant fabric preferably has an oxygen index (O.I) measured by JIS K 7201-2 of 26 or more, more preferably 26 to 50, more preferably 32 to 50, and particularly preferably. 37-48. Thereby, a flame retardance becomes high.

The heat-resistant fabric conforms to ISO 6330-1984, 2A-E specified in the international performance standard ISO 11613-1999, which is a test for measuring washing resistance in the sense that it does not exhibit poor appearance due to fibrillation. It is preferable that no whitening is observed even after washing 5 times. Thereby, the product value can be maintained high. The light resistance is preferably 2-3 or higher in both the carbon arc lamp test of JIS L 0842.7.2 (a) and the xenon arc lamp test of JIS L 0843. Thereby, the discoloration by light is low and a product value can be maintained high.

The heat-resistant protective clothing using the heat-resistant fabric of the present invention is suitable as work clothing for fire fighting suits, emergency crews, life crews, marine rescue workers, military personnel, oil-related facility workers, chemical factory workers, etc. It is. In the case of fire fighting clothes, it is preferable to use the heat resistant fabric of the present invention for the outer layer. This is because the heat resistance is high.

Hereinafter, the flame retardant fiber blended with the sheath component will be described.
(1) Meta-aramid fibers Meta-aramid fibers are, for example, manufactured by Du Pont in the United States, trade name "Nomesque" (same product name by Toray DuPont, Japan), Teijin, trade name "Conex", etc. There is. The oxygen index (OI) is 29-30.
(2) Flame-retardant wool As flame-retardant wool, there is flame-retardant wool treated with titanium and zirconium salt, which is called Zapro processing, using a wool such as a general merino type. As the wool, non-modified wool may be used, or the scale may be removed and shrink-proofed. The use of such non-modified wool or modified wool improves moisture absorption, blocks radiant heat, and keeps comfort even when sweating and getting wet in high temperature and harsh environments. This is because the heat resistance for protecting the human body can be exhibited. The oxygen index (OI) is 27-33.
(3) Flame retardant rayon Examples of flame retardant rayon include Provan processing (ammonia curing processing using tetrakishydroxymethylphosphonium salt developed by Albright & Wilson), Pyropatex CP processing developed by Ciba Geigy (N -Methylol dimethylphosnopropionamide processing), the brand name “Viscose FR” of Lenzing, Austria. The oxygen index (OI) is 26.
(4) Flame Retardant Cotton Flame retardant cotton such as Provan processing (processing in which tetrakishydroxymethylphosphonium salt is attached to cotton by ammonia curing method), Pyropatex CP processing (N-methyloldimethylphosnopropionamide processing), etc. Can be used. The oxygen index (OI) is 26.
(5) Flame-retardant acrylic fiber An acrylic fiber obtained by copolymerizing a vinyl chloride monomer as a flame retardant with acrylonitrile can be used. There is a product name "Protex" manufactured by Kaneka Corporation. The oxygen index (OI) is 29-37.
(6) Polyetherimide fiber The polyetherimide (PEI) fiber includes, for example, “ULTEM” (oxygen index (OI) 32) manufactured by SABIC Innovative Plastics. This fiber has a tensile strength of about 3 cN / dtex. The fineness of the polyetherimide single fiber is preferably 3.9 dtex (3.5 denier) or less, more preferably 2.8 dtex (2.5 denier) or less. If it is 3.9 dtex (3.5 denier) or less, it is flexible and has a good texture, and is suitable as work clothes. The preferred average fiber length of the polyetherimide fiber is in the range of 30 to 180 mm, more preferably 45 to 150 mm, and particularly preferably 50 to 125 mm. If it is the said range, it will be easy to spin.
(7) Polyarylate fiber As the polyarylate fiber, there is a trade name “Vectran” manufactured by Kuraray Co., Ltd. This fiber has a strength of 18 to 22 cN / dtex, an elastic modulus of 600 to 741 cN / dtex, a melting point or decomposition temperature of 300 ° C., and an oxygen index (OI) of 27 to 28.
(8) Polybenzoxazole fiber As polybenzoxazole (PBO) fiber, there is a product name “Zylon” manufactured by Toyobo Co., Ltd. This fiber has a tensile strength of 37 cN / dtex, an elastic modulus of 270 MPa, a melting point or decomposition temperature of 670 ° C., and an oxygen index (OI) of 64.

Next, the core-sheath spun yarn will be described. First, a check spun yarn is used as a core component. The core component is para-aramid fiber yarn that has been spun. Here, the check spun yarn refers to a yarn obtained by drafting a long fiber bundle (tow), cutting (stripping), and twisting it into a spun yarn. A direct spinning method in which draft-twisting is performed by one fine spinning machine may be used, or a slur bar may be once twisted to form a spun yarn (Perlock method or converter method) in two or more steps. The direct spinning method is preferable. By using the check yarn, a high strength can be maintained and a core-sheath structure spun yarn excellent in integrity with the sheath fiber can be obtained.

The preferred fineness of the check spun yarn is preferably in the range of 5.56 to 20.0 tex (single yarn, 50 to 180 single yarn), more preferably 6.67 to 16.7 tex (meter count). 60 to 150 single yarn). If the fineness is in the above range, the strength is high and it is suitable for heat-resistant protective clothing and the like from the viewpoint of texture and the like. The number of twists is preferably 350 to 550 times / m, more preferably 400 to 500 times / m in the 125th single yarn having a metric count. When the number of twists is in the above range, the integrity with the coated fiber is further increased. The preferred fiber length is distributed in the range of 30 to 180 mm, and the average fiber length is in the range of 45 to 150 mm, preferably 50 to 125 mm. Within this range, the strength can be maintained higher.

In the present invention, if the fineness of the single spun yarn is S ₀ (tex) and the number of twists is T ₀ (times / m), the twist coefficient Ks ₀ of the single yarn is calculated by the following equation. .
Ks ₀ = T ₀ · √S ₀

When displaying the spun yarn count, assuming that the count of the single yarn is C ₀ (m / g) and the number of twists is T ₀ (times / m), the twist coefficient Kc ₀ of the single yarn is as follows: Calculate with mathematical formula.
Kc ₀ = T ₀ / √C ₀

Next, an apparatus and method for producing the core-sheath structured yarn of the present invention will be described. FIG. 1 is a perspective view showing a main part of a ring spinning machine in one embodiment of the present invention. Two large and small cylindrical bodies 2 and 3 having different diameters are provided for each weight on the front bottom roller 1 that is actively rotated. The two cylindrical bodies 2 and 3 are directly connected coaxially in the axial direction. Two cylindrical front top rollers 4 and 5 having different diameters are placed on the two cylindrical bodies 2 and 3. The difference in diameter between the two front top rollers 4 and 5 is substantially the same as the difference in diameter between the lower two cylindrical bodies 2 and 3, but the size is opposite to that of the lower two cylindrical bodies 2 and 3. The two front top rollers 4 and 5 are covered with a rubber cot, and are fitted on a common arbor 6 to which a load is applied so as to be independently rollable. The short fiber bundle 16 pulled out from the roving bobbin is supplied from the guide bar to the back roller 8 through the trumpet feeder 7.

The short fiber bundle 15 is a para-aramid check fiber bundle of core fibers, and the short fiber bundle 16 is a coated fiber bundle. Although not shown, the trumpet feeder 7 can be swung in the axial direction of the front bottom roller 1, and the swiveling width can be adjusted. The short fiber bundle B sent from the back roller 8 and passed through the draft apron 9 is held and spun by the large diameter side cylindrical body 3 and the small diameter side cylindrical front top roller 5. The short fiber bundle A is spun by being supplied to the small-diameter columnar body 2 and the large-diameter cylindrical front top roller 4 via the yarn guide 14.

Since the delivery speed of the short fiber bundle 16 spun from the large diameter side cylindrical body 3 is higher than the spinning speed of the short fiber bundle 15 spun from the small diameter side cylindrical body 2, the two are connected via the snell wire 10. When the spun

short fiber bundles

15 and 16 are twisted together, the short fiber bundle 16 is entangled around the short fiber bundle 15, and the short fiber bundle 15 serves as a core and the short fiber bundle 16 serves as a sheath. A structural spun yarn 17 is formed.

The overfeed rate of the short fiber bundle 16 with respect to the short fiber bundle 15 is preferably 5 to 9%, more preferably 6 to 8%. When the overfeed rate is within the above range, the short fiber bundle 16 can wrap the short fiber bundle 15 in a “twist” shape and cover the core fiber with a coverage of almost 100%.

The formed multi-layered spun yarn 17 is wound around the thread tube 13 on the weight via the anti-node ring 11 and the traveler 12. Even if the gripping positions of the

short fiber bundles

15 and 16 on the cylindrical bodies 2 and 3 are somewhat different from one weight to another, the ratio of the feeding speeds of the two is always constant. There is no possibility that the properties of the thread 17 vary from one weight to another. Further, when the trumpet feeder 7 is swung as far as possible in the axial direction of the front bottom roller 1, the friction area of the front top roller 5 with the short fiber bundle 16 of the rubber cot coating is dispersed to prevent premature wear of the rubber cot coating. can do. Although not shown, it is desirable that the yarn guide 14 is swung in the axial direction of the front bottom roller 1 to reduce wear of the rubber cot coating of the cylindrical front top roller 4.

The preferred twisting direction of the core-sheath type multi-layer structure spun yarn is the same as that of the check yarn, and the most preferred twist number T _max (times / m) is the fineness of the single yarn after coating the sheath fiber. Regardless, it is determined by the check spun yarn fineness S ₀ (tex) and its twist number T ₀ (times / m), and the following equation is established.
T _max = Rs · T ₀ · √S ₀
Here, if the proportionality constant Rs = 0.495, the core fiber and the sheath fiber show the highest degree of integrity like a bolt and a nut, and the single yarn strength of the core-sheath multi-layer structure spun yarn is the maximum value. I take the.

When said single yarns to count display, the most preferred twist T _max (times / m) is determined by the stretch-broken yarn single yarn count C ₀ (m / g) and its twist T ₀ (times / m) The following equation is established.
T _max = Rc · T ₀ / √C ₀
Here, when the proportionality constant Rc = 15.7, the highest unity is shown, and the single yarn strength of the multilayer structure spun yarn takes the maximum value.

The multilayer structure spun yarn 20 obtained as described above is shown in FIG. In FIG. 2, the core component fiber 21 is a check-spun para-aramid fiber yarn, and the sheath component fiber 22 includes PBI fiber and meta-aramid fiber, and covers the periphery of the core component 21, so that the integrity is good. Even after washing, damage due to wear of para-aramid fiber yarns is reduced, or the ratio of para-aramid fibers appearing on the surface of the spun yarn decreases, and even if wear or washing causes damage such as wear The appearance is not deteriorated. Similarly, there is no fear of discoloration or strength reduction. In any case, deterioration of the quality can be prevented.

The fabric for protective clothing of the present invention is preferably formed by twisting two core-sheath spun yarns (single yarns) into a double yarn and making it a woven fabric. The reason for using twin yarn is that it has a strength that is more than twice that of single yarn and provides a binding force to prevent yarn breakage during weaving. It is to do. As an example, the twin yarn is manufactured using a twisting machine such as a double twister. As the name suggests, the double twister is excellent in productivity because it can be twisted twice with one rotation of the spindle. However, since there are 6 rubbing points on a very long twisted yarn path, the precious covering portion tends to be peeled off and disturbed to easily expose the core portion. A ring twister at the same two points is preferable, and an up twister with a very short twisted yarn path at the two points is most preferable.

In the fabric of hydrophilic fiber typified by cotton, the single yarn is glued as warp yarn. When weaving, the warp yarns repeatedly rub against each other every time the loom opens, and each time they receive tension, they rotate in a direction to return twist. As a result, the surface fluff of the warp yarn is entangled, and further fluff is pulled out from the yarn to reduce the tying force, and eventually the loom is stopped upon reaching cutting. If the fiber is hydrophilic, starch and the like are easily glued to the yarn, and the surface fluff is hardened with a glue, so that the conjugation force does not decrease during weaving, and no warp yarn breakage occurs. Moreover, after weaving, it can be easily removed by washing with water during the scouring process.

On the other hand, since wool and many synthetic fibers are hydrophobic, starch and the like do not act effectively. Even if it can be applied to the surface of the yarn using a special glue, no method has been found at this time that can be removed easily and inexpensively by means such as washing with water during the scouring process after weaving.

The warp yarn breakage in a loom is much more dependent on the conjugation force related to rubbing / entanglement / peeling of the surface fluff than the single fiber strength (cN / dtex) constituting the yarn. Accordingly, the warp yarn is preferably a twin yarn.

The twist direction / twist factor K _{1 of the} single yarn is set to S or Z as that of the double yarn, and the twist factor K _{2 in} that case is set depending on the woven fabric. Taking wool as an example, if it is desired to obtain a grain feeling and Shari as georgette or voile to single yarn Z twisting, ply yarns also a so-called strong twine set slightly larger a K ₂ as Z twist . On the other hand, if you want a lot of fluff on the surface of the fabric, like saxony or furano, to make it soft and bulging or slimy, double yarn is S twisted versus single yarn Z twisted to promote shrinking and raising. As a so-called sweet twist with K ₂ set to be small.

When the spun yarn is indicated by a count, it is preferably in the range of 1/28 to 1/52, the single yarn twist coefficient Kc ₁ is in the range of 81 to 87, and the twist direction of the double yarn is the twist of the single yarn. The direction is opposite and the twist coefficient Kc ₂ is preferably in the range of 78-84. However, twist factor Kc ₁ having a single fiber, twist factor Kc ₂ twin yarns, following calculated by formula.
Kc ₁ = T ₁ / √C ₁
Kc ₂ = T ₂ / √C ₁
Here, T ₁ represents the number of twists of single yarn (times / m), T ₂ represents the number of twists of twin yarn (times / m), and C ₁ represents the number of single yarns (m / g).

Within the above range, the twisted structure is stable, the yarn packing property is high, and the fabric can be made into a soft and soft texture.

The obtained double yarn is twisted and used as a woven fabric for warp and weft. As the woven fabric structure, plain weave, twill weave, also called satin weave, satin weave, and other changed weave can be used. When making a knitted fabric, any of flat knitting, circular knitting and warp knitting can be applied. Any organization may be used. When air is included in the knitted fabric, it is knitted into a double-bonded pile fabric. Among the woven fabrics, the mat weave shown in FIG. 3 is particularly preferable, and this mat woven fabric is called a flat +3/3 mat weave. The plain weave part is a plain structure composed of 8 warps and wefts, and the 3/3 mat weave part has three warps and wefts aligned, and this part protrudes from the surface. Therefore, it has a non-slip effect, and even if the flat structure is torn, it stops at the mat-woven portion and is hard to break. This is called Rip Stop structure in the sense of tearing prevention.

The weight (unit weight) per unit of the protective clothing fabric of the present invention is preferably in the range of 100 to 340 g / m ² . If it is the said range, it can be set as lighter and more comfortable work clothes. More preferably, it is in the range of 140 to 300 g / m ² , and particularly preferably in the range of 180 to 260 g / m ² .

It is preferable to add antistatic fibers to the fabric so that it will not be charged during activity. Examples of the antistatic fiber include metal fiber, carbon fiber, metal particles, and fibers kneaded with carbon particles. The antistatic fiber is preferably added in the range of 0.1 to 1% by mass, more preferably in the range of 0.3 to 0.7% by mass with respect to the spun yarn. Antistatic fiber yarns can also be added during weaving. For example, “Beltron” manufactured by KB Seiren, “Kurabo” manufactured by Kuraray, carbon fiber, metal fiber, etc. are preferably added in the range of 0.1 to 1% by mass.

Hereinafter, more specific description will be given using examples. The present invention is not limited to the following examples.

The measurement methods in Examples and Comparative Examples of the present invention were as follows.
<Oxygen index (O.I) test>
Measured according to JIS K 7201-2.
<Heat resistance test>
According to ISO 11613-1999, measurement was performed at 180 ° C. for 5 minutes.
<Flameproof test>
Measured according to EN532.
<Flame resistance>
Measured were carbonization length when indirect flame was burned with a Bunsen burner for 12 seconds at the lower end of a vertically arranged fabric sample specified by the JIS L 1091A-4 method, afterflame time when the flame was removed, and residual dust time. .
<Washing resistance>
Washed 5 times according to ISO 6330-1984, 2A-E specified in international performance standard ISO 11613-1999.
<Charge voltage test>
The voltage immediately after charging was measured by the triboelectric charge decay measurement method specified in JIS L1094.5.4 method.
<Total heat loss>
Measured according to ASTM F 1868 Part C.
<Other physical properties>
Measured according to JIS or industry standards.

(Examples 1 to 4)
1. Used fiber (1) Core component As a core component, para-aramid fiber, a check-up spun yarn of Teijin's trade name “Technola” (twisted number Z direction 45 times / 10 cm), yarn fineness 8.0 tex (meter number: 1) / 125) (single fiber fineness 1.7 dtex, average fiber length 100 mm, black original product) was used.
(2) Sheath component The following three types of fibers were blended.
(i) PBI fiber Tow (790000dtex (711000 denier), 444,000 fibers) with a PBI single fiber fineness of 1.8dtex manufactured by PBI Performance Products, Inc., USA, is obtained as a square cut with a fiber length of 51mm. Thus, a fiber bundle (sliver) was produced. The PBI fiber was a product (yellow).
(ii) Meta-aramid fiber The trade name “Conex” (fiber length 76/102 mm bias cut, fineness 2.2 dtex) manufactured by Teijin Limited was used.
(iii) Antistatic fiber As the antistatic fiber, a trade name “Bertron” manufactured by KB Seiren, single fiber fineness 5.6 dtex, fiber length: 89 mm square cut was used.

2. Production of spun yarn double yarn (1) Core-sheath spun yarn By the method shown in FIG. 1, 25.6% by mass of the para-aramid fiber (black original product) is used as the core, and 73.9% by mass in total of PBI fiber and para-aramid fiber. A core-sheath spun yarn was prepared using a fiber bundle (sliver) obtained by card-spinning 0.5% by mass of antistatic fibers as a sheath. The twist direction of the core-sheath spun yarn was Z, the number of twists was 63 times / 10 cm, and the fineness was 312.5 dtex. The color tone of the yarn obtained is summarized in Table 1.
(2) Twist yarn The core-sheath spun yarn was twisted with an up twister to obtain a double yarn. The twist direction of the twin yarn was S, the number of twists was 60 times / 10 cm, and the fineness was 625 dtex.

3. Fabrication of Woven Fabric A fabric of a flat +3/3 mat weave structure shown in FIG. 3 was fabricated using a rapier loom using the above-mentioned double yarn as warp and weft. The conditions and results of the resulting fabric are summarized in Table 2.

(Comparative Example 1)
The core sheath was the same as in Example 1 except that the sheath component was 73.9% by mass of meta-aramid fiber (manufactured by Teijin Ltd., trade name “Conex”, fiber length 76/102 mm bias cut, fineness 2.2 dtex, beige color) Made spun yarn and fabric. The color tone of the blended yarn is shown in Table 1, and the conditions and results of the fabric are collectively shown in Table 2.

As shown in Table 1, although PBI fibers have a limited color, yarns of various tones were obtained by uniformly blending meta-aramid fibers having different tones.

Table 2 shows the following.
(1) Combustibility, especially carbonization length is short, which is a great advantage of PBI fiber. It can be judged that it exhibits extremely excellent surface integrity.
(2) The oxygen index of the woven fabric mixed with PBI fibers is high, and the flame retardancy is extremely high.
(3) When PBI fibers are mixed, the frictional voltage becomes 150 V or less, and the measurement is impossible. This is estimated to be due to the fact that the moisture content of the PBI fiber is 14.6%. A fabric having a low frictional voltage is less likely to generate static electricity and has high safety.
(4) In the woven fabric as in the case of the core-sheath spun yarn, although the PBI fibers have a limited color, woven fabrics of various colors were obtained by uniformly blending meta-aramid fibers having different colors.

(Example 5, Comparative Example 2)
In this example, an actual fireproof garment was assumed, and a test was conducted by laminating a fabric composed of three layers of an outer layer, a middle layer, and an inner layer.
(1) Outer layer The fabric obtained in Example 1 and Comparative Example 1 was used.
(2) Middle layer (moisture permeable waterproof layer, moisture barrier)
Moisture permeable waterproof membrane on a base fabric made of a plain woven fabric (mass of 77 g / m ² ) using 85% by mass of meta-aramid fiber (fineness 2.2 dtex, fiber length 76/102 mm bias cut) and 15% by mass of wool. As an intermediate layer, a polytetrafluoroethylene film laminated with a mass of 105 g / m ² was used.
(3) Inner layer (thermal barrier, inner liner)
A 16-sheet honeycomb fabric (mass 213 g / m ² ) using a blended spun yarn of 85% by mass of meta-aramid fiber (fineness 2.2 dtex, fiber length 76/102 mm bias cut) and 15% by mass of wool was used.
The measurement results of the above laminated products are summarized in Table 3. Table 3 was measured by the ISO11613 European method.

Table 3 shows that all test items passed. The total heat loss by ASTM F 1868 Part C of the three-layer laminate is as shown in Table 4.

Table 4 shows that the total heat loss is high when the fabric of the present invention is used for the outer layer. In general, if the value of total heat loss is high, the heat flux emanating from the body due to fire fighting activities also increases, so it is far from the risk of heat stroke caused by protective prejudice, and it is considered that comfort in clothes increases. It is estimated that the reason for this high total heat loss is that the moisture content of the PBI fiber is 14.6%.

(Examples 6 to 8)
Replaced with PBI fiber and antistatic fiber blend of sheath component, PBI fiber, antistatic fiber and meta-aramid fiber (made by Teijin Limited, trade name "Conex", fiber length 76 / 102mm bias cut fineness 2.2dtex, beige This was carried out in the same manner as in Example 1 except that the color) blended product was used. The oxygen index of the obtained yarn is shown in Table 5, and the conditions and results of the fabric are shown together in Table 6.

As shown in Table 5, it can be seen that the core-sheath yarns of Examples of the present invention have high oxygen index and high flame retardancy. In addition, three kinds of orange spun yarn could be obtained.

Table 6 shows the following.
(1) It is a great advantage of PBI fibers that the flammability, especially the carbonization length, decreases significantly with an increase in the mixed use ratio of PBI fibers. It can be judged that it exhibits extremely excellent surface integrity.
(2) The oxygen index of the woven fabric mixed with PBI fibers is high, and the flame retardancy is extremely high.
(3) When PBI fibers are mixed, the frictional voltage becomes 150 V or less, and the measurement is impossible. This is estimated to be due to the fact that the moisture content of the PBI fiber is 14.6%. A fabric having a low frictional voltage is less likely to generate static electricity and has high safety.
(4) The change in the washing dimension increases with the increase in the PBI fiber mixture ratio, with respect to the m-aramid fiber having a moisture content of 2 to 3%, the moisture content of the PBI fiber is 14.6%. It is presumed to be caused by When the moisture content is high, the difference between the swelling and shrinkage of the fibers during washing increases, and the dimensions are likely to change.
(5) The degree of discoloration under the irradiation of carbon arc and xenon arc lamp for measuring light resistance tends to deteriorate as the PBI fiber mixture ratio increases.

(Examples 9 to 15)
The same procedure as in Example 1 was conducted except that the blending rate of the sheath component of the multilayer structure spun yarn was as shown in Table 7. In Table 7, the washing test is a washing test for measuring fabric damage. The PBI fiber was a toe-breaked check fiber, and a product (yellow) or black original was used. The sheath component blend is a sliver blend, and the contents of each fiber are as follows.
(1) The flame-retardant wool fiber was an Australian-made, merino-type unmodified wool (average fiber length: 75 mm), and was dyed in an olive green color by an ordinary method using an acid dye. Zapro processed to give flame retardancy.
(2) The flame retardant rayon uses the product name "Viscose FR" (average fineness 3.3dtex, fiber length 89mm mix cut) of Lenzing, Austria, and is converted into a sky blue color using a reactive dye. Stained.
(3) The flame-retardant cotton used was propane-processed cotton (process in which tetrakishydroxymethylphosphonium salt was attached to the cotton by an ammonia curing method). In this case, it was left as it was without being dyed.
(4) As the flame-retardant acrylic fiber, trade name “Protex M” (average fineness 3.3 dtex, fiber length 82/120 mm bias cut) manufactured by Kaneka Corporation was used. It was dyed in Oriental Blue using a cationic dye by a conventional method.
(5) Polyetherimide (PEI) fiber uses “ULTEM” (oxygen index (O.I) 32) manufactured by SABIC Innovative Plastics, single fiber fineness 3.3 dtex (3 denier), fiber length 76/102 mm bias cut did. It was dyed red using a disperse dye by a conventional method.
(6) Polyarylate fiber As the polyarylate fiber, Kuraray Co., Ltd., trade name “Vectran”, single fiber fineness 3.3 dtex (3 denier), fiber length 76/102 mm bias cut was used. The oxygen index (O.I) is 27-28. In this case, an original brown color was used as the polyarylate fiber.
(7) Polybenzoxazole fiber As polybenzoxazole (PBO) fiber, Toyobo Co., Ltd., trade name “Zylon”, single fiber fineness 3.3 dtex (3 denier), fiber length 76/102 mm bias cut was used. The oxygen index (O.I) is 64. The PBO fiber produced (light yellow) was used as it was.

From Table 7, using para-aramid fiber as the core component, PBI fiber and other flame retardant fibers (flame retardant wool fiber, flame retardant rayon fiber, flame retardant cotton fiber, flame retardant acrylic fiber, PEI fiber, polyarylate A multi-layer structure spun yarn having a sheath component of a blended fiber with a fiber or PBO fiber) has high washing resistance in the sense that it can be car-matched by color mixing and does not exhibit poor appearance due to fibrillation, and has heat resistance and difficulty. It was confirmed that the flammability was high.

The heat-resistant protective clothing using the heat-resistant fabric of the present invention is suitable as work clothing for fire fighting suits, emergency crews, life crews, marine rescue workers, military personnel, oil-related facility workers, chemical factory workers, etc. It is. In particular, it is a para-aramid fiber yarn in which the core component is check spun, and the sheath component is a blended fiber including PBI fiber and meta-aramid fiber, so that the fabric has high heat resistance and flame retardancy and has various colors. be able to.

DESCRIPTION OF SYMBOLS 1 Front bottom roller 2 Large diameter cylindrical body 3 Small cylindrical body 4,5 Front top roller 6 Arbor 7 Trumpet feeder 8 Back roller 9 Draft apron 10 Snell wire 11 Anti-node ring 12 Traveler 13 Thread tube 14 Yarn guide 15 Short fiber bundle ( Para-aramid checkered fiber bundle of core fiber)
16 Short fiber bundle (Coated fiber bundle)
17, 20 Multilayer structure spun yarn 21 Core component fiber 22 Sheath component fiber

Claims

A para-aramid fiber yarn in which the core component is check spun, and a sheath component is a multilayer structure spun yarn containing polybenzimidazole fiber,
The sheath component is blended including polybenzimidazole fiber and flame retardant fiber (however, excluding the para-aramid fiber yarn and the polybenzimidazole fiber),
The polybenzimidazole fiber and the flame retardant fiber are at least two different colors,
The multilayer structure spun yarn is characterized in that the polybenzimidazole fiber and the flame retardant fiber are apparently different in color tone.
The multi-layer structure spun yarn according to claim 1, wherein the polybenzimidazole fiber is a produced or original fiber.
The multilayer structure spun yarn according to claim 1 or 2, wherein the flame-retardant fiber is at least one selected from an original fiber, a cotton dyed fiber and a yarn dyed.
The polybenzimidazole fiber is 10% by mass or more and 90% by mass or less, and the flame retardant fiber is 10% by mass or more and 90% by mass or less when the sheath component is 100% by mass. The multilayer structure spun yarn according to any one of the above.
The multi-layer structure spun yarn according to any one of claims 1 to 4, wherein the flame-retardant fiber has an oxygen index (O.I) measured by JIS K 7201-2 of 26 or more.
The flame retardant fiber is at least one selected from meta-aramid fiber, polyarylate fiber, polybenzoxazole fiber, polyetherimide fiber, flame retardant wool, flame retardant rayon, flame retardant cotton and flame retardant acrylic fiber. The multilayer structure spun yarn according to any one of claims 1 to 5, which is a single fiber.
The multilayer structure spun yarn according to any one of claims 1 to 6, wherein the coated fiber is further blended with an antistatic fiber.
The multilayer structure spun yarn according to any one of claims 1 to 7, wherein the multilayer structure spun yarn has a metric count of 28 to 52 (fineness: 357 to 192 decitex).
A heat-resistant fabric using the multilayered spun yarn according to any one of claims 1 to 8.
In the flameproof test of EN532, the heat resistant fabric has no flame, no holes, no melt, an average flame time of 2 seconds or less, and an average dust time of 2 seconds or less. The heat resistant fabric according to claim 9.
The heat-resistant fabric according to claim 9 or 10, wherein the heat-resistant fabric does not melt, drop, separate, or ignite at a heat resistance test of ISO11613: 1999 at 180 ° C for 5 minutes, and the shrinkage rate is 5% or less. Fabric.
The heat-resistant fabric according to any one of claims 9 to 11, wherein the heat-resistant fabric has an oxygen index (O.I) measured by JIS K 7201-2 of 26 or more.
The heat resistant fabric according to any one of claims 9 to 12, wherein the flame retardant fiber of the heat resistant fabric is post-dyed.
A heat-resistant protective clothing using the heat-resistant fabric according to any one of claims 9 to 13.