JP2019173226A - Woven or knitted fabric - Google Patents

Abstract

To provide a woven or knitted fabric excellent in flame retardancy, flame shielding property, low smoking property and processability.SOLUTION: There is provided a woven or knitted fabric containing a non-melting fiber A having high temperature shrinkage factor of 3% or less, and a thermoplastic fiber B having LOI value according to JIS K 7201-2 (2007) of 25 or more and crimped number according to JIS L 1015 (2010) of 5 (/25 mm) or more, and having a smoking inhibitor.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a woven or knitted fabric.

  Conventionally, in applications that require flame retardancy, a method of kneading a polyester, nylon, or cellulosic fiber with a flame retardant agent at the raw yarn stage or a post-processing method has been employed.

  For example, a flame retardant fabric (Patent Document 1) composed of a blended yarn of a flame retardant polymer meta-aramid fiber, a flame-retardant treated polyester fiber and modacrylic fiber, or a composite yarn of meta-aramid fiber and polyphenylene sulfide (PPS) fiber (Patent Document 2), and a curtain fabric (Patent Document 3) in which a layer of flame-retardant polyester fiber or the like is laminated on a flame-resistant fiber layer are known.

JP 11-293542 A Japanese Patent Laid-Open No. 01-272836 JP 2005-334425 A

  However, although the fabric described in Patent Document 1 is used as a spun yarn in which a meta-aramid fiber having a high limit oxygen index LOI value is blended with other fibers, the fiber is likely to fall off in the process until it is made into a fabric. However, problems remain in terms of flame retardancy and processability. In the case of a general meta-aramid, since it shrinks and hardens rapidly due to temperature rise, stress concentration occurs locally in the event of a fire, etc., and the textile form cannot be maintained, and the flame is blocked for a long time. It is also considered difficult.

  Moreover, although it is disclosed that the composite yarn described in Patent Document 2 is excellent in chemical resistance and LOI value, in the case of a blended yarn, as in Patent Document 1, a process until forming a fabric is disclosed. The fibers are easy to fall off, and there is room for improvement in terms of flame retardancy and processability. In fact, Patent Document 2 only evaluates with yarn, and it cannot be said that there is a specific idea until the flame is cut off for a long time as a textile form. In addition, when the filament form is used, twisting is likely to occur when twisted, and when the filament form is used to form a textile form, it is difficult to obtain a uniform fabric. The problem remains in terms of sex. In addition, since the composite yarn described in Patent Document 2 contains polyphenylsulfone (PPS), it tends to be incompletely combusted and tends to decompose into smoke such as moophenol and phenylene sulfend.

  Furthermore, in the curtain fabric described in Patent Document 3, a flame retardant is added to a fiber such as polyester fiber and dried to provide the flame retardant. Even if the flame retardant itself has an excellent flame retarding effect, a problem remains in terms of its durability. Further, since the curtain fabric specifically described as an example in Patent Document 3 uses a flame-retardant polyester fiber for either one of the warp and the weft, the flame fabric exhibits flame retardancy but does not touch for a long time. There is room for improvement in the ability to withstand the flames, the fabric structure being easily collapsed, and the ability to block the flames.

  Accordingly, an object of the present invention is to provide a knitted or knitted fabric that is excellent in flame retardancy, flame barrier properties, and low smoke generation, and also excellent in workability.

In order to solve the above problems, the present invention employs any of the following means.
(1) Non-melt fiber A having a high temperature shrinkage rate of 3% or less, and a LOI value in accordance with JIS K 7201-2 (2007) of 25 or more, and compliant with JIS L 1015 (2010) A woven or knitted fabric comprising a thermoplastic fiber B having a reduced number of 5 (pieces / 25 mm) or more and comprising a smoke suppressant.
(2) The smoke suppressant is a phenol compound, a molybdenum compound, a borate compound, magnesium silicate, zinc phosphate, magnesium hydroxide, a tin compound, a silicone compound, a nickel compound, a palladium compound, alumina trihydrate, The woven or knitted fabric according to (1), which is at least one selected from aluminum hydroxide, ferrocene, fumaric acid, maleic acid and reaction products thereof.
(3) The woven or knitted fabric according to (1) or (2), wherein 0.1 to 50% by mass of the smoke suppressant is contained in 100% by mass of the woven or knitted fabric.
(4) The woven or knitted fabric according to any one of (1) to (3), wherein 10% by mass or more of the non-molten fiber A is contained in 100% by mass of the constituent fibers of the woven or knitted fabric.
(5) The woven or knitted fabric according to any one of (1) to (4), wherein 10% by mass or more of the thermoplastic fiber B is contained in 100% by mass of the constituent fibers of the woven or knitted fabric.
(6) Said (1)-(5) which contains fiber C other than the said non-melting fiber A and the said thermoplastic fiber B in 60 mass% or less in 100 mass% of constituent fibers of the said woven or knitted fabric. ) The woven or knitted fabric according to any one of the above.
(7) The woven or knitted fabric according to any one of (1) to (6), wherein the non-melt fiber A has a thermal conductivity of 0.060 W / m · K or less.
(8) The woven or knitted fabric according to any one of (1) to (7), wherein the non-molten fiber A is one or more selected from flameproof fibers and meta-aramid fibers.
(9) The woven or knitted fabric according to any one of (1) to (8), wherein the thermoplastic fiber B has a glass transition point of 120 ° C or lower.
(10) The thermoplastic fiber B is a flame retardant polyester, anisotropic molten polyester, flame retardant poly (acrylonitrile butadiene styrene), flame retardant polysulfone, poly (ether-ether-ketone), poly (ether-ketone). -Ketone), polyethersulfone, polyarylate, polyarylene sulfide, polyphenylsulfone, polyetherimide, polyamideimide, phenol, and fibers made of a resin selected from the group consisting of the above (1) to ( The woven or knitted fabric according to any one of 9).
(11) The woven or knitted fabric according to any one of (1) to (10), wherein the thermoplastic fiber B includes a sulfur atom.

  The woven or knitted fabric of the present invention is a woven or knitted fabric having excellent flame retardancy, flame barrier properties and low smoke generation, and excellent workability by having the above-described configuration.

It is a figure for demonstrating the flame-proof evaluation test method.

  The woven or knitted fabric of the present invention has a non-melt fiber A having a high-temperature shrinkage rate of 3% or less, a LOI value based on JIS K 7201-2 (2007) of 25 or more, and JIS L 1015 (2010). And a thermoplastic fiber B having a crimp number of 5 (pieces / 25 mm) or more, and a smoke suppressant.

  In the present invention, the non-melt fiber A having a high temperature shrinkage rate of 3% or less constitutes a woven or knitted fabric together with the thermoplastic fiber B or the like having a crimp number of 5 (pieces / 25 mm) or more, but the woven or knitted fabric approaches the flame. When heat is applied, the thermoplastic fiber B melts, and the melted thermoplastic fiber B spreads in a thin film along the surface of the non-molten fiber A (aggregate). As the temperature rises, both A and B fibers will eventually carbonize, but the non-melt fiber A has a high temperature shrinkage rate of 3% or less, so it is difficult to shrink even at high temperatures and it is difficult to open holes. Can block the flame. In this respect, it is preferable that the high temperature shrinkage rate is low, but even if it does not shrink, even if it expands greatly due to heat, the structure collapses and causes pores. Therefore, the high temperature shrinkage rate is preferably −5% or more. Especially, it is preferable that a high temperature shrinkage rate is 0 to 2%.

The high-temperature shrinkage is as follows: (i) The fiber used as the raw material of the woven or knitted fabric is allowed to stand for 12 hours in a standard state (20 ° C., relative humidity 65%), and then a tension of 0.1 cN / dtex is applied to the original length L0. And (ii) exposed to a dry heat atmosphere at 290 ° C. for 30 minutes without applying a load to the fiber, sufficiently cooled in a standard state (20 ° C., relative humidity 65%), and further The length L1 is measured by applying a tension of 0.1 cN / dtex to the fiber, and (iii) is a numerical value obtained from L0 and L1 by the following formula.
High temperature shrinkage = [(L0−L1) / L0] × 100 (%)

  In the present invention, since the woven or knitted fabric as described above contains a smoke suppressant, when the non-molten fiber A and the thermoplastic fiber B are carbonized, it is possible to promote complete combustion / vaporization of the non-carbonized fiber components, Can be suppressed. Furthermore, when heat is applied to the woven or knitted fabric, the smoke suppressant spreads in a thin film shape, so that the carbonized film can be strengthened.

  In the present invention, as the non-molten fiber A, it is preferable to use one having a thermal conductivity of 0.060 W / m · K or less. When the thermal conductivity of the non-molten fiber A is within this range, the heat insulation performance is also excellent.

The thermal conductivity [W / m · K] is a basic thermal constant of a material and is a heat transfer coefficient of the material alone. Expresses the ease of heat transfer in the material, and refers to the value obtained by dividing the heat flow density (heat energy passing through the unit area per unit time) by the temperature difference between the front and back surfaces of the material. Specifically, the thermal conductivity of the fiber is a woven / knitted test piece having a thickness of 0.5 mm using the fiber to be measured, and the thermal diffusivity of the test piece is determined according to ISO 22007-3 (2008). The specific heat of the test piece was measured according to JIS K7123 (1987), and the specific gravity of the test piece was further measured according to JIS K7112 (1999). Based on the measurement results of these thermal diffusivity, specific heat and specific gravity, Ask from.
Thermal conductivity = thermal diffusivity x specific heat x specific gravity

  In the present invention, the non-molten fiber A refers to a fiber that maintains its fiber shape without being liquefied when exposed to a flame. As the non-melted fiber used in the present invention, any non-melting fiber may be used as long as the high temperature shrinkage rate is within the range defined by the present invention. Specific examples include meta-aramid fiber and flame resistant fiber.

  In general, meta-aramid fibers have a high temperature shrinkage rate and do not satisfy the high temperature shrinkage rate specified in the present invention. However, the meta-aramid fiber has a high temperature shrinkage rate within the range specified by the present invention by suppressing the high temperature shrinkage rate. If it exists, since it is highly elastic and can improve the sewing property of a woven or knitted fabric, it can be preferably used. The flame-resistant fiber is a fiber that has been flame-resistant using a fiber selected from acrylonitrile-based, pitch-based, cellulose-based, phenol-based fiber, and the like as a raw material. These may be used alone or in combination of two or more.

  Of these, flame-resistant fibers are preferred from the viewpoint of low high temperature shrinkage, and among various flame-resistant fibers, acrylonitrile-based flame-resistant fibers are preferably used as fibers having a small specific gravity and being flexible and excellent in flame retardancy. Such flame-resistant fibers can be obtained by heating and oxidizing acrylic fibers as precursors in high-temperature air.

  Examples of commercially available non-molten fibers A that can be used in the present invention include flame resistant fiber “PYRON” (registered trademark) manufactured by Zoltek and used in Examples and Comparative Examples described later, and Toho Tenax Co., Ltd. Pyromex. (Pyromex) and the like.

  If the content of the non-molten fiber A in the woven or knitted fabric is too low, the function as an aggregate tends to be insufficient. On the other hand, if the content is too high, the thermoplastic fibers are difficult to spread into a sufficient film shape. The content of the molten fiber A is preferably 10% by mass or more, more preferably in the range of 15 to 60% by mass, and most preferably in the range of 30 to 50% by mass.

  Subsequently, the thermoplastic fiber B that will spread as a film-like substance has a LOI value of 25 or more in accordance with JIS K 72021-2 (2007). The LOI value is a volume percentage of the minimum oxygen amount necessary for sustaining the combustion of a substance in a mixed gas of nitrogen and oxygen, and it can be said that the higher the LOI value, the more difficult it is to burn. Therefore, the thermoplastic fiber B having a LOI value of 25 or more is difficult to burn, even if it is ignited, it immediately extinguishes when the fire source is released, and a carbonized film is usually formed in the part where the fire spreads slightly. The carbonized part prevents the spread of fire.

  The LOI value of the thermoplastic fiber B is preferably 55 or less, and more preferably in the range of 25 to 50 from the viewpoint of carbonizing at a high temperature.

  Further, the thermoplastic fiber B used in the present invention has a LOI value of 25 or more and a crimp number of 5 (pieces / 25 mm) in accordance with JIS L 1015 (2010). In the present invention, a thermoplastic fiber B having a LOI value of 25 or more and a non-molten fiber A are mixed. However, the non-molten fiber A is relatively straight and falls off during knitting and knitting because it is difficult to crimp. It's easy to do. However, when the number of crimps of the thermoplastic fiber B is 5 (pieces / 25 mm) or more, the thermoplastic fibers B are less likely to fall off due to the three-dimensional spiral structure caused by crimping. That is, by mixing the non-melting fiber A and the thermoplastic fiber B, not only the thermoplastic fiber B but also the non-melting fiber A is difficult to fall off due to the crimping of the thermoplastic fiber B. Since it is excellent in flame retardancy and can suppress fiber dropout in the woven or knitted fabric manufacturing process, it becomes a woven or knitted fabric excellent in workability, durability and quality.

  If the number of crimps of the thermoplastic fiber B is too large, uniform kneading of the fibers becomes difficult, and there is a possibility that the formation and mechanical strength of the woven or knitted fabric may be lowered. Per piece / 25 mm) or less. Furthermore, 10-40 (pieces / 25 mm) is more preferable, and 10-35 (pieces / 25 mm) is more preferable from the viewpoint of crimping processability and suppression of fiber dropout in the woven / knitted fabric manufacturing process.

  The thermoplastic fiber B used in the present invention is not particularly limited as long as the LOI value and the number of crimps are within the ranges specified in the present invention. Specific examples thereof include flame retardant polyester (polyethylene terephthalate, polytriflate). Methylene terephthalate, polyalkylene terephthalate, etc.), anisotropic molten polyester, flame retardant poly (acrylonitrile butadiene styrene), flame retardant polysulfone, poly (ether-ether-ketone), poly (ether-ketone-ketone), polyether Mention may be made of fibers composed of thermoplastic resins selected from the group of sulfones, polyarylates, polyarylene sulfides, polyphenylsulfones, polyetherimides, polyamideimides and mixtures thereof. These may be used alone or in combination of two or more.

  Among these, polyphenylene sulfide fiber (hereinafter also referred to as PPS fiber) is most preferable from the viewpoint of high LOI value and easy availability.

PPS fibers preferably used in the present invention, the polymer constituent units _{- (C 6 H 4 -S)} - which is a synthetic fiber made of a polymer whose main structural unit. Typical examples of these PPS polymers include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers thereof, block copolymers, and mixtures thereof. As a particularly preferred PPS polymer, polyphenylene sulfide containing a p-phenylene unit represented by — (C ₆ H ₄ —S) —, preferably 90 mol% or more, as the main structural unit of the polymer is desirable. From the viewpoint of mass, polyphenylene sulfide containing 80% by mass, more preferably 90% by mass or more of p-phenylene units is desirable.

  As a method for producing the PPS fiber, a method in which a polymer having the above-mentioned phenylene sulfide structural unit is melted at a melting point or higher and spun from a spinneret to form a fiber is preferable. The spun fiber is an unstretched PPS fiber as it is. Most of the unstretched PPS fibers have an amorphous structure and a high elongation at break. On the other hand, since such fibers have poor dimensional stability due to heat, stretched yarns are commercially available in which the fiber is stretched and oriented following spinning to improve the strength and thermal dimensional stability of the fibers. Specifically, “Torcon” (registered trademark) (manufactured by Toray Industries, Inc.), “Procon” (registered trademark) (manufactured by Toyobo Co., Ltd.), etc. are in circulation. In the present invention, the unstretched PPS fiber and the stretched yarn can be used in combination as long as the object of the invention is achieved. In addition, it does not matter even if it uses together the drawn yarn and the undrawn yarn of the other kind of fiber which satisfy | fills the scope of the present invention instead of the PPS fiber.

  The thermoplastic fiber B preferably contains a sulfur atom. In that case, not only a fiber made of a resin containing a sulfur atom but also a fiber provided with a sulfur atom by post-processing is preferred.

  The thermoplastic fiber B used in the present invention is used by a method in which the thermoplastic resin is used alone or in combination with a different material, and may be in any form of filament yarn or staple. When a staple is spun and used, the fiber length is preferably within a range of 30 to 60 mm, and more preferably within a range of 38 to 51 mm. If the fiber length is in the range of 30 to 60 mm, it can be made into a spun yarn in a general spinning process, and can be easily blended with different materials.

  Further, the thickness of the single fiber of the thermoplastic fiber B is not particularly limited, but the single fiber fineness is preferably in the range of 0.1 to 10 dtex from the viewpoint of passing through the spinning process. .

  The total fineness when used as a filament yarn and the yarn count when used as a spun yarn are not particularly limited and may be within the range satisfying the provisions of the present invention, and may be appropriately selected in consideration of the desired thickness of the knitted or knitted fabric. Good.

  The content of the thermoplastic fiber B as described above in the woven or knitted fabric is 10% by mass or more in 100% by mass of the constituent fibers in order to reliably form a film-like substance and to further improve the flame retardancy and flame barrier properties. It is preferable that it is in the range of 30-70 mass%. In addition, 100 mass% of the constituent fibers of the woven or knitted fabric means that the total mass of the fibers used during weaving / knitting is 100%.

  In the present invention, fibers C other than the non-molten fibers A and the thermoplastic fibers B may be contained. Examples of the fiber C include a fiber having a LOI value of less than 25 that tends to be crimped and a low fuming fiber. In the case of using a fiber that tends to be crimped as the fiber C, the effect of the crimping can be obtained at a low cost, and in the case of using a low smoke generating fiber as the fiber C, the smoke suppression effect of the woven or knitted fabric can be obtained. It can be improved.

  Specific examples of the fiber C include thermoplastic cellulose fibers, acrylic fibers, nylon fibers, and polyester fibers (polyethylene terephthalate fibers, polytrimethylene terephthalate fibers, and the like). These may be used alone or in combination of two or more. Polyethylene terephthalate fiber (hereinafter referred to as PET fiber) is most preferable from the viewpoint of crimp processability and availability. Most preferred from the viewpoint of smoke suppression and availability are phenol fibers and polyethylene terephthalate fibers.

The preferred content of the fiber C in 100% by mass of the constituent fibers of the knitted or knitted fabric is 0 to 60% by mass, more preferably 10 to 50% by mass. The non-melt fiber A and the thermoplastic fiber B (further The fiber C) may be used in any form of spun yarn or filament yarn.

  In the case of spun yarn, each of the non-melt fiber A and the thermoplastic fiber B (further fiber C) may be used as a spun yarn, or the non-melt fiber A and the thermoplastic fiber B (further fiber C) are mixed at a predetermined ratio. And it is good as a blended yarn. The blended yarn can be obtained, for example, by first uniformly mixing using a fiber opening device, then forming a sliver with a carding machine, drawing with a drawing machine, roving and spinning. A plurality of the spun yarns obtained may be twisted together.

  In the case of blending non-melt fiber A and thermoplastic fiber B (and fiber C), it is preferable to use short fibers having the same length because a more uniform spun yarn can be obtained. The lengths do not have to be exactly the same, and there may be a difference of about ± 5% with respect to the length of the non-molten fiber A. From this viewpoint, it is preferable that each fiber has a fiber length in the range of 30 to 60 mm.

  On the other hand, in the case of filament yarn, the non-melt fiber A and the thermoplastic fiber by a false twisted yarn of each of the non-melt fiber A and the thermoplastic fiber B (and the fiber C), or air mixed fiber and composite false twist. A composite yarn in which B (further thermoplastic fiber C) is combined can be used.

  The woven or knitted fabric of the present invention constituted by the fibers as described above has a smoke suppressant. Since the woven or knitted fabric as described above contains a smoke suppressant, complete combustion of the fiber constituents is promoted during combustion to suppress smoke generation and to strengthen the carbonized film.

  Examples of the smoke suppressant include phenol compounds, molybdenum compounds, borate compounds, magnesium silicate, zinc phosphate, magnesium hydroxide, tin compounds, silicone compounds, nickel compounds, palladium compounds, alumina trihydrate, water Examples thereof include aluminum oxide, ferrocene, fumaric acid, maleic acid and reaction products thereof, and one or more selected from such groups can be preferably used. Examples of the molybdenum compound include ammonium dimolybdate, ammonium molybdate, molybdenum trioxide, calcium zinc molybdate compound, and zinc molybdate compound. Examples of the borate compound include zinc borate, calcium borate, and aluminum borate. Examples of the silicone compound include silicone acrylic compounds.

  Among the above smoke suppressants, phenol compounds, borate compounds, and silicone acrylic compounds are particularly preferable. However, the smoke suppressant is 0.1 to 50% by mass in 100% by mass of the woven or knitted fabric, more preferably 0.1 to 0.1% by mass. It is preferable to contain in the range of 40 mass%. Without affecting the formation of the carbonized film of the non-molten fiber A and the thermoplastic fiber B, it is possible to selectively promote the decomposition of the fiber constituent components that do not become the carbonized film, and as a result, it is possible to further suppress smoke generation. Note that 100% by mass of the woven or knitted fabric means that the mass of the woven or knitted fabric finally obtained including the smoke suppressant is 100%.

  The smoke suppressant may be applied to the knitted or knitted fabric knitted / woven with the above-described fibers, may be applied to the fibers before knitting / weaving, or may be kneaded into the fibers themselves. Good. Specific methods for applying the woven or knitted fabric later include, for example, immersing the woven or knitted fabric in a desired concentration of smoke suppressant treatment solution, then squeezing with a mangle, applying with a spray, roll coating, knife coating, etc. Then, the method of drying after that can be illustrated.

  Some smoke suppressants can take the shape of the fiber itself. Specifically, for example, the phenol compound may be a phenol fiber. In the case where the fibrous smoke suppressant can also correspond to any of the fibers A to C, the content is handled as each content. For example, when the phenol compound is a fiber having a length of 5 mm and a crimp number of 15/25 mm, it functions as a smoke suppressant and also functions as a fiber C. Therefore, fiber A 20 g, thermoplastic fiber B 20 g, phenol fiber If the composition is 10 g, the content of the fiber C is 20% by mass, and the content of the smoke suppressant is 20% by mass.

  In the present invention, the woven fabric is woven using the above-described spun yarn or filament yarn using an air jet loom, a water jet loom, a rapier loom, a projectile loom, a shuttle loom or the like. In the warp preparation process, warp gluing may be performed or no gluing may be performed, but in the case of using a yarn containing flame-resistant yarn fiber, gluing is performed in order to suppress fuzz during weaving of the flame-resistant yarn. It is preferable to carry out. The woven structure may be selected from plain weave, twill weave, satin weave and their changed structures according to the texture and design. Furthermore, a multi-woven structure such as a double weave may be used.

  In the case of knitted fabrics, the above-described spun yarn or filament yarn is used to make a weft knitting machine such as a flat knitting machine, an old fashion knitting machine, a circular knitting machine, a computer jacquard knitting machine, a sock knitting machine, a cylindrical knitting machine, or a tricot knitting machine. Knitting using a warp knitting machine such as a Russell knitting machine, an air jet loom, or a Milanese knitting machine. A draft yarn feeder for inserting spandex yarn may be used. The knitted fabric structure may be selected according to the desired texture and design, and in the weft knitting, there are tengu knitting, rubber knitting, pearl knitting, tuck knitting, floating knitting, lace knitting, and their changing structure. In the warp knitting, the single / denby, single / bandaique, single / cord, berlin, dougle / denby, atlas, chord, half tricot, satin, sharkskin, etc. Is mentioned.

  After weaving or knitting, after desizing and scouring by a normal method, it may be heat-set to a predetermined width and density using a tenter, or may be used as it is. The set temperature is good enough to obtain the effect of suppressing the high temperature shrinkage, and is preferably 160 to 240 ° C, more preferably 190 to 230 ° C.

  Resin processing may be performed at the same time as heat setting or in a separate process after heat setting for the purpose of improving wear resistance, improving texture, etc. within a range not impairing the effects of the present invention. Depending on the type of resin used, the resin processing consists of a pad dry cure method in which a woven or knitted fabric is dipped in a resin tank, then squeezed with a padder, dried and fixed, and a pad steam method in which the resin is reacted and fixed in a steam tank. Either can be selected.

  The woven or knitted fabric of the present invention thus obtained is not only flame retardant, but also excellent in low smoke generation and flame barrier properties, and is excellent in fire spread effect, so it is used for clothing materials, wall materials, floor materials, ceiling materials, covering materials, etc. It is suitable for doing. In particular, it is suitable for use as a fireproof protective clothing, a fireproofing covering material for urethane sheet materials such as automobiles and airplanes, and a fireproofing material for bed mattresses.

The basis weight of the woven or knitted fabric of the present invention is preferably 50 g / m ² or more, more preferably 100 g / m ² or more in order to further improve the flame shielding performance. Moreover, in order to improve flame-shielding performance, it is also preferable that the thickness of the woven or knitted fabric conforming to the JIS L 1096-A method (2010) is 0.08 mm or more.

  Further, the density of the woven or knitted fabric of the present invention is not particularly limited, and is appropriately selected depending on the required flame shielding performance. If the density is small, the heat insulation is improved by increasing the air layer. However, it may be determined in consideration of ease of handling and target heat insulation / flame insulation.

<Flame resistance test>
The test was conducted according to 8.1.1 A-1 method (45 ° micro burner method) of JIS L 1091 (flammability test method for textile products, 1999). That is, after flame time after heating for 1 minute (less than 3 seconds), afterglow time (5 seconds or less), a combustion area (30 cm ² or less), burn length of (20 cm or less) was measured, then Chakuen 3 seconds after flame time (3 seconds or less) in, afterglow time (5 seconds or less), measured combustion area (30 cm ² or less), and partitioned. If these values are in (parentheses), it corresponds to the “category 3” of the evaluation category according to JIS L 1091, and it was judged that it was combustible.

<Evaluation of flame barrier properties>
Ignition was performed by a method according to JIS L 1091 (Flameability test method for textile products, 1999) according to 8.1.1 A-1 method (45 ° micro burner method), and the flame shielding property was evaluated as follows. That is, as shown in FIG. 1, a micro burner 1 having a flame length L of 45 mm is set up in a vertical direction, and a specimen 2 is arranged at an angle of 45 degrees with respect to a horizontal plane. Flameproofness was evaluated in a test in which the combustor 4 was placed through a spacer 3 having a thickness of 2 mm and burned. For the combustible 4, qualitative filter paper grade 2 (1002) sold by GE Healthcare Japan Co., Ltd., which was left in the standard state for 24 hours in advance to make the moisture content uniform, ignites the micro burner 1. The time until the combustor 4 was ignited was measured in seconds. This measurement was performed 3 times and the average value was adopted.

  When the combustion body 4 ignited within 3 minutes of flame contact, “no flame shielding” was indicated and indicated as “x”. If the combustion body 4 does not ignite even after being exposed to flame for 3 minutes or longer, it is said that “there is flameproof performance”, but the longer the flameproof time, the better. Indicated as ◎.

《Smokeability evaluation》
Smoke particles measured according to JIS C 60695-6.1 6.1, smoke specific attenuation area σ _r (m ² / g), that is, per unit mass reduction Δm (g) of the combustion material The total area (m ² ) of the shadow projected by. The measurement was performed 3 times and the average value was adopted.

《Fiber loss rate》
The fiber loss rate of the spun yarn in the present invention, the mass A ₀ of the fiber as a raw material of the woven or knitted fabric is measured, and mixed by opening machine, then further mixed by blow room installation cotton machine, and then through the carding machine The obtained sliver was drawn with a drawing machine and then twisted with a roving machine to obtain a roving yarn. Subsequently, it was twisted with a spinning machine, drawn and twisted to obtain a spun yarn. The mass A ₁ of the obtained spun yarn is measured, and is a numerical value obtained from A ₀ and A ₁ by the following formula.
Fiber loss rate = [(A ₀ −A ₁ ) / A ₀ ] × 100 (%)

《Weight weight》
JIS L 1096 was measured in accordance with 8.3 (A method) of (2010), expressed in 1 m ² per mass (g / ^{m 2).} The measurement was performed twice and the average value was adopted.

"thickness"
Measured in accordance with 8.4 (Method A) of JIS L 1096 (2010). The measurement was performed 10 times and the average value was adopted.

<< LOI value >>
The LOI value was measured according to JIS K7201-2 (2007).

《Glass transition point》
The glass transition point was measured three times according to JIS K 7121 (2012), and the average value was adopted.

<< crimp number >>
Measured according to JIS L 1015 (2010) 8.12.1. The measurement was performed 20 times and the average value was adopted.

<Used fiber>
<Non-melting fiber A-1>
1.7 dtex Zoltek flameproof fiber “PYRON” (registered trademark), length 6 mm, high temperature shrinkage 1.6%, thermal conductivity 0.033 W / m · K
<Non-melting fiber A-2>
1.67 dtex meta-aramid fiber, length 6 mm, high temperature shrinkage 2.8%, thermal conductivity 0.055 W / m · K
<Thermoplastic fiber B-1>
PPS fiber (containing 35% by mass of unstretched PPS fiber in 100% by mass of PPS fiber), length 5.1 mm, LOI value 34, glass transition temperature 90 ° C., crimp number 7 (pieces / 25 mm)
<Thermoplastic fiber B-2>
PPS fiber (contains 40% by mass of PPS fiber in 100% by mass of PPS fiber), length 5.1 mm, LOI value 34, glass transition temperature 90 ° C., crimp number 7 (pieces / 25 mm)
<Fiber C-1>
PET fiber (containing 35% by mass of PET unstretched yarn in 100% by mass of PET fiber), length 5.1 mm, LOI value 20, glass transition temperature 68 ° C., crimp number 15 (pieces / 25 mm)
<Fiber C-2>
Acrylic fiber, length 5.1 mm, LOI value 20, high temperature shrinkage 35%, thermal conductivity 1.02 W / m · K, crimp number 13 (pieces / 25 mm)
<Other fibers C-3>
Nylon fiber (containing 33% by mass of nylon unstretched yarn in 100% by mass of nylon fiber), length 5.1 mm, LOI value 21, glass transition temperature 58 ° C., crimp number 15 (pieces / 25 mm)
<Fiber C-4>
Flame retardant rayon fiber, length 5.1mm, LOI value 27, crimp number 5 (pieces / 25mm)
<Fiber C-5>
PPS fiber (containing 35% by mass of unstretched PPS fiber in 100% by mass of PPS fiber), length 5.1 mm, LOI value 34, glass transition temperature 90 ° C., crimp number 2 (pieces / 25 mm)

[Example 1]
(spinning)
Unmelted fiber A-1 and thermoplastic fiber B-1 were mixed by a fiber spreader, then further mixed by a blended cotton machine, and then passed through a carding machine to obtain a sliver. The mass of the obtained sliver was 310 gelen / 6 yards (20.09 g / 5.46 m). Subsequently, it was drawn by setting a total draft of 8 times with a drawing machine, and a sliver of 290 gelen / 6 yards (18.79 g / 5.46 m) was obtained. Subsequently, it was twisted to 0.55 T / 2.54 cm by a roving machine and drawn 7.4 times to obtain a roast yarn of 250 gelen / 6 yards (16.20 g / 5.46 m). Subsequently, it was twisted to 16.4 T / 2.54 cm with a fine spinning machine, stretched to a total draft of 30 times, and twisted to obtain a spun yarn No. 30 with a cotton count. The spun yarn thus obtained was twisted with a double twister at 64.7 T / 2.54 cm to give a No. 30 twin yarn. The mass ratio of the non-melt fiber A-1 and the thermoplastic fiber B-1 of the spun yarn was 40:60.

(Weaving)
The spun yarn thus obtained was woven using a rapier loom with a plain weave of warp 50 / inch (2.54 cm) and weft 50 / inch (2.54 cm).

(Scouring and heat set)
After scouring in warm water at 80 ° C. containing a surfactant for 20 minutes, it was dried with a 130 ° C. tenter and further heat-set with a 230 ° C. tenter. The yarn density of the fabric base material after heat setting was 52 warps / inch (2.54 cm) and 51 wefts / inch (2.54 cm). The fabric base material had a basis weight of 100 g / m ² and a density of 50 kg / m ³ . The fiber loss rate was 19%. Further, the fabric substrate was dipped in a 10 g / L silicone acrylic compound and 2 g / L magnesium hydroxide mixed treatment solution, and then squeezed with a mangle and dried to obtain a fabric.

The obtained woven fabric had a basis weight of 105 g / m ² and a density of 50 kg / m ³ , and was dense and soft, but also provided sufficient tension. As a result of conducting the flame resistance test, even when heated for 1 minute, the combustion body did not ignite, the combustion area was 8 cm ² or less, and the combustion length was 7 cm. . Further, this fabric did not break or perforate even when bent by 90 ° or more, and had excellent bending workability. Furthermore, in the flame barrier evaluation, the combustion body did not ignite for 33 minutes and had a sufficient flame barrier. Furthermore, the specific light reduction area of the smoke was 0.05 (m ² / g).

[Example 2]
Using the spun yarn No. 30 described in Example 1, a knitted base material was knitted using a 20G circular knitting machine by means of a tentacle knitting. The obtained knitted base material had a wal number of 25 wales / inch (2.54 cm), a course number of 28 courses / inch (2.54 cm), and a loop length of 0.39 cm / 1 loop. After scouring in warm water at 80 ° C. containing a surfactant for 20 minutes, it was dried with a 130 ° C. tenter and further heat-set with a 230 ° C. tenter. The yarn density of the knitted base material after heat setting was 31 wal / inch (2.54 cm) and 30 course / inch (2.54 cm). The knitted base material had a basis weight of 98 g / m ² and a density of 53 kg / m ³ . The fiber loss rate was 19%. Further, the knitted fabric substrate was immersed in a 10 g / L silicone acrylic compound, 3 g / L zinc borate mixed treatment solution, and then squeezed with a mangle and dried to obtain a knitted fabric.

The finally obtained knitted fabric had a basis weight of 103 g / m ² and a density of 52 kg / m ³ , and was dense and soft, but had sufficient elasticity. As a result of performing a flame resistance test, the combustion body did not ignite even when heated for 1 minute, and the combustion area was 7 cm ² or less and the combustion length was 8 cm, which was sufficiently flame retardant. . Further, this knitted fabric did not break or perforate even when bent at 90 ° or more, and had excellent bending workability. Furthermore, in the flame barrier evaluation, the combustion body did not ignite for 32 minutes and had sufficient flame barrier properties. Furthermore, the specific light reduction area of the smoke was 0.03 (m ² / g).

[Example 3]
A woven fabric was obtained in the same manner as in Example 1 except that 40:20:40 of non-molten fiber A-2, thermoplastic fiber B-2, and fiber C-1 were used. The yarn density of the woven fabric substrate after refining and heat setting was 51 warps / inch (2.54 cm) and 51 wefts / inch (2.54 cm). The finally obtained woven fabric had a basis weight of 110 g / m ² and a density of 50 kg / m ³ . The fiber loss rate was 6%. As a result of conducting the flame resistance test, even when heated for 1 minute, the combustion body did not ignite, the combustion area was 15 cm ² or less, and the combustion length was 13 cm. . Further, this fabric did not break or perforate even when bent by 90 ° or more, and had excellent bending workability. Furthermore, in the flameproof evaluation, the combustor did not ignite for 21 minutes and had a sufficient flameproofness. Furthermore, the specific light reduction area of the smoke was 0.05 (m ² / g).

[Comparative Example 1]
Non-melt fiber A-1 and fiber C-5 were blended to make the mass ratio 40:60, and the fabric base material was immersed in a 10 g / L silicone acrylic compound, 2 g / L magnesium hydroxide mixed solution. A woven fabric was obtained in the same manner as in Example 1 except that it was not present.

The woven fabric base material after refining and heat setting has a yarn density of 51 yarns / inch (2.54 cm), a weft of 51 yarns / inch (2.54 cm), a basis weight of 78 g / m ² , and a density of 64 kg / m ³ . there were. The finally obtained woven fabric had a basis weight of 80 g / m ² and a density of 66 kg / m ³ . As a result of performing a flame resistance test, the combustion body did not ignite even when heated for 1 minute, and the combustion area was 10 cm ² or less and the combustion length was 9 cm, which was sufficiently flame retardant. . Further, this fabric did not break or perforate even when bent by 90 ° or more, and had excellent bending workability. Furthermore, in the flameproof evaluation, the combustion body did not ignite for 29 minutes and had a sufficient flameproofness. However, the specific light reduction area of smoke was 12 (m ² / g), and the fiber loss rate was as high as 48%.

[Comparative Example 2]
A woven fabric was obtained in the same manner as in Example 1 except that the fibers C-2, C-3, and C-4 were mixed and the mass ratio was 40:20:40.

The yarn density of the woven fabric substrate after refining and heat setting was 51 warps / inch (2.54 cm) and 51 wefts / inch (2.54 cm). Moreover, the fabric weight was 100 g / m ² and the density was 53 kg / m ³ . The fiber loss rate was 3%. Moreover, the fabric finally obtained had a basis weight of 102 g / m ² and a density of 56 kg / m ³ . As a result of conducting the combustion resistance test, a hole was opened in the portion directly above the burner in less than 3 seconds by holding the burner over the test piece, and the test piece itself was ignited and burned. Therefore, it cannot be said that it has a flame retardance. Further, as described above, the test specimen itself ignited and burned, and it can be said that it does not have flameproofing properties without being measured. Furthermore, the specific light reduction area of the smoke was 0.6 (m ² / g).

[Comparative Example 3]
A non-melt fiber A-1 and fiber C-5 were blended to obtain a woven fabric in the same manner as in Example 1 except that the mass ratio was 40:60.

The fabric base material after refining and heat setting has a yarn density of warp 51 / inch (2.54 cm), weft 51 / inch (2.54 cm), basis weight 78 g / m ² , and density 59 kg / m ³ . there were. Moreover, the fabric finally obtained had a basis weight of 82 g / m ² and a density of 60 kg / m ³ . As a result of performing the flame resistance test, even when heated for 1 minute, the combustion body did not ignite, the combustion area was 10 cm ² or less, and the combustion length was 11 cm. . Further, this fabric did not break or perforate even when bent by 90 ° or more, and had excellent bending workability. Furthermore, in the flame shielding evaluation, the combustion body did not ignite for 26 minutes and had sufficient flame shielding properties. However, the specific light reduction area of the smoke was 10 (m ² / g), and the fiber loss rate was very high at 45%.

[Comparative Example 4]
Non-melt fiber A-2 and fiber C-2 were blended to obtain a woven fabric in the same manner as in Example 1 except that the mass ratio was 40:60.

The woven fabric substrate after refining and heat setting has a yarn density of 51 yarns / inch (2.54 cm), a weft of 51 yarns / inch (2.54 cm), a basis weight of 100 g / m ² , and a density of 64 kg / m ³ . there were. The fiber loss rate was 5%. Further, the finally obtained woven fabric had a basis weight of 102 g / m ² and a density of 66 kg / m ³ . As a result of conducting the combustion resistance test, a hole was opened in the portion directly above the burner in less than 3 seconds by holding the burner over the test piece, and the test piece itself was ignited and burned. Therefore, it cannot be said that it has a flame retardance. Further, as described above, the test specimen itself ignited and burned, and it can be said that it does not have flameproofing properties without being measured. Furthermore, the specific light reduction area of the smoke was 0.33 (m ² / g).

  Table 1 summarizes the evaluation results of Examples 1 to 3 and Comparative Examples 1 to 4.

  The present invention is effective for prevention of smoke and fire spread in a fire, and is suitable for use in wall materials, floor materials, ceiling materials, etc. that are required to have flame retardancy, and particularly for railways, furniture, bedding, etc. It is suitable for use as a fire blocking material.

1 Micro burner 2 Specimen 3 Spacer 4 Combustion body L Flame length
th spacer thickness

Claims (11)

  A non-melt fiber A having a high temperature shrinkage rate of 3% or less, a LOI value based on JIS K 7201-2 (2007) of 25 or more, and a crimped number based on JIS L 1015 (2010) A woven or knitted fabric comprising 5 (pieces / 25 mm) or more of thermoplastic fibers B and comprising a smoke suppressant.   The smoke suppressant is a phenol compound, molybdenum compound, borate compound, magnesium silicate, zinc phosphate, magnesium hydroxide, tin compound, silicone compound, nickel compound, panadium compound, alumina trihydrate, aluminum hydroxide The woven or knitted fabric according to claim 1, which is at least one selected from ferrocene, ferrocene, fumaric acid, maleic acid and reaction products thereof.   The woven or knitted fabric according to claim 1 or 2, wherein 0.1 to 50 mass% of the smoke suppressant is contained in 100 mass% of the woven or knitted fabric.   The woven or knitted fabric according to any one of claims 1 to 3, wherein 10% by mass or more of the non-molten fiber A is contained in 100% by mass of the constituent fibers of the woven or knitted fabric.   The woven or knitted fabric according to any one of claims 1 to 4, wherein the thermoplastic fiber B is contained in an amount of 10 mass% or more in 100 mass% of the constituent fibers of the woven or knitted fabric.   The fiber C other than the non-melting fiber A and the thermoplastic fiber B is contained in 100% by mass of the constituent fibers of the woven or knitted fabric in a range of 60% by mass or less. Woven and knitted fabric.   The woven or knitted fabric according to any one of claims 1 to 6, wherein the non-molten fiber A has a thermal conductivity of 0.060 W / m · K or less.   The woven or knitted fabric according to any one of claims 1 to 7, wherein the non-molten fiber A is at least one selected from flameproof fibers and meta-aramid fibers.   The knitted or knitted fabric according to any one of claims 1 to 8, wherein a glass transition point of the thermoplastic fiber B is 120 ° C or lower.   The thermoplastic fiber B is a flame retardant polyester, anisotropic molten polyester, flame retardant poly (acrylonitrile butadiene styrene), flame retardant polysulfone, poly (ether-ether-ketone), poly (ether-ketone-ketone). A fiber made of a resin selected from the group consisting of polyethersulfone, polyarylate, polyarylene sulfide, polyphenylsulfone, polyetherimide, polyamideimide, phenol, and mixtures thereof. The woven or knitted fabric described.   The woven or knitted fabric according to any one of claims 1 to 10, wherein the thermoplastic fiber B contains a sulfur atom.