JP2014091890A - Cloth for thermoconductive activity protection garment and thermoconductive activity protection garment using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated cloth for thermoconductive activity garments having high thermal insulation property and comfort, and to provide thermoconductive activity garments using the same.SOLUTION: The laminated cloth for thermoconductive activity protection garments includes an outer layer, a thermoconductive layer, and an inner layer, the respective layers are superposed in this order, and the inner layer is located at a skin side. In the laminated cloth for thermoconductive activity protection garments, (i) the outer layer is a cloth composed of fibers with LOI value (a limiting oxygen index) measured by JIS L 1091 E method of 21 or more, (ii) the inner layer is a cloth composed of fibers with the LOI value (the limiting oxygen index) measured by the JIS L 1091 E method of 21 or more, tensile elasticity of 80-800 cN/dtex, thermal conductivity of 6.0 WmKor less, and specific gravity of 3.0 g/cmor less, and (iii) the thermoconductive layer has at least unidirectional thermal conductivity of 100 WmKor more.

Description

  The present invention relates to a heat-resistant and highly heat-resistant laminated fabric for heat-insulating activity protective clothing and a heat-insulating activity protective clothing using the same.

Conventionally, flame-retardant organic fiber fabrics such as aramid, polyphenylene sulfide, polyimide, polybenzimidazole, and the like are used as heat-insulating activity clothes worn by firefighters during fire fighting operations.
In recent years, for the purpose of improving the safety and comfort of firefighters, (a) the outer material is composed of meta-aramid fibers and para-aramid fibers, (b) the intermediate layer has moisture permeability and waterproof properties, (c ) A heat-insulating layer comprising a composite comprising a non-woven fabric of meta-aramid fibers and a woven fabric of meta-aramid fibers, a fabric having a composite structure comprising the above (a) to (c) and excellent in flame retardancy and heat-shielding properties. The protective clothing used (Patent Document 1) has been proposed. For these fabrics, for the purpose of preventing radiant heat generated by a fire, many fabrics made of these flame retardant fibers are subjected to surface treatment by coating or vapor deposition with metal aluminum or the like (for example, (See claims 3 to 4 of Patent Document 1). However, when the coated fabric is used as a protective garment, there is a drawback that its weight becomes very heavy. Furthermore, from the viewpoint of creating an air layer, it is most useful to make a laminated structure for improving heat insulation, but this laminated structure has a feeling of stiffness and suppresses the significant increase in the weight of protective clothing. very difficult.

  In addition, for the purpose of improving the heat shielding property without significantly increasing the weight, and further improving the feeling of wearing without the feeling of stiffness, a heat-resistant laminated structure using napping (Patent Document 2) has been proposed. Although this has a certain effect in terms of improving heat insulation, the accumulation of heat generated from the body also increases, so comfort is impaired, and if the raising level and weight are lowered, the heat insulation is also reduced as it is have.

Japanese Patent Laid-Open No. 2000-21280 JP 2009-263809 A

  An object of the present invention is to provide a laminated fabric for a thermal insulation activity protective clothing having high thermal insulation properties and comfort and a thermal insulation protective clothing using the same.

  By arranging a specific heat conductive layer between the outer layer and the inner layer, the present inventor can suppress heat conducted to the skin side, and can provide a laminated fabric having heat insulation, light weight and comfort. The headline and the present invention were completed.

That is, the present invention is a laminated fabric including an outer layer, a heat conductive layer, and an inner layer, wherein each layer is laminated in this order, and the inner layer is the skin side,
(I) The outer layer is a fabric composed of fibers having a LOI value (limit oxygen index) measured by JIS L 1091 E method of 21 or more,
(Ii) The inner layer has an LOI value (limit oxygen index) measured by JIS L 1091 E method of 21 or more, a tensile elastic modulus of 80 to 800 cN / dtex, a thermal conductivity of 6.0 Wm ⁻¹ · K ⁻¹ or less, A fabric composed of fibers having a specific gravity of 3.0 g / cm ³ or less,
(Iii) The heat conductive layer has a thermal conductivity of at least one direction of 100 Wm ⁻¹ · K ⁻¹ or more.
It is a laminated fabric for heat shielding activity protective clothing.

  The laminated fabric of the present invention is lightweight, has comfort and high heat shielding properties. The laminated fabric of the present invention is useful as work clothes in a high temperature environment such as fire fighting clothes.

Hereinafter, the present invention will be described in detail.
The laminated fabric of the present invention is a laminated fabric comprising an outer layer, a heat conductive layer, and an inner layer, wherein each layer is laminated in this order, and the inner layer is the skin side.

(Outer layer)
The outer layer is a fabric composed of fibers having a LOI value (limit oxygen index) measured by JIS L 1091 E method of 21 or more.
The limiting oxygen index (LOI) is preferably 24 or greater. The critical oxygen index is the oxygen concentration (%) of the atmosphere necessary to continue combustion, and if it is 21 or more, it means that the combustion does not continue in normal air and self-extinguishes, and has high heat resistance. It can be demonstrated. By using a fabric having a limiting oxygen index (LOI) of 21 or more as the outer layer, high heat resistance can be exhibited.
Examples of fibers constituting the outer layer include meta-aramid fibers, para-aramid fibers, polybenzimidazole fibers, polyimide fibers, polyamideimide fibers, polyetherimide fibers, polyarylate fibers, polyparaphenylenebenzobisoxazole fibers, and novoloids. Examples thereof include fiber, polyclar fiber, flame retardant acrylic fiber, flame retardant rayon fiber, flame retardant polyester fiber, flame retardant cotton fiber, and flame retardant wool fiber. In particular, meta-aramid fibers such as polymetaphenylene isophthalamide, para-aramid fibers for the purpose of improving the strength of woven fabrics and knitted fabrics, that is, polyparaphenylene terephthalamide, or fibers obtained by copolymerizing this with a third component Etc. are useful. An example of the polyparaphenylene terephthalamide copolymer is copolyparaphenylene 3.4′-oxydiphenylene terephthalamide represented by the following formula.

(Here, m and n represent positive integers.)
Long fibers or short fibers may be used as the fibers constituting the outer layer. Further, two or more types of fibers may be mixed or spun.

The fabric used for the outer layer may be used in the form of a woven fabric, a knitted fabric, a non-woven fabric, or the like, but a woven fabric is particularly preferable. The woven fabric may be any woven structure such as plain weave, twill weave, and satin weave. Moreover, in the woven fabric and the knitted fabric, two types of fibers may be used, and weaving and knitting may be performed.
As the fabric used for the outer layer, a meta-aramid fiber and a para-aramid fiber are preferably exemplified by being mixed and used in the form of a spun yarn. The mixing ratio of the para-based aramid fibers is preferably 5% by weight or more based on the total fibers constituting the fabric. However, since the para-based aramid fibers are easily fibrillated, the mixing ratio is 60% by weight or less. It is preferable to suppress.

In addition, it is preferable to use what has a fabric weight in the range of 160-400 g / m < ² > for the fabric used for an outer layer (surface material layer). If the basis weight is less than 160 g / m ² , sufficient heat resistance may not be obtained. On the other hand, if the basis weight exceeds 400 g / m ² , the feeling of wearing in a protective suit is hindered. Therefore, it is not preferable.

(Thermal conduction layer)
The laminated fabric of this invention has a heat conductive layer between an outer layer and an inner layer. Thermally conductive layer, at least one direction of the thermal conductivity ^{100Wm -1} · ^K -1 or more, preferably ^{500Wm -1} · ^K -1 or more, more preferably ^{1000Wm -1} · ^K -1 or more. By disposing a heat conductive layer between the outer layer and the inner layer, heat conducted to the skin side can be suppressed, so that the heat shielding performance is improved. If the thermal conductivity is less than 100 Wm ⁻¹ · K ⁻¹ , sufficient movement cannot be achieved and the heat shielding performance is lowered.
The heat conductive layer may be a layer independent of the outer layer or the inner layer, or may be disposed on the surface of the outer layer or the inner layer. Moreover, the heat conductive layer may be distribute | arranged between the outer layer and the intermediate | middle layer mentioned later, or an intermediate | middle layer and an inner layer. The heat conductive layer may be bonded to a plurality of layers of the outer layer, the intermediate layer, and the inner layer.

The heat conduction layer is made by depositing metal on each layer, or coating it by mixing resin, etc. with metal powder or highly heat conductive powder, or depositing metal deposited fiber, metal powder or highly heat conductive powder. A kneaded fiber may be used as a fabric, and the production method and the combination method are not particularly limited.
The thickness of the heat conductive layer is preferably 200 μm or less, and more preferably 100 μm or less. As a result, it may be possible to further suppress the heat conduction in the thickness direction, and at the same time to impair the flexibility of the outer layer and the inner layer. If the thickness exceeds 300 μm, the heat transmitted to the skin side in the thickness direction increases and the heat shielding performance decreases. Moreover, since it lacks flexibility in practical use, the comfort is greatly impaired.

The basis weight of the heat conductive layer is preferably 10 to 500 g / m ² , more preferably 30 to 200 g / m ² . When the basis weight is in this range, it is more reliable to suppress heat conduction in the thickness direction.
The heat conductive layer is preferably a metal or metal oxide foil. It is preferable that a heat conductive layer consists of at least 1 type of metal chosen from copper, gold | metal | money, silver, and aluminum.
Examples of the heat conductive layer include a foil, a woven fabric, a knitted fabric, a nonwoven fabric, a mesh-like material, or a punched punched sheet including at least one form or a composite structure. The heat conductive layer is preferably a mesh. The heat conductive layer is preferably a fabric made of fibers. Moreover, in the heat shielding activity protective clothing, it is possible to partially take such a structure. In particular, in the case of a foil itself or the like that does not have air permeability, partial application is necessary to maintain comfort.

(Inner layer)
The inner layer is a fabric composed of fibers. The fiber constituting the inner layer has a LOI value (limit oxygen index) measured by JIS L 1091 E method of 21 or more, preferably 26 or more, more preferably 30 or more.
The fibers constituting the inner layer have a tensile modulus of 80 to 800 cN / dtex, preferably 120 to 500 cN / dtex, more preferably 150 to 350 cN / dtex. When the tensile elastic modulus is less than 80 cN / dtex, there are not enough fibers depending on the movement and posture of the person who is markedly stretched when specified as a heat-shielding protective clothing. It may not be possible. Further, when the tensile elastic modulus exceeds 800 cN / dtex, there is a case where the stretch at a low tensile force of the fabric is low, and a so-called “stretching” wearing period that impedes the movement of the wearer is given. Although it is possible to avoid this by using spun yarn, depending on conditions, it is necessary that the tensile elastic modulus is 800 cN / dtex or less in order to exhibit a sufficient effect under any yarn or fabric conditions.

The fibers constituting the inner layer have a thermal conductivity of 6.0 Wm ⁻¹ · K ⁻¹ or less, preferably 5.0 × 10 ⁻⁶ m ² · s ⁻¹ or less.
The fibers constituting the inner layer have a specific gravity of 3.0 g / cm ³ or less, preferably 2.0 g / cm ³ or less.
The reason why the fibers constituting the inner layer are required to have a thermal conductivity of 6.0 Wm ⁻¹ · K ⁻¹ or less and a specific gravity of 3.0 g / cm ³ or less is This is because the temperature of the fiber or the fabric itself may increase too much due to excessive accumulation in the fiber or the space near the fiber. Also, there is a risk that the heat stays in a narrow area and the part is burned. It is important that the heat escape without moderate concentration, that is, it is important to absorb heat up to a certain level in the initial stage of heating and accumulate the heat without spreading the heat above that level. is there. Although the specific heat is the capacity of heat per weight. In the case of the present invention, the heat capacity per volume needs to be a certain level or more.

  The fiber constituting the fabric used for the inner layer is not limited to the material and its configuration as long as the above conditions are satisfied. As the fibers constituting the fabric used for the inner layer, organic polymers, carbon fibers, and metal fibers can be used. As an organic polymer, aramid fiber, polybenzimidazole fiber, polyimide fiber, polyamideimide fiber, polyetherimide fiber, polyarylate fiber, polyparaphenylene benzobisoxazole fiber, novoloid fiber, which have been practically used or studied for protective clothing applications. Polycral fiber, flame retardant acrylic fiber, flame retardant rayon fiber, flame retardant polyester fiber, flame retardant cotton fiber, flame retardant wool fiber and the like.

Examples of metal fibers include stainless steel fibers, aluminum fibers, and copper fibers.
As the fibers constituting the fabric used for the inner layer, it is also possible to use fibers in which fine particles having high heat conductivity such as metal or carbon are kneaded or adhered to the surface in order to improve heat conduction. That is, the fiber is mainly composed of carbon fiber or an organic polymer, and may contain one or more fine particles of particles such as carbon black and metal oxide.

(Middle layer)
The laminated fabric of the present invention preferably has an intermediate layer between the outer layer and the inner layer. The intermediate layer is preferably a fabric in which a moisture permeable waterproof film is laminated and fixed to a fabric made of fibers having a LOI value (limit oxygen index) of 25 or more according to JIS L 1091 E method.
Having this intermediate layer increases moisture permeability and waterproofness, and is therefore suitable as a laminated fabric for heat shielding activity clothing used for fire fighting activities. The critical oxygen index of the fibers constituting the intermediate layer is preferably 21 or more, more preferably 26 or more. Examples of the moisture permeable and waterproof film include a microporous polytetrafluoroethylene film, a microporous polyolefin film, and a polyurethane film. The thickness of the moisture permeable waterproof film is preferably 200 micrometers or less, more preferably 100 micrometers or less. As a method of laminating and fixing the moisture-permeable and waterproof film to the fabric, any known method such as dot bonding can be adopted as long as the necessary moisture-permeable effect is secured.
When the laminated fabric has an intermediate layer, the heat conductive layer can be disposed between the outer layer and the intermediate layer, or between the intermediate layer and the inner layer. A heat conductive layer can be disposed on at least one surface of the intermediate layer.

(Lining layer)
Since the laminated fabric of the present invention is used for heat shielding activity protective clothing, it may have a lining layer on the skin side of the inner layer. The lining layer can improve heat insulation performance and comfort performance.
The fabric weight used for the backing layer is preferably 20 to 200 g / m ² , more preferably 40 to 140 g / m ² .
For the backing layer, a woven fabric, a nonwoven fabric, a knitted fabric or the like made of a flame retardant fiber such as a meta-type aramid fiber, a para-type aramid fiber, a polybenzimidazole fiber, and a polyimide fiber is used.

(Manufacture of laminated fabric)
The laminated fabric of the present invention includes, for example, an outer layer fabric, a heat conductive layer, an inner layer fabric, an intermediate layer fabric interposed therebetween as necessary, and a fabric that forms a backing layer further inside the inner layer as necessary. In addition, these fabrics can be manufactured by overlapping and sewing by a known method. In addition, the laminated fabric of the present invention allows the outer layer, the heat conductive layer, and the inner layer to overlap, attach a fastener, sew these fabrics, and remove the fasteners so that the fabrics can be separated as necessary. May be.

(Heat shield activity protective clothing)
The present invention includes a heat-shielding action protective garment using the above-mentioned laminated fabric. The heat shielding activity protective clothing can be manufactured by sewing the above-mentioned laminated fabric by a known method. At this time, the outer layer fabric, the heat conductive layer, and the inner layer fabric need not be joined to each other, and may be overlapped and stitched. Further, as described above, the inner layer fabric may be configured to be removable from the outer layer fabric using a fastener or the like.

  Hereinafter, the present invention will be described in more detail with reference to examples.

1. Each physical property in the examples was measured by the following methods.
(1) Basis weight It measured by the method based on JISL1096.
(2) Limiting oxygen index (LOI)
It measured by the method based on JIS L 1091 (E method).
(3) Thermal conductivity of fiber and sheet-like material Using thermal diffusivity measuring apparatus (manufactured by ULVAC-RIKO Co., Ltd., Model: LaserPIT), in the case of an object or fiber by the optical alternating current method, the longitudinal direction (fiber axis Direction) thermal diffusivity (α). The test piece is a bundle of single fibers, and is measured by measuring under the conditions of irradiation light, semiconductor laser, temperature sensor E thermocouple (wire diameter 100 μm, silver paste adhesion), and 25 ° C. in a vacuum atmosphere. The diffusivity was measured.
Next, the thermal conductivity (κ) is calculated from the specific heat capacity (C _p ) measured by the JIS K 7123 method and the density (ρ) measured by the density gradient tube method (N-heptane / carbon tetrachloride, 25 ° C.). Calculated by the formula.
κ = αρC _p
(4) Specific gravity It measured by the method based on JISK7112 (The measurement method of the density and specific gravity of a plastic-non-foamed plastic).
(5) Tensile modulus Measured by a method based on JIS L 1013 (chemical fiber filament yarn test method) 8.10.
(6) Thermal insulation test By the method based on ISO9151, it exposed to the flame of regulation, and time (HTI24) until a temperature rise reaches 24 degreeC was measured. The longer this time, the better the protection performance.

2. Each material was prepared by the following method and procedure.
(1) Outer layer, fabric A to fabric G
Polymetaphenylene isophthalamide fiber (manufactured by Teijin, trade name “Conex”, average single fiber fineness 2.2 dtex, tensile elastic modulus 83 cN / dtex, fiber length 51 mm) and copolyparaphenylene 3,4′-oxydiphenylene terephthalate Made of heat-resistant fiber mixed with amide fiber (made by Teijin, trade name “Technola”, average single fiber fineness 1.5 dtex, tensile elastic modulus 520 cN / dtex, fiber length 51 mm) at a mixing weight ratio of 90:10 A woven fabric woven into a plain weave ripstop using 40 spun spun yarn was prepared by a known method and scoured to remove the glue and oil on the fabric surface. This fabric was used as an outer layer. The fabric A has a basis weight of 300 g / m ² . Fabrics B to G were prepared in the same manner. The difference from the fabric A creation is that the weave density is changed so that the basis weight is different. The basis weight adjustment was performed by adjusting the density according to the number of driving. Table 1 shows the basis weight of the fabrics B to G.
(2) Intermediate layer / woven fabric H
Polymetaphenylene isophthalamide fiber (manufactured by Teijin, trade name “Conex”, average single fiber fineness 2.2 dtex, tensile elastic modulus 83 cN / dtex, fiber length 51 mm) and copolyparaphenylene-3,4′-oxydiphenylene From heat-resistant fiber mixed with terephthalamide fiber (manufactured by Teijin, trade name “Technola”, average single fiber fineness 1.7 dtex, tensile elastic modulus 520 cN / dtex, fiber length 51 mm) at a mixing weight ratio of 90:10 A woven fabric (weighing 45 g / m ² , LOI value 25) woven with 40th spun yarn was laminated with a moisture-permeable and waterproof film made of polytetrafluoroethylene (manufactured by Japan Gore-Tex, weight per unit 35 g / m ² ). I used something.
(3) Thermal Conductive Layer An aluminum foil (thermal conductive layer) was a base foil made of Sumilight aluminum foil. A JTC foil, which is an electrolytic copper foil made of JX Nippon Mining & Metals, was used as the copper foil (heat conductive layer). Nichirei magnet steel paper was used for the steel foil (heat conducting layer). Austenitic SUS304 made by Nisshin Steel was used for the stainless steel foil.

  In Example 5, aluminum was vapor-deposited inside the outer layer fabric (woven fabric A) (* 1 in the table). In Example 6, aluminum was vapor-deposited on the outer side of the inner layer fabric (fabric 1) (* 2 in the table).

(4) Inner layer / fabric 1, 2
Polyraphenylene terephthalamide fiber yarn (manufactured by Teijin Twaron, trade name “Twaron”, total fineness 1670 dtex, tensile elastic modulus 500 cN / dtex) is used as a raw yarn for both warp and width, and a basis weight of 220 g / m ² And 240 g / m ² twill fabric. The basis weight adjustment was performed by adjusting the density according to the number of driving.
・ Fabrics 3, 4, 5
Polyraphenylene terephthalamide fiber yarn (manufactured by Teijin Twaron, trade name “Twaron”, total fineness 440 dtex, tensile elastic modulus 500 cN / dtex) is used as a raw yarn for both warp and width, using a rapier loom, with a basis weight of 80 g / m ² 50 g / m ² and 160 g / m ² twill fabrics were made. The basis weight adjustment was performed by adjusting the density according to the number of driving.
・ Fabric 6
Using a rapier loom using a carbon fiber yarn (produced by Toho Tenax, trade name “Tenax”, total fineness 670 dtex, tensile elastic modulus 1240 cN / dtex) as the raw yarn, and using a rapier loom, a twill weave of 220 g / m ² Created. The basis weight adjustment was performed by adjusting the density according to the number of driving.
(5) Lining layer / textile I
Copolyparaphenylene-3,4'-oxydiphenylene terephthalamide fiber yarn (manufactured by Teijin, trade name “Technola”, average single fiber fineness 0.83 dtex, total fineness 830 dtex, tensile elastic modulus 520 cN / dtex) Both were used as raw yarns to produce plain fabrics with a basis weight of 60 g / m ² . The basis weight adjustment was performed by adjusting the density according to the number of driving.

Examples 1-9, Comparative Examples 1-6
Each fabric of the outer layer, intermediate layer, heat conductive layer, inner layer, and backing layer (additional backing) shown in Table 1 was layered to obtain a laminated fabric. The evaluation results of the obtained laminated fabric are shown in Table 1.

  The laminated fabric of the present invention has light weight, comfort and high heat shielding properties, and by using the laminated fabric, it is useful for use in protective clothing, which is useful as work clothing in high-temperature environments such as fire fighting clothing. .

Claims (14)

A laminated fabric comprising an outer layer, a heat conductive layer and an inner layer, wherein each layer is laminated in this order, and the inner layer is the skin side,
(I) The outer layer is a fabric composed of fibers having a LOI value (limit oxygen index) measured by JIS L 1091 E method of 21 or more,
(Ii) The inner layer has an LOI value (limit oxygen index) measured by JIS L 1091 E method of 21 or more, a tensile elastic modulus of 80 to 800 cN / dtex, a thermal conductivity of 6.0 Wm ⁻¹ · K ⁻¹ or less, A fabric composed of fibers having a specific gravity of 3.0 g / cm ³ or less,
(Iii) The heat conductive layer has a thermal conductivity of at least one direction of 100 Wm ⁻¹ · K ⁻¹ or more.
Laminated fabric for heat shield activity protective clothing.   The laminated fabric according to claim 1, wherein the heat conductive layer is disposed on a surface of the outer layer or the inner layer.   The laminated fabric according to claim 1 or 2, wherein the heat conductive layer has a thickness of 200 µm or less. Laminated fabric according to any one of claims 1 to 3 weight per unit area of the heat conducting layer is 10 to 500 g / ^{m 2.}   The laminated fabric according to any one of claims 1 to 4, wherein the heat conductive layer is a mesh-like material.   The laminated fabric according to any one of claims 1 to 5, wherein the heat conductive layer is a fabric made of fibers.   The laminated fabric according to any one of claims 1 to 6, wherein the heat conductive layer is a metal or metal oxide foil.   The laminated fabric according to any one of claims 1 to 7, wherein the heat conductive layer is made of at least one metal selected from copper, gold, silver and aluminum.   A cloth having an intermediate layer between an outer layer and an inner layer, the intermediate layer being laminated and fixed with a moisture permeable waterproof film on a cloth made of fibers having a LOI value (limit oxygen index) of 25 or more according to JIS L 1091 E method. The laminated fabric according to claim 1.   The laminated fabric according to claim 9, wherein the heat conductive layer is disposed between the outer layer and the intermediate layer, or between the intermediate layer and the inner layer.   The laminated fabric according to claim 9, wherein a heat conductive layer is disposed on at least one surface of the intermediate layer.   The laminated fabric according to any one of claims 1 to 11, wherein the fibers constituting the inner layer fabric are made of organic polymer or carbon fiber.   The laminated fabric according to any one of claims 1 to 12, which has a backing layer on the skin side of the inner layer.   Thermal barrier activity protective clothing using the laminated fabric according to any one of claims 1 to 13.