JP2013133567A - Meta-type wholly aromatic polyamide laminated protective garment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored meta-type wholly aromatic polyamide laminated protective garment having little color deterioration under exposure to light.SOLUTION: A fabric is formed by using spun-dyed meta-type wholly aromatic polyamide fibers having a constant value or less of solvent content remaining in the fibers. The fabric is used as the outermost layer of the laminated protective garment. Specifically, the laminated protective garment is made using the fabric using the spun-dyed meta-type wholly aromatic polyamide fibers where the residual amount of solvent in the fibers is ≤0.1 mass% as the outermost layer.

Description

  The present invention relates to a protective garment comprising a laminated fabric. More specifically, the present invention relates to a meta-type wholly aromatic polyamide laminated protective garment that uses, as an outermost layer, a cloth containing an original meta-type wholly aromatic polyamide fiber that has a small color change due to exposure.

  Meta-type wholly aromatic polyamide fibers such as polymetaphenylene terephthalamide fiber exhibit excellent heat resistance and dimensional stability because most of the molecular skeleton is composed of aromatic rings. Taking advantage of these characteristics, meta-type wholly aromatic polyamide fibers are used as fibers constituting heat-resistant protective clothing worn by firefighters during fire fighting (see Patent Document 1).

In such use in the clothing field, it is common to use colored fibers. As methods for obtaining colored fibers, there are known post-dyeing methods in which fibers are dyed and dyed with a dye, or original methods in which pigments are added to a spinning dope to make fibers.
However, a colored meta-type wholly aromatic polyamide fiber has a defect that it causes discoloration or discoloration by light irradiation, and depending on the degree of discoloration, it may not be usable as protective clothing.

  Therefore, as a post-dyeing method for dyeing with a dye, a method for suppressing the fading of the dyed meta-type wholly aromatic polyamide fiber by adding a hindered amine light-proofing agent has been proposed (see Patent Document 2). . However, in the method described in Patent Document 2, decomposition of the dye progresses with respect to light irradiation for a long time, and long-term resistance to discoloration has not yet been satisfactory.

  On the other hand, in the original deposition method in which a pigment is added to the spinning dope and fiberized, a yellowish photo-fading colorant is kneaded into the wholly aromatic polyamide that browns when irradiated with light to prolong the time until discoloration. And a method of suppressing the apparent discoloration by making the color lighter (see Patent Document 3). However, in the method described in Patent Document 3, the effect is small in hues other than yellow, and has not been a fundamental solution.

Japanese Patent Laid-Open No. 2006-016709 JP 2003-239136 A JP-A-2-229281

  The present invention has been made in view of the background art described above, and an object of the present invention is to provide a colored meta-type wholly aromatic polyamide laminated protective clothing having a small discoloration under exposure.

  The inventors of the present invention have made extensive studies in order to solve the above problems. As a result, if a fabric is formed using an original meta-type wholly aromatic polyamide fiber having a solvent content remaining in the fiber of a certain value or less, and the fabric is used as the outermost layer of the laminated protective garment, the change due to exposure will occur. The present inventors have found that a meta-type wholly aromatic polyamide laminated protective clothing having a small amber color can be obtained, and have completed the present invention. Specifically, a laminated protective garment is created using a cloth using an original meta-type wholly aromatic polyamide fiber having a residual solvent amount of 0.1% by mass or less in the fiber as an outermost layer.

  That is, the present invention is a protective garment comprising a laminated fabric, wherein the protective garment includes a fabric containing a meta-type wholly aromatic polyamide fiber as an outermost layer, and the meta-type wholly aromatic polyamide fiber is a residual material. This is a meta-type wholly aromatic polyamide laminated protective clothing which is an original meta-type wholly aromatic polyamide fiber having a solvent amount of 0.1% by mass or less with respect to the entire fiber mass.

The meta-type wholly aromatic polyamide laminated protective garment of the present invention is a protective garment having a small discoloration due to exposure. Therefore, in addition to the properties inherent to meta-type wholly aromatic polyamide fibers such as flame retardancy and heat resistance, it is possible to realize protective clothing in which the discoloration of the product is suppressed even when used for a long time under exposure.
Moreover, the original meta type wholly aromatic polyamide fiber used in the laminated protective garment of the present invention has low shrinkage at high temperatures and excellent thermal dimensional stability. For this reason, stable use can be continued even in applications where flame exposure, radiant heat, or the like exists.

  Therefore, the meta-type wholly aromatic polyamide laminated protective garment according to the present invention exhibits excellent resistance to discoloration in a long-time exposure and also exhibits excellent dimensional stability at high temperatures. The industrial value in this field is extremely large, and it can be suitably used as a heat-resistant protective clothing worn by firefighters during fire fighting operations.

<Original meta-type wholly aromatic polyamide fiber>
The original meta type wholly aromatic polyamide fibers constituting the outermost layer of the laminated protective clothing of the present invention have the following specific physical properties. The physical properties, configuration, production method, and the like of the original meta-type wholly aromatic polyamide fiber used in the present invention will be described below.

[Physical properties of original meta-type wholly aromatic polyamide fiber]
[Residual solvent amount]
Since the original meta-type wholly aromatic polyamide fiber is usually produced from a spinning stock solution in which a polymer is dissolved in an amide solvent and a pigment is kneaded, the solvent necessarily remains in the fiber. However, in the original meta-type wholly aromatic polyamide fiber of the present invention, the amount of the solvent remaining in the fiber is 0.1% by mass or less with respect to the mass of the fiber. It is essential that the content is 0.1% by mass or less, and more preferably 0.08% by mass or less.

When the solvent remains in the fiber in excess of 0.1% by mass with respect to the fiber mass, the residual solvent volatilizes during processing and use in a high temperature atmosphere exceeding 200 ° C. Inferior to environmental safety. In addition, when used under exposure, it causes discoloration of the fabric.
In order to reduce the amount of residual solvent in the fiber to 0.1% by mass or less, in the fiber manufacturing process, the components or conditions of the coagulation bath are adjusted so that the coagulation form does not have a skin core, and plasticization is performed at a specific magnification. Stretching is performed, and specific heat treatment is performed.

In the present invention, the “residual solvent amount in the fiber” refers to a value obtained by the following method.
(Measurement method of residual solvent amount)
About 8.0 g of fiber is collected, dried at 105 ° C. for 120 minutes, allowed to cool in a desiccator, and the fiber mass (M1) is weighed. Subsequently, this fiber is subjected to reflux extraction using a Soxhlet extractor in methanol for 1.5 hours to extract an amide solvent contained in the fiber. The fiber after extraction is taken out, vacuum-dried at 150 ° C. for 60 minutes, allowed to cool in a desiccator, and the fiber mass (M2) is weighed. The amount of solvent (amide solvent mass) N (%) remaining in the fiber is calculated by the following formula using M1 and M2 obtained.
N (%) = [(M1-M2) / M1] × 100

[Maximum heat shrinkage]
The original meta-type wholly aromatic polyamide fiber used in the present invention preferably has a maximum heat shrinkage of 7.5% or less at a temperature rising rate of 100 ° C./min and a temperature range of 25 to 500 ° C. More preferably, it is 0% or less. If the maximum heat shrinkage rate exceeds 7.5%, the product dimensions change when used in a high-temperature atmosphere, and problems such as product breakage occur.

The “maximum heat shrinkage rate” in the present invention refers to a value obtained by the following method.
(Maximum heat shrinkage measurement method)
As a measuring device, a thermomechanical analyzer EXSTAR6000 made by SII is used, a fiber sample is divided into 480 dtex, and this is sandwiched between chucks and used as a measurement sample. The shrinkage rate with respect to the initial length of the sample fiber at each temperature is measured under the following conditions, and the shrinkage rate at the temperature at which the shrinkage rate is maximum among the obtained shrinkage rate results at each temperature is defined as the maximum heat shrinkage rate.
<Measurement conditions>
Measurement sample length: 10 mm
Temperature increase rate: 100 ° C./min
Measurement temperature range: 25-500 ° C
Load applied to fiber sample: 1.2 cN

[Brightness index L *]
The brightness index L * of the original meta-type wholly aromatic polyamide fiber used in the present invention is not particularly limited, and can take all the hues that can be colored by the original application. However, in the present invention, the effect is remarkable in the dark-colored original meta-type wholly aromatic polyamide fiber. Accordingly, the lightness index L * value of the fiber is preferably 40 or less.

[Light-changing chromaticity with a xenon arc fade meter (color difference: ΔE *)]
When the lightness index L * value is 40 or less, the original meta-type wholly aromatic polyamide fiber used in the present invention has a color difference before and after irradiation for 80 hours at 1.1 W / m ² with a xenon arc fade meter, that is, a light change. The fading degree (ΔE *) is 24.0 or less. It is preferably 23.0 or less, and more preferably 22.0 or less. When the light discoloration chromaticity (color difference: ΔE *) exceeds 24.0, the discoloration of the fiber due to light irradiation is remarkable, which is not preferable.

In addition, “light-changing chromaticity (color difference: ΔE *) by a xenon arc fade meter” refers to a value obtained by the following method.
(How to calculate light chromaticity (color difference: ΔE *) with a xenon arc fade meter)
The photochromic chromaticity (color difference: ΔE *) by a xenon arc fade meter is determined using unirradiated cotton and light irradiated cotton irradiated with 1.1 W / m ² for a certain time with a xenon arc fade meter. First, the diffuse reflectance in a -10 degree visual field is measured using the light source D65, and the lightness index L * value, the chromaticness index a *, and the b * value are calculated by a normal calculation process. The measurement light irradiation area is 30 mmΦ. The light discoloration chromaticity (color difference: ΔE *) is obtained from the following equation using the obtained value in accordance with JIS Z-8730. The photochromic chromaticity (color difference: ΔE *) by the xenon arc fade meter in the present invention was specified at an irradiation time of 80 hours.
[Formula 1]
ΔE * = ((ΔL *) ² + (Δa *) ² + (Δb *) ² ) ^1/2

[Light-changing chromaticity with a carbon arc fade meter (color difference: ΔE *)]
When the lightness index L * value is 40 or less, the original meta-type wholly aromatic polyamide fiber used in the present invention has a color difference before and after irradiation for 72 hours at 135 V / 17 A with a carbon arc fade meter, that is, a photochromic chromaticity ( ΔE *) is 3.5 or less. It is preferably 3.3 or less, and more preferably 3.1 or less. When the light discoloration chromaticity (color difference: ΔE *) by the carbon arc fade meter exceeds 3.5, the discoloration of the fiber due to light irradiation is remarkable.

In addition, “light-changing chromaticity (color difference: ΔE *) by a carbon arc fade meter” refers to a value obtained by the following method.
(How to determine the light change chromaticity (color difference: ΔE *) with a carbon arc fade meter)
The light-changing chromaticity (color difference: ΔE *) measured by the carbon arc fade meter was measured using the above-mentioned xenon arc fade meter using unirradiated cotton and light-irradiated cotton irradiated at 135V / 17A for a certain time with a carbon arc fade meter. It is obtained in the same manner as the photochromic chromaticity (color difference: ΔE *). That is, first, the diffuse reflectance in the -10 degree visual field was measured using the light source D65, and the lightness index L * value, chromaticness index a *, and b * value were calculated by a normal calculation process. Using the value, it is determined by the above formula in accordance with JIS Z-8730. At this time, the measurement light irradiation area is 10 mmΦ. In addition, the light change chromaticity (color difference: ΔE *) by the carbon arc fade meter in the present invention was specified at an irradiation time of 72 hours.

[Ratio of light-changing chromaticity (color difference: ΔE *) with high residual solvent-borne fiber]
The original meta-type wholly aromatic polyamide fiber used in the present invention has a photochromic chromaticity (color difference: ΔE *) before and after irradiation for 72 hours at 135V / 17A with a carbon arc fade meter, and the amount of residual solvent in the fiber is It is 75% or less based on the photochromic chromaticity (color difference: ΔE *) of the original meta-type wholly aromatic polyamide fiber to which the same amount of the same pigment of 0.4% by mass or more is added. It is preferably 72% or less, and more preferably 70% or less. When the ratio of the photochromicity (color difference: ΔE *) with the same-colored original fiber having a residual solvent amount of 0.4% by mass or more exceeds 75%, the color of the fiber due to light irradiation is markedly altered. Therefore, it is not preferable.
In addition, “light change chromaticity (color difference: ΔE *) by carbon arc fade meter” for confirming the ratio of light change chromaticity (color difference: ΔE *) with the high residual solvent amount original fiber is irradiation time. 72 hours is a value obtained by carrying out the same method as described above.

[Configuration of meta-type wholly aromatic polyamide]
The meta-type wholly aromatic polyamide constituting the original meta-type wholly aromatic polyamide fiber used in the present invention is composed of a meta-type aromatic diamine component and a meta-type aromatic dicarboxylic acid component. Other copolymer components such as para type may be copolymerized within the range not impairing the purpose.

Particularly preferred as a raw material for the original meta-type wholly aromatic polyamide fiber used in the present invention is a meta-type mainly composed of a metaphenylene isophthalamide unit from the viewpoint of mechanical properties, heat resistance and flame retardancy. It is a wholly aromatic polyamide.
As the meta-type wholly aromatic polyamide composed of metaphenylene isophthalamide units, the metaphenylene isophthalamide units are preferably 90 mol% or more of the total repeating units, more preferably 95 mol% or more, particularly preferably. 100 mol%.

[Raw material for meta-type wholly aromatic polyamide]
(Meta-type aromatic diamine component)
Examples of the meta-type aromatic diamine component used as a raw material for the meta-type wholly aromatic polyamide include metaphenylene diamine, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, and the like, halogens in these aromatic rings, Examples of derivatives having a substituent such as an alkyl group having 1 to 3 carbon atoms, such as 2,4-toluylenediamine, 2,6-toluylenediamine, 2,4-diaminochlorobenzene, 2,6-diaminochlorobenzene, etc. can do. Of these, metaphenylenediamine alone or a mixed diamine containing metaphenylenediamine in an amount of 85 mol% or more, preferably 90 mol% or more, particularly preferably 95 mol% or more is preferable.

(Meta-type aromatic dicarboxylic acid component)
Examples of the raw material of the meta type aromatic dicarboxylic acid component constituting the meta type wholly aromatic polyamide include a meta type aromatic dicarboxylic acid halide. Examples of the meta-type aromatic dicarboxylic acid halide include isophthalic acid halides such as isophthalic acid chloride and isophthalic acid bromide, and derivatives having substituents such as halogen and alkoxy groups having 1 to 3 carbon atoms on the aromatic ring, such as 3 -Chloroisophthalic acid chloride etc. can be illustrated. Of these, isophthalic acid chloride itself or a mixed carboxylic acid halide containing isophthalic acid chloride in an amount of 85 mol% or more, preferably 90 mol% or more, particularly preferably 95 mol% or more is preferable.

[Method for producing meta-type wholly aromatic polyamide]
The production method of the meta-type wholly aromatic polyamide constituting the original meta-type wholly aromatic polyamide fiber used in the present invention is not particularly limited. For example, the meta-type aromatic diamine component and the meta-type aromatic dicarboxylic acid are used. It can be produced by solution polymerization or interfacial polymerization using an acid chloride component as a raw material.
The molecular weight of the meta-type wholly aromatic polyamide is not particularly limited as long as it can form fibers. In general, in order to obtain a fiber having sufficient physical properties, a polymer having an intrinsic viscosity (IV) measured in a concentrated sulfuric acid at 30 ° C. with a polymer concentration of 100 mg / 100 mL sulfuric acid is in a range of 1.0 to 3.0. Appropriate polymers in the range of 1.2 to 2.0 are particularly preferred.

<Method for Producing Original Meta-type Fully Aromatic Polyamide Fiber>
The original meta-type wholly aromatic polyamide fiber used in the present invention is prepared using the meta-type wholly aromatic polyamide obtained by the above production method, for example, a spinning solution preparation process, a spinning / coagulation process described below, It can be manufactured through a plastic stretching bath stretching step, a washing step, a relaxation treatment step, and a heat treatment step.

[Spinning liquid preparation process]
In the spinning solution preparation step, the meta-type wholly aromatic polyamide is dissolved in an amide solvent and a pigment is added to prepare a spinning solution (original meta-type wholly aromatic polyamide polymer solution). In preparing the spinning solution, an amide solvent is usually used, and examples of the amide solvent used include N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and dimethylacetamide (DMAc). be able to. Of these, NMP or DMAc is preferably used from the viewpoints of solubility and handling safety.
The solution concentration may be appropriately selected from the viewpoint of coagulation rate and polymer solubility in the next spinning and coagulation step. For example, the polymer is polymetaphenylene isophthalamide and the solvent is DMAc. In the case of, it is usually preferred to be in the range of 10 to 30% by mass.

(Pigment)
Examples of the pigment used in the present invention include organic pigments such as azo, phthalocyanine, perinone, perylene, and anthraquinone, and inorganic pigments such as carbon black, ultramarine, bengara, titanium oxide, and iron oxide. However, it is not limited to these.
The mixing method of the meta type wholly aromatic polyamide and the pigment is to prepare an amide solvent slurry in which the pigment is uniformly dispersed in the amide solvent, and the meta type wholly aromatic polyamide is dissolved in the amide solvent. The method of adding to the solution, or the method of adding the pigment powder directly to the solution in which the meta-type wholly aromatic polyamide is dissolved in the amide solvent, is not particularly limited. The spinning solution thus obtained (original meta-type wholly aromatic polyamide polymer solution) is formed into a fiber through the following steps, for example.

(Pigment amount)
As a pigment compounding quantity, it is 10.0 mass% or less with respect to meta type wholly aromatic polyamide, Preferably it is 5.0 mass% or less. If added in an amount of more than 10.0% by mass, the physical properties of the resulting fiber will be unfavorable.

[Spinning and coagulation process]
In the spinning / coagulation step, the spinning solution obtained above (original meta-type wholly aromatic polyamide polymer solution) is spun into a coagulation solution and coagulated.
The spinning device is not particularly limited, and a conventionally known wet spinning device can be used. Moreover, the number of spinning holes, the arrangement state, the hole shape and the like of the spinneret are not particularly limited as long as they can be stably wet-spun. For example, the number of holes is 500 to 30,000, and the spinning hole diameter is 0.05. A multi-hole spinneret for ˜0.2 mm sufu may be used.
Further, the temperature of the spinning solution (original meta-type wholly aromatic polyamide polymer solution) when spinning from the spinneret is suitably in the range of 10 to 90 ° C.

  As a coagulation bath used to obtain the fiber used in the present invention, an aqueous solution containing an amide solvent concentration of 45 to 60% by mass not containing an inorganic salt is used in a temperature range of 10 to 35 ° C. of the bath solution. If the amide solvent concentration is less than 45% by mass, the skin has a thick structure, the cleaning efficiency in the cleaning process is lowered, and it is difficult to make the residual solvent amount of the obtained fiber 0.1% by mass or less. In addition, when the amide solvent concentration exceeds 60% by mass, uniform solidification cannot be performed until reaching the inside of the fiber, and therefore, the residual solvent amount of the fibrils may be 0.1% by mass or less. It becomes difficult. In addition, the range of 0.1-30 seconds is suitable for the immersion time of the fiber in a coagulation bath.

[Plastic stretching bath stretching process]
In the plastic drawing bath drawing step, the fiber is drawn in the plastic drawing bath while the fiber obtained by coagulation in the coagulation bath is in a plastic state.
It does not specifically limit as a plastic drawing bath liquid, A conventionally well-known bath liquid can be employ | adopted.

  In order to obtain the fiber used in the present invention, the draw ratio in the plastic drawing bath needs to be in the range of 3.5 to 5.0 times, more preferably in the range of 3.7 to 4.5 times. And In the production of the fiber used in the present invention, the solvent removal from the coagulated yarn can be promoted by plastic drawing in a plastic drawing bath within a specific magnification range. It can be 1 mass% or less.

When the draw ratio in the plastic drawing bath is less than 3.5 times, the solvent removal from the coagulated yarn becomes insufficient, and it is difficult to reduce the residual solvent amount of the fibrils to 0.1% by mass or less. It becomes. Further, the breaking strength becomes insufficient, and handling in a processing process such as a spinning process becomes difficult. On the other hand, when the draw ratio exceeds 5.0 times, single yarn breakage occurs, resulting in poor process stability.
The temperature of the plastic stretching bath is preferably in the range of 10 to 90 ° C. Preferably process stability is good in the range of 20-90 degreeC of temperature.

[Washing process]
In the washing step, the fiber drawn in the plastic drawing bath is thoroughly washed. Washing is preferably performed in multiple stages because it affects the quality of the resulting fiber. In particular, the temperature of the cleaning bath in the cleaning step and the concentration of the amide solvent in the cleaning bath liquid affect the state of extraction of the amide solvent from the fibers and the state of penetration of water from the cleaning bath into the fibers. For this reason, it is preferable to control the temperature condition and the concentration condition of the amide solvent by setting the washing process in multiple stages for the purpose of bringing them into an optimum state.

The temperature condition and the amide solvent concentration condition are not particularly limited as long as the quality of the finally obtained fiber can be satisfied. However, if the initial cleaning bath is set to a high temperature of 60 ° C. or higher, water enters the fiber at a stretch, and a huge void is generated in the fiber, resulting in deterioration of quality. For this reason, it is preferable that the first washing bath has a low temperature of 30 ° C. or lower.
When the solvent remains in the fiber, environmental safety in processing of the product using the fiber and use of the product formed using the fiber is not preferable. For this reason, the amount of solvent contained in the fiber used in the present invention is 0.1% by mass or less, more preferably 0.08% by mass or less.

[Dry heat treatment process]
In the dry heat treatment step, the fiber that has undergone the washing step is dried and heat treated. Although it does not specifically limit as a method of dry heat processing, For example, the method of using a hot roller, a hot plate, etc. can be mentioned. By undergoing the dry heat treatment, the original meta-type wholly aromatic polyamide fiber used in the present invention can be finally obtained.

  In order to obtain the fiber used for this invention, it is necessary to make the heat processing temperature in a dry heat treatment process into the range of 260-350 degreeC, and it is more preferable to set it as the range of 270-340 degreeC. When the heat treatment temperature is less than 260 ° C., the fiber is insufficiently crystallized and the shrinkage of the fiber is increased. On the other hand, when it exceeds 350 ° C., the crystallization of the fiber becomes too large, and the elongation at break is significantly reduced. Moreover, making dry-heat-treatment temperature into the range of 260-350 degreeC contributes to the improvement of the breaking strength of the fiber obtained.

[Crimping process, etc.]
The original meta-type wholly aromatic polyamide fiber subjected to the dry heat treatment may be further crimped as necessary. Further, after the crimping process, it may be cut into an appropriate fiber length and provided to the next step. In some cases, it may be wound up as a multifilament yarn.

<Cloth including original meta type wholly aromatic polyamide fiber>
The fabric containing the original meta-type wholly aromatic polyamide fiber which is the outermost layer of the laminated protective clothing of the present invention contains the above-mentioned original meta-type wholly aromatic polyamide fiber as a main component. The content of the meta-type wholly aromatic polyamide fiber in the fabric is 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100%.

In addition, in the cloth containing the original meta-type wholly aromatic polyamide fiber, the component contained in addition to the original meta-type wholly aromatic polyamide fiber is not particularly limited. For example, fibrous and pulp-like components can be mentioned. Examples of fibers include polybenzimidazole fiber, polyimide fiber, polyamideimide fiber, polyetherimide fiber, polyarylate fiber, polyparaphenylenebenzobisoxazole fiber, novoloid fiber, flame retardant acrylic fiber, polyclar fiber, and flame retardant polyester fiber. Examples include flame retardant cotton fiber, flame retardant wool fiber, para-type wholly aromatic polyamide fiber, and the like. Among these, it is particularly preferable to mix para-type wholly aromatic polyamide fibers from the viewpoint of fiber strength and heat resistance.
The mixed form of the fibers is not particularly limited, but it is preferable to use a mixed spun yarn form. After forming the spun yarn form, the spun yarn can be used to form a fabric.

[Fabric form]
The form of the cloth containing the original meta-type wholly aromatic polyamide fiber that is the outermost layer of the laminated protective clothing of the present invention is not particularly limited. In this invention, any form, such as a woven fabric, a knitted fabric, and a nonwoven fabric, may be sufficient.
The fabric weight is preferably in the range of 150 to 350 g / m ² . If the basis weight is less than 150 g / m ² , sufficient heat resistance may not be obtained, and if the basis weight exceeds 350 g / m ² , the feeling of wearing will be hindered because it becomes heavy when used as protective clothing. It is not preferable.

<Laminated protective clothing>
The layered protective garment of the present invention includes a fabric including the above-described original meta-type wholly aromatic polyamide fiber as an outermost layer. If the fabric containing the above-mentioned original meta-type wholly aromatic polyamide fiber is used as the outermost layer, the configuration of the laminated protective clothing is not particularly limited, but preferably, the surface layer and the inner layer are arranged in this order. It is preferable that the layers have a structure in which the layers are overlapped, and any of these layers has a configuration in which a fiber fabric mainly composed of wholly aromatic polyamide fibers is used. Since the original meta type wholly aromatic polyamide fiber fabric used as the outermost layer suppresses discoloration due to exposure, it is preferably used as a surface layer of a laminated protective clothing.

  The layered protective clothing of the present invention preferably has a composite structure composed of a surface layer and an inner layer, but the layers do not have to be joined to each other, Good. Further, the inner layer can be configured to be removable from the surface layer using a fastener or the like, and can be structured to be easily washed.

(Processing of surface layer)
Preferably, the surface layer of the layered protective garment (the front side surface of the layered protective garment) using the original meta-type wholly aromatic polyamide fiber fabric is subjected to water repellency treatment to increase the water resistance. The water-repellent treatment may be performed on both surfaces of the surface layer, but it is more preferable that the water-repellent processing is performed on at least the surface side of the protective clothing surface.
The water-repellent processing can be performed by a processing method such as a coating method, a spray method, or an immersion method using a fluorine-based water-repellent resin according to a known method. In the protective clothing using the water-resistant fabric subjected to such water-repellent processing, water can be prevented from entering the gap during the fire extinguishing work, and the wearing performance of the protective clothing is improved. be able to.

(Inner layer)
The inner layer of the laminated protective garment is preferably a fabric having moisture permeability and waterproofness. For example, the composite_body | complex which bonded together the woven / knitted fabric which consists of a fully aromatic polyamide fiber to both surfaces of the thin film with moisture permeability waterproofness is mentioned. The thin film used here is not particularly limited as long as it has moisture permeability and waterproofness, but it is particularly preferable to use a polytetrafluoroethylene thin film having chemical resistance. Examples of the method of bonding a woven or knitted fabric made of wholly aromatic polyamide fiber to the film include a laminate.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, these Examples and Comparative Examples are for helping understanding of the present invention, and the scope of the present invention is not limited by these descriptions.

<Measurement method>
Each physical property value in Examples and Comparative Examples was measured by the following method.

[Intrinsic viscosity (IV)]
The polymer was dissolved in 97% concentrated sulfuric acid and measured at 30 ° C. using an Ostwald viscometer.

[Brightness index L *]
The lightness index L * value was calculated by measuring the diffuse reflectance in a -10 degree visual field with the light source D65 and performing normal arithmetic processing.

[Fineness]
Based on JIS L1015, the measurement based on the A method of positive fineness was implemented, and it described with the apparent fineness.

[Residual solvent amount]
About 8.0 g of fiber was collected, dried at 105 ° C. for 120 minutes, allowed to cool in a desiccator, and the fiber mass (M1) was weighed. Subsequently, the fiber was subjected to reflux extraction using a Soxhlet extractor in methanol for 1.5 hours to extract an amide solvent contained in the fiber. The fiber after extraction was taken out, vacuum-dried at 150 ° C. for 60 minutes, allowed to cool in a desiccator, and the fiber mass (M2) was weighed. The amount of solvent (amide solvent mass) N (%) remaining in the fiber was calculated by the following formula using M1 and M2 obtained.
N (%) = [(M1-M2) / M1] × 100

[Maximum heat shrinkage]
As a measuring device, a thermomechanical analyzer EXSTAR6000 made by SII is used, a fiber sample is divided into 480 dtex, and this is sandwiched between chucks and used as a measurement sample. The shrinkage ratio with respect to the initial length of the sample fiber at each temperature was measured under the following conditions, and the shrinkage ratio at the temperature at which the shrinkage ratio was maximum among the obtained shrinkage ratio results at each temperature was defined as the maximum heat shrinkage ratio.
(Measurement condition)
Measurement sample length: 10 mm
Temperature increase rate: 100 ° C./min
Measurement temperature range: 25-500 ° C
Load applied to fiber sample: 1.2 cN

[Light-changing chromaticity with xenon arc fade meter (color difference: ΔE *)]
-10 degree field of view with light source D65 using unirradiated cotton (unirradiated fabric) and light irradiated cotton (light irradiated fabric) irradiated at 1.1 W / m ² for 24 hours and 80 hours with a xenon arc fade meter The light reflectance index L * value, the chromaticness index a *, and the b * value were calculated by a normal calculation process. At this time, the measurement light irradiation area was 30 mmΦ. The light discoloration chromaticity (color difference: ΔE *) was obtained from the following equation using the obtained value in accordance with JIS Z-8730.
[Formula 1]
ΔE * = ((ΔL *) ² + (Δa *) ² + (Δb *) ² ) ^1/2

[Light-changing chromaticity with a carbon arc fade meter (color difference: ΔE *)]
Using non-irradiated cotton and light-irradiated cotton irradiated at 135V / 17A for 24 hours and 72 hours with a carbon arc fade meter, the diffuse reflectance in the -10 degree field of view is measured with the light source D65, and normal calculation processing is performed. The brightness index L * value and the chromaticness index a *, b * value were calculated. At this time, the measurement light irradiation area was 10 mmΦ. The light discoloration chromaticity (color difference: ΔE *) was determined by the same formula as the light discoloration chromaticity (color difference: ΔE *) obtained by the above xenon arc fade meter.

[Ratio of light change chromaticity (color difference: ΔE *)]
The ratio of the numerical values of the examples to the comparative numerical values of the same color was determined by using the light change chromaticity (ΔE *) before and after 72 hours irradiation at 135V · 17A with a carbon arc fade meter.

[Heat insulation against flame]
A temperature increase test at 24 ° C. was performed by a method based on ISO 9151. Specifically, the layered protective garment for test was exposed to a prescribed flame, and the time until the temperature rise in the layered protective garment reached 24 ° C. was measured to evaluate the heat shielding property against the flame.

[Heat insulation against radiant heat]
The measurement was carried out by a method based on ISO 6942; 2002 (Cu). Specifically, the laminated protective garment for test was exposed to a prescribed heat source, and the time until the temperature rise in the laminated protective garment reached 24 ° C. was measured to evaluate the heat shielding property against radiant heat.

<Example 1>
[Spinning liquid adjustment process]
In a reaction vessel under a dry nitrogen atmosphere, 721.5 parts by mass of N, N-dimethylacetamide (DMAc) having a moisture content of 100 ppm or less was weighed, and 97.2 parts by mass (50.18 mol) of metaphenylenediamine was added to the DMAc. %) Was dissolved and cooled to 0 ° C. To this cooled DMAc solution, 181.3 parts by mass (49.82 mol%) of isophthalic acid chloride (hereinafter abbreviated as IPC) was added while gradually stirring to carry out a polymerization reaction.
Next, 66.6 parts by mass of calcium hydroxide powder having an average particle size of 10 μm or less was weighed and slowly added to the polymer solution after completion of the polymerization reaction to carry out a neutralization reaction. After the addition of calcium hydroxide was completed, the mixture was further stirred for 40 minutes to obtain a transparent polymer solution. When polymetaphenylene isophthalamide was isolated from the obtained polymer solution and the intrinsic viscosity (IV) was measured, it was 1.65. The polymer concentration in the polymer solution was 17%.
In the polymer solution, Pigment Blue 15 powder having a polymer ratio of 0.95% by mass was uniformly dispersed and subjected to vacuum depressurization to prepare a spinning solution (spinning dope).

[Spinning and coagulation process]
The spinning dope was spun from a spinning nozzle having a hole diameter of 0.07 mm and a hole number of 500 into a coagulation bath having a bath temperature of 30 ° C. The composition of the coagulation liquid was water / DMAc = 45/55 (parts by mass), and was spun by discharging into a coagulation bath at a yarn speed of 7 m / min.

[Plastic stretching bath stretching process]
Subsequently, the film was stretched at a stretching ratio of 3.7 times in a plastic stretching bath having a composition of water / DMAc = 45/55 at a temperature of 40 ° C.

[Washing process]
After stretching, the film was washed with a 20 ° C. water / DMAc = 70/30 bath (immersion length 1.8 m), followed by a 20 ° C. water bath (immersion length 3.6 m), and then a 60 ° C. hot water bath (immersion length 5). 4m) and thoroughly washed.

[Dry heat treatment process]
The washed fiber was subjected to a dry heat treatment with a heat roller having a surface temperature of 300 ° C. to obtain an original meta type wholly aromatic polyamide fiber.

[Crimping and cutting process]
After imparting crimps to the fiber obtained through the crimper, the fiber was cut with a cutter to make a short fiber of 51 mm, thereby obtaining an original meta-type wholly aromatic polyamide raw cotton. Table 1 shows various measurement results for the obtained raw cotton.

[Production of woven fabric]
A woven fabric (weight per unit: 239 g / m ² , thickness: 0.8 mm) in which the raw cotton cut to 51 mm is made into a spun yarn (count: 30/2) through a normal spinning process, and the spun yarn is woven into 2/1 twill. Was made. Scouring treatment was performed by a known method to remove the paste and oil on the fabric surface. Table 1 shows the measurement results of the color change of the obtained fabric.

[Production of laminated protective clothing]
(Surface layer)
As the surface layer, the woven fabric obtained above was used.

(Inner layer)
A woven fabric made from the meta-type wholly aromatic polyamide fiber obtained above on one side of a moisture permeable and waterproof polytetrafluoroethylene film (manufactured by Japan Gore-Tex Co., Ltd., basis weight: 35 g / m ² ) 75 g / m ² ). Subsequently, a circular knitted fabric using a spun yarn made from the meta-type wholly aromatic polyamide fiber obtained above (the basis weight: 180 g / m ² , honeycomb mesh) in order to impart heat insulation to the other surface of the film Structure) was bonded to obtain a composite. The obtained composite was used as the inner layer.

(Lamination process)
The two layers of the surface layer and the inner layer were overlapped and stitched to obtain the laminated protective clothing of the present invention.

[Heat insulation of laminated protective clothing]
The heat shielding property of the obtained laminated protective clothing was evaluated. The results are shown in Table 1.

<Comparative Example 1>
An original meta-type wholly aromatic polyamide raw cotton was produced in the same manner as in Example 1 except that in the spinning and coagulation step, the composition of the coagulation liquid was changed to water / DMAc (quantity ratio) = 70/30. Table 1 shows various measurement results for the obtained raw cotton.

[Production and evaluation of fabrics]
A woven fabric was obtained in the same manner as in Example 1 using the obtained raw cotton. Table 1 shows the evaluation results of the obtained woven fabric.

[Production of laminated protective clothing]
A laminated protective garment was prepared in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained heat-resistant protective clothing.

<Comparative example 2>
An original meta-type wholly aromatic polyamide raw cotton was produced in the same manner as in Example 1 except that the composition of the coagulation liquid was changed to water / DMAc (quantity ratio) = 30/70 in the spinning / coagulation step. Table 1 shows various measurement results for the obtained raw cotton.

[Production and evaluation of fabrics]
A woven fabric was obtained in the same manner as in Example 1 using the obtained raw cotton. Table 1 shows the evaluation results of the obtained woven fabric.

[Production of laminated protective clothing]
A laminated protective garment was prepared in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained heat-resistant protective clothing.

<Example 2>
An original meta-type wholly aromatic polyamide raw cotton was produced in the same manner as in Example 1 except that Pigment Blue 60 / Pigment Black 7 mixed pigment (Navy Blue) was used as the pigment. Table 1 shows various measurement results for the obtained raw cotton.

[Production and evaluation of fabrics]
A woven fabric was obtained in the same manner as in Example 1 using the obtained raw cotton. Table 1 shows the evaluation results of the obtained woven fabric.

[Production of laminated protective clothing]
A laminated protective garment was prepared in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained heat-resistant protective clothing.

<Comparative Example 3>
In the spinning / coagulation step, an original meta-type wholly aromatic polyamide raw cotton was produced in the same manner as in Example 2 except that the composition of the coagulation liquid was changed to water / DMAc (quantity ratio) = 30/70. Table 1 shows various measurement results for the obtained raw cotton.

[Production and evaluation of fabrics]
A woven fabric was obtained in the same manner as in Example 1 using the obtained raw cotton. Table 1 shows the evaluation results of the obtained woven fabric.

[Production of laminated protective clothing]
A laminated protective garment was prepared in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained heat-resistant protective clothing.

<Example 3>
An original meta-type wholly aromatic polyamide raw cotton was produced in the same manner as in Example 1 except that Pigment Black 7 was used as a pigment. Table 1 shows various measurement results for the obtained raw cotton.

[Production and evaluation of fabrics]
A woven fabric was obtained in the same manner as in Example 1 using the obtained raw cotton. Table 1 shows the evaluation results of the obtained woven fabric.

[Production of laminated protective clothing]
A laminated protective garment was prepared in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained heat-resistant protective clothing.

<Comparative example 4>
In the spinning / coagulation step, an original meta-type wholly aromatic polyamide raw cotton was produced in the same manner as in Example 3 except that the composition of the coagulation liquid was changed to water / DMAc (quantity ratio) = 30/70. Table 1 shows various measurement results for the obtained raw cotton.

[Production and evaluation of fabrics]
A woven fabric was obtained in the same manner as in Example 1 using the obtained raw cotton. Table 1 shows the evaluation results of the obtained woven fabric.

[Production of laminated protective clothing]
A laminated protective garment was prepared in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained heat-resistant protective clothing.

  The laminated protective garment of the present invention is a protective garment in which discoloration due to prolonged exposure and thermal contraction due to high-temperature heating such as flame exposure and radiant heat are suppressed. For this reason, it can be suitably used for fire fighting clothes and heat-resistant work clothes that require these characteristics.

Claims (6)

A protective clothing made of laminated fabric,
The protective garment includes a cloth containing a meta-type wholly aromatic polyamide fiber as an outermost layer,
The meta-type wholly aromatic polyamide fiber is a meta-type wholly aromatic polyamide laminated protective clothing which is an original meta-type wholly aromatic polyamide fiber having a residual solvent amount of 0.1% by mass or less based on the entire fiber mass. 2. The meta type according to claim 1, wherein the original meta type wholly aromatic polyamide fiber has a color difference (ΔE *) before and after irradiation for 80 hours at 1.1 W / m ² with a xenon arc fade meter of 24.0 or less. Fully aromatic polyamide laminated protective clothing.   2. The meta type wholly aromatic polyamide fiber according to claim 1, wherein the original meta type wholly aromatic polyamide fiber has a color difference (ΔE *) before and after irradiation for 72 hours at 135 V · 17 A using a carbon arc fade meter of 3.5 or less. Polyamide laminated protective clothing.   The original meta-type wholly aromatic polyamide fiber has the same color difference (ΔE *) before and after irradiation for 72 hours at 135V · 17A using a carbon arc fade meter, and the residual solvent amount in the fiber is 0.4% by mass or more. The meta-type wholly aromatic polyamide laminated protective clothing according to claim 1, which is 75% or less with respect to the color difference (ΔE *) of the original meta-type wholly aromatic polyamide fiber to which the same amount of pigment is added.   The meta according to any one of claims 1 to 4, wherein the original meta-type wholly aromatic polyamide fiber has a temperature increase rate of 100 ° C / min and a maximum heat shrinkage of 7.5% or less at a temperature range of 25 to 500 ° C. Type fully aromatic polyamide laminated protective clothing.   The meta-type wholly aromatic polyamide laminated protective clothing according to any one of claims 1 to 5, wherein the fabric including the meta-type wholly aromatic polyamide fiber is a surface layer.