JP2014210984A - Spun yarn and fabric and clothing - Google Patents

Abstract

The present invention provides a spun yarn having protection performance from flame, heat, arc, and the like, having a high dyeing fastness and hardly yellowing with time, and a fabric and clothing using the spun yarn. A spun yarn is obtained using 50 to 80% by weight of meta-aramid fiber, 10 to 30% by weight of acrylic fiber, 5 to 20% by weight of para-aramid fiber, and 1 to 3% by weight of antistatic fiber, and then as necessary. Obtain fabrics and apparel. [Selection figure] None

Description

  The present invention relates to a spun yarn having protection performance from flame, heat, arc, and the like, having high dyeing fastness, and hardly yellowing with time, and a fabric and clothing using the spun yarn.

People working in the vicinity of energized electrical equipment, etc., and rescue workers responding to accidents in electrical equipment, etc. are exposed to the danger of electric arcs and fires that can occur due to the arc phenomenon. An electric arc is generated in the atmosphere when the potential difference between the two electrodes ionizes atoms in the atmosphere to conduct electricity.
Various types of protective clothing and fabrics and yarns have been proposed so far to protect themselves from such dangers or to reduce the risks.

  For example, Patent Literature 1 discloses a yarn in which meta-aramid fiber, para-aramid fiber, and modacrylic fiber are configured at a specific ratio. Patent Document 2 discloses a yarn in which meta-aramid fibers, para-aramid fibers, and modacrylic fibers having a specific crystallinity have a specific ratio. Patent Document 3 discloses a yarn in which a meta-aramid fiber, a para-aramid fiber, a modacrylic fiber, and an antistatic fiber having a specific crystallinity have a specific ratio. Patent Document 4 discloses a yarn in which meta-acrylic fibers, para-aramid fibers, and modacrylic fibers including antimony are configured at a specific ratio. Patent Document 5 discloses a yarn in which meta-aramid fiber and para-aramid fiber, modacrylic fiber, flame-retardant rayon, and antistatic fiber are configured at a specific ratio. Further, Patent Document 6 discloses a flame retardant fabric containing essentially flame retardant cellulose fiber and FR modacrylic fiber. In all of these, modacrylic fiber contributes to flame retardancy in the same manner as aramid fiber.

  However, when modacrylic fibers are used, there is a problem that the fastness of dyed yarns and fabrics is low. In addition, the fiber is easily yellowed by light and heat, and its use and processing method are restricted. In particular, modacrylic fibers containing halogen such as chlorine as a copolymer component have a problem that they are easily yellowed.

Special table 2007-529648 Special table 2009-503278 Special table 2011-527734 gazette International Publication No. 2010/141554 Pamphlet International Publication No. 2011-126999 Pamphlet JP 2010-502849 gazette

  The present invention has been made in view of the above-mentioned background, and its purpose is to provide a spun yarn having a protection performance from flame, heat, arc, etc., having high dyeing fastness, and hardly yellowing with time, and The object is to provide a fabric and apparel using the spun yarn.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventor has determined the type and weight ratio of fibers constituting the spun yarn (weight ratio of each fiber with respect to the total weight of the spun yarn), so that flame, heat, arc The present inventors have found that a spun yarn having a protective performance from the above, having a high dyeing fastness, and hardly yellowing with time can be obtained, and the present invention has been completed by intensive studies.

  Thus, according to the present invention, “a spun yarn comprising 50 to 80% by weight of meta-aramid fiber, 10 to 30% by weight of acrylic fiber, 5 to 20% by weight of para-aramid fiber, and 1 to 3% by weight of antistatic fiber. Is provided.

  At that time, the spun yarn preferably contains 65 to 75% by weight of meta-aramid fiber, 15 to 25% by weight of acrylic fiber, 5 to 15% by weight of para-aramid fiber, and 2 to 3% by weight of antistatic fiber. The antistatic fiber is preferably selected from the group consisting of carbon fiber, metal fiber, organic fiber with metal plating, and organic fiber containing conductive particles. The meta-aramid fiber preferably contains an organic dye. In the meta-aramid fiber, the crystallinity is preferably in the range of 15 to 50%. The meta-aramid fiber is preferably capable of carrier dyeing. In the meta-aramid fiber, the residual solvent amount is preferably 0.1% by mass or less. Moreover, it is preferable that the said acrylic fiber is a fiber which consists of a synthetic polymer on a straight line in which the repeating unit of an acrylonitrile group contains 85% or more by mass ratio. In the acrylic fiber, it is preferable that the repeating unit of the acrylonitrile group is 85% or more by mass ratio and the halogenated monomer unit is less than 15% by mass ratio. Moreover, it is preferable that cellulose fiber, polyester fiber, or polyamide fiber is further contained in the spun yarn. In that case, it is preferable that the said cellulose fiber is a rayon. Moreover, it is preferable that at least one of the fibers constituting the spun yarn contains a flame retardant.

Moreover, according to this invention, the fabric containing the said spun yarn is provided. In such a fabric, the fabric weight is preferably in the range of 120 to 300 g / m ² . Moreover, it is preferable that the shrinkage rate after 10 washing cycles is 5% or less. Moreover, it is preferable to maintain the category 2 arc rating in the arc resistance test according to ASTM F-1959-99.
Moreover, according to this invention, the clothing which uses the said fabric is provided.

  According to the present invention, a spun yarn having protection performance from flame, heat, arc, etc., high dyeing fastness, and hardly yellowing with time, and a fabric and a garment using the spun yarn are obtained. .

Hereinafter, embodiments of the present invention will be described in detail.
First, in the present invention, the acrylic fiber is a synthetic fiber using acrylonitrile as a raw material, as defined by Japanese Industrial Standard (JIS) and International Standard (ISO), and the repeating unit of acrylonitrile group is 85% by mass. A fiber composed of the above-described linear synthetic polymer is preferable. When the repeating unit of the acrylonitrile group is less than 85% by mass ratio, there is a possibility that high dyeing fastness, suppression of yellowing, retention of aesthetics with time, etc. may not be obtained. At that time, in the acrylic fiber, the repeating unit of the acrylonitrile group is 85% or more by mass ratio, and the halogenated monomer unit such as vinyl chloride, vinylidene chloride, vinyl bromide or the like is less than 15% by mass ratio. (More preferably 1% or more and less than 15%).

  The acrylic fiber is preferably produced by the following steps. Polyacrylonitrile (preferably polyacrylonitrile which is a polymer having an average molecular weight of 100,000 obtained by free radical polymerization) is dissolved in a solvent such as N, N-dimethylformaldehyde or hydrous sodium thiocyanate. Furthermore, by passing the solution through a spinneret (spinneret) having a plurality of holes, the resulting filament coagulates in an aqueous solution of the solvent. Here, the resulting filament is washed, stretched, dried, and crimped (crimped) to finally obtain an acrylic fiber. The single fiber fineness of the acrylic fiber is preferably in the range of 1 to 15 dtex.

  The acrylic fiber may optionally contain a flame retardant in order to supplement the flame retardant performance according to its use and purpose of use, and the flame retardant may be included in the fiber or applied to the outer periphery. Further, it is possible to perform a flame-retardant treatment at any stage before and after each stage of spinning, weaving, and sewing, and any known method can be adopted as a treatment method for inclusion and application. As the flame retardant, known ones such as phosphorus flame retardants and bromine flame retardants can be arbitrarily adopted.

  The spun yarn of the present invention contains the acrylic fiber in an amount of 10 to 30% by weight (preferably 15 to 25% by weight) relative to the weight of the spun yarn. When the acrylic fiber content is smaller than the above range, the dyeing fastness and dyeability may be lowered, which is not preferable. Conversely, when the content of acrylic fibers is larger than the above range, the content of other fibers is relatively lowered, which is not preferable.

  In the present invention, “aramid” refers to a polyamide in which at least 85% of amide bonds (—CONH—) are directly bonded to two aromatic rings. Various additives may be used for this aramid. Also, other polymeric materials in amounts up to 10% by weight can be mixed with aramid, or 10% of the diamine component constituting the aramid is replaced with another diamine component or the diacid chloride constituting the aramid For example, a copolymer in which 10% of the components are replaced with other diacid chloride components can be used. Meta-aramid is an aramid in which amide bonds are in the meta position, and para-aramid is an aramid in which the amide bonds are in the para position. Specifically, examples of meta-aramid include polymetaphenylene isophthalamide. On the other hand, examples of para-aramid include polyparaphenylene terephthalamide and copolyparaphenylene 3,4'-oxydiphenylene terephthalamide. Of course, it is not limited to these.

  The spun yarn of the present invention contains the metaaramid fiber composed of the metaaramid in an amount of 50 to 80% by weight (preferably 65 to 75% by weight) relative to the weight of the spun yarn. When the meta-aramid fiber is included in the spun yarn within this range, the energy / heat transfer when exposed to a flash fire or the like can be prevented, and the protection performance from flame, heat, arc, etc. is improved. When the content of the meta-aramid fiber is smaller than the above range, it is not preferable because the energy / heat transfer when exposed to a flash fire cannot be prevented, and the protection performance from flame, heat, arc, etc. is lowered. On the contrary, when the content of the metaaramid fiber is larger than the above range, the content of other fibers is relatively lowered, which is not preferable.

  Here, in order to further improve the arc protection, the meta-aramid fiber preferably has a crystallinity in the range of 15 to 50% (more preferably 20 to 25%). When the crystallinity is smaller than the above range, the shrinkage property due to heat becomes large, and when exposed to an arc, there is a possibility that holes are easily formed in the fabric with the energy. Conversely, if the crystallinity is greater than 50%, it may be difficult to form fibers. A method for measuring the crystallinity will be described later.

  Further, it is preferable that the meta-aramid fiber is excellent in dyeability when carrier dyeing is possible. In order to enable the carrier dyeing of the meta-aramid fiber, the meta-aramid fiber may be produced by the method described in JP 2010-84237 A. That is, the following manufacturing method.

[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 meta-type aromatic dicarboxylic acid component that is a raw material for 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 is not particularly limited. For example, it is produced by solution polymerization or interfacial polymerization using a meta-type aromatic diamine component and a meta-type aromatic dicarboxylic acid chloride component as raw materials. be able to.

<Method for producing meta-type wholly aromatic polyamide fiber>
The easy-dyeing meta-type wholly aromatic polyamide fiber of the present invention uses, for example, a spinning solution preparation process, spinning / coagulation process, plasticity described below, using the meta-type wholly aromatic polyamide obtained by the above production method. It is manufactured through a drawing bath drawing process, a washing process, a relaxation treatment process, and a heat treatment process.

[Spinning liquid preparation process]
In the spinning solution preparation step, the meta type wholly aromatic polyamide is dissolved in an amide solvent to prepare a spinning solution (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 concentration of the solution may be appropriately selected from the viewpoint of the coagulation rate and the solubility of the polymer in the next spinning and coagulation step. For example, the polymer is polymetaphenylene isophthalamide and the solvent is NMP. In the case of, it is usually preferred to be in the range of 10 to 30% by mass.

[Spinning and coagulation process]
In the spinning / coagulation step, the spinning solution (meta-type wholly aromatic polyamide polymer solution) obtained above is spun into a coagulating 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. The temperature of the spinning solution (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 for obtaining fibers, an aqueous solution containing an NMP concentration of 45 to 60% by mass not containing an inorganic salt is used at a bath temperature of 10 to 35 ° C. If the NMP concentration is less than 45% by mass, the skin has a thick structure, the cleaning efficiency in the cleaning process is lowered, and it becomes difficult to make the residual solvent amount of the fibrils 0.1% by mass or less. Further, when the NMP concentration exceeds 60% by mass, uniform solidification cannot be performed until reaching the inside of the fiber, and therefore, it becomes difficult to make the residual solvent amount of the fibrils 0.1% by mass or less, Moreover, acid resistance is also insufficient. 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 a fiber, the draw ratio in the plastic drawing bath needs to be in the range of 3.5 to 5.0 times, and more preferably in the range of 3.7 to 4.5 times. In the present invention, the solvent removal from the coagulated yarn can be promoted by plastic drawing in a range of a specific magnification in the plastic drawing bath, and the residual solvent amount of the fibril is 0.1 mass% or less. be able to. 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 production stability. The temperature of the plastic stretching bath is preferably in the range of 10 to 90 ° C. When the temperature is preferably in the range of 20 to 90 ° C, the process condition is good.

[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 concentration condition of the amide solvent are not particularly limited as long as the quality of the finally obtained fiber can be satisfied, but if the initial washing bath is at a high temperature of 60 ° C. or higher, water Intrusion into the fiber occurs at a stretch, generating huge voids in the fiber, leading to quality degradation. For this reason, it is preferable that the first washing bath has a low temperature of 30 ° C. or lower.

[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 a dry heat treatment, an easily dyeable meta-type wholly aromatic polyamide fiber can be finally obtained. In order to obtain an easily dyeable meta-type wholly aromatic polyamide fiber, the heat treatment temperature in the dry heat treatment step needs to be in the range of 260 to 330 ° C, and more preferably in the range of 270 to 310 ° C. When the heat treatment temperature is less than 260 ° C., the fiber is insufficiently crystallized and the target acid resistance is insufficient. On the other hand, when the temperature exceeds 330 ° C., the crystallization of the fibers becomes too large, and the dyeability is greatly reduced. Moreover, making dry-heat-treatment temperature into the range of 260-330 degreeC contributes to the improvement of the breaking strength of the fiber obtained.
Further, in the meta-aramid fiber, it is preferable that the residual solvent amount is 0.1% by mass or less because it is environmentally friendly, and it is preferable that yellowing with time is difficult. In addition, it is good to manufacture with the said manufacturing method in order to make a residual solvent amount into 0.1 mass% or less.

  The spun yarn of the present invention contains 5 to 20% by weight (more preferably 5 to 15% by weight) of the para-aramid fiber made of the above-mentioned para-aramid relative to the weight of the spun yarn. When the para-aramid fiber is included in the spun yarn within this range, the tear resistance of the fabric after exposure to flame is improved. When the content of the para-aramid fiber is smaller than the above range, the tear resistance of the fabric after exposure to flame may decrease, which is not preferable. Conversely, when the content of the para-aramid fiber is larger than the above range, the para-aramid fiber has a high elastic modulus, which not only impairs the wearing comfort of the fabric and clothes using the spun yarn but also relatively other fibers. The content of is reduced, which is not preferable.

  The spun yarn of the present invention contains 1 to 3% by weight (preferably 2 to 3% by weight) of the antistatic fiber relative to the weight of the spun yarn. By using antistatic fibers, yarns, fabrics, and clothes with reduced chargeability are obtained, and as a result, apparent electric field strength and troublesome static electricity are reduced. When the content of the antistatic fiber is smaller than the above range, the chargeability may not be reduced, which is not preferable. On the other hand, when the content of the antistatic fiber is larger than the above range, the elastic modulus of the antistatic fiber is high, so that the wearing comfort of the fabric or clothes using the spun yarn is not preferable. Although the antistatic fiber is not particularly limited, a carbon core / nylon sheath fiber, a metal-plated fiber, or the like can be preferably exemplified.

  In the spun yarn of the present invention, other fibers such as cellulose fiber (for example, rayon), polyester fiber, polyamide fiber, etc. are further added for the purpose of improving color developability, wear resistance, moisture absorption / release properties, and comfort. May be added. At that time, in the same manner as the acrylic fiber, a flame retardant may optionally be included in order to supplement the flame retardant performance depending on the intended use and purpose of use, and the flame retardant may be included in the fiber or applied to the outer periphery. . In addition, it is preferable that content of this other fiber is 30 weight% or less with respect to the weight of a spun yarn.

The method for producing the spun yarn of the present invention is not particularly limited, and may be a known method. For example, it may be produced by known spinning techniques such as ring spinning, core spinning and air jet spinning, and high-order air spinning techniques such as Murata Air Jet spinning that uses air to twist staple fibers. .
The spun yarn thus obtained has a protection performance against flame, heat, arc, etc., has a high dyeing fastness, and hardly yellows over time.

Next, the fabric of the present invention is a fabric including the spun yarn. Here, the spun yarn may be included in the fabric as a single yarn, or after further twisting the spun yarn as necessary, two or more are aligned (if necessary, other fibers may also be included). The yarns may be combined with each other by pulling them together at the same time, and then twisted in the direction opposite to the twisting direction and included in the fabric as necessary. The spun yarn (or composite yarn) and other fibers may be woven or knitted.
The fabric structure is preferably a woven fabric such as plain weave or twill weave, but may be knitted fabric or non-woven fabric. The production method of the fabric is not particularly limited, and a known knitting machine such as a rapier loom or a gripper loom can be used.

The fabric weight is preferably in the range of 120 to 300 g / m ² . When the basis weight is smaller than the range, the protection performance from flame, heat, arc, etc. may be lowered. On the other hand, when the basis weight is larger than the above range, the weight becomes heavier and the wearing comfort may be impaired.
Further, such a fabric may be a fabric that has been dyed with an organic dye or dyed with a fabric, so-called post-dyeing. Post-dyeing is preferable because it can handle various colors, can meet a wide range of user needs, can handle more vivid colors, can be recolored, and can handle small lots.

In addition, since such a spun yarn is used for such a fabric, it has a protection performance against flame, heat, arc, etc., has a high dyeing fastness, and hardly yellows over time. Specifically, by using the present invention, various fastnesses of light resistance, friction, sweat and washing are improved. This is of great significance for practical, safety and industrial applications, especially in protective clothing used in harsh environments, which can extend the service life.
At that time, it is preferable to maintain the category 2 arc rating in the arc resistance test according to ASTM F-1959-99.
Moreover, in the said fabric, it is preferable that the shrinkage | contraction rate after 10 washing cycles is 5% or less. In order to reduce the shrinkage after 10 washing cycles to 5% or less, for example, the mixing ratio of cellulose fibers may be suppressed to 30% or less.

Next, the garment of the present invention is a garment using the above-mentioned fabric. Since such a garment uses the above-mentioned fabric, it has a protection performance from flame, heat, arc, etc., has high dyeing fastness, and hardly yellows over time.
Such clothing includes fire fighting clothes, fire prevention clothes, office work clothes, racing suits for motor sports, work clothes, gloves, hats, vests, and the like. The work clothes include work clothes for ironworks and steel factories, work clothes for welding work, work clothes in an explosion-proof area, and the like. The gloves include working gloves used in the aircraft industry, the information equipment industry, the precision equipment industry, etc. that handle precision parts.

  Next, although the Example and comparative example of this invention are explained in full detail, this invention is not limited by these. In addition, each measurement item in an Example was measured with the following method.

(1) Residual solvent amount of meta-aramid fiber About 8.0 g of the original 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 remaining in the fiber (amide solvent mass) was calculated by the following formula using M1 and M2 obtained.
Residual solvent amount (%) = [(M1-M2) / M1] × 100

(2) Crystallinity of meta-aramid fiber Obtained by bundling pre-dyed fibers (raw fibers) in a bundle of about 1 mm diameter and measuring with an X-ray diffractometer (trade name: RIGAKU RINT TTRIII) under the following conditions: Converted from the profile.
(Measurement condition)
X-ray source: Cu-Kα ray Fiber sample stage: 50 rpm rotation 2θ scanning: 5-50 °
Continuous measurement: 0.1 °
Width measurement: 1 ° / min scanning Specifically, air scattering and incoherent scattering were corrected from the measured diffraction profile by linear approximation to obtain a total scattering intensity profile. The undried yarn profile of the meta-type wholly aromatic polyamide fiber that is amorphous was fitted to the obtained total scattering intensity, and the difference was defined as the crystal scattering intensity. The degree of crystallinity was determined from the following equation using the area (integrated value) of the crystal scattering intensity and the total scattering intensity.
Crystallinity (%) = [crystal scattering intensity / total scattering intensity] × 100

(3) Fabric Dyeing Method Cationic Dye (Nippon Kayaku Co., Ltd., trade name: Kayacryl ED Brill G-ED / Kayacryl ED Flavine 10G-E) 5% owf, Ospin TAN (cationic dye dye; Tokai Seiyaku Co., Ltd.) Manufactured) 2% owf pH 4, bath ratio 1:50, 100 ° C. × 30 minutes Under the above conditions, the temperature was raised from 20 ° C. to 100 ° C. at 1 ° C / min, and maintained at 100 ° C. for 30 minutes. The temperature was lowered to 60 ° C at a rate of ° C / min to finish dyeing and dry.

(4) Fabric dyeability (colorimetry)
The colorability (C * value) was measured with a Macbeth spectrophotometer Color-Eye 3100.

(5) Washing fastness It evaluated according to the measuring method prescribed | regulated to JISL0844 (A method). For the determination, JIS-L0804 gray scale for color change was used.

(6) Friction fastness It evaluated according to the measuring method prescribed | regulated to JISL0849. For the determination, JIS-L0804 gray scale for color change was used.

(7) Light fastness It evaluated according to the measuring method prescribed | regulated to JISL0842. For the determination, JIS-L0804 gray scale for color change was used.

(8) Flame resistance of fabric (limit oxygen index)
Based on the JIS L1096 E method, the oxygen concentration required to continue burning 50 mm or more was defined as the limiting oxygen index (LOI).

(9) Arc Resistance Test In accordance with ASTM F-1959-99 “Standard Test Method for Determining Arc Thermal Performance Values of Materials for Fabrics”, Hitachi Chemical Co., Ltd. HAT-100 was used as an arc resistance tester. Used to evaluate the arc resistance of the fabric of the present invention.

(10) Fabric basis weight Measured according to JIS L 1096.

[Manufacture of acrylic fiber raw cotton]
For the polymerization of acrylonitrile monomer, water is used as a polymerization medium, the polymerization reaction temperature is set to 60 ° C., the water / monomer ratio is set to 3.2, and the hydrogen ion concentration in the polymerization reaction kettle is set to an acidic region of pH 2.8. , And the range in which the catalyst promptly undergoes oxidation / reduction reactions. A polymerization terminator was added to the polymer taken out from the polymerization reaction kettle to stop the reaction. After adding a polymerization terminator to the aqueous polymer solution, the unreacted monomer was recovered. As a method for recovering the unreacted monomer, a method was adopted in which the aqueous polymer solution was led to a direct distillation tower (not shown), where polymer / water and water / unreacted monomer were separated to recover the unreacted monomer.

The acrylonitrile polymer thus obtained was dissolved in a solvent to prepare a spinning dope. Dimethyl sulfoxide was used as a solvent at this time. A solution comprising 20% by weight of the acrylonitrile polymer and 80% by weight of the organic solvent was prepared.
The spinning dope thus obtained was extruded into a coagulating liquid through a spinneret disposed in a coagulating bath, and coagulated into a fiber tow shape composed of a large number of fiber groups. The acrylic fiber tow that came out of the coagulation liquid was introduced into the washing tank in the washing step at a predetermined speed, and washed by removing the solvent adhering to the fiber surface or remaining with hot water.

The acrylic fiber tow after the removal of the solvent was subsequently introduced into a drawing tank in the drawing process, and passed through hot water to be drawn 4.6 times. This drawing was performed while the acrylic fiber tow passed through the washing tank and the drawing tank. The acrylic fiber tow after stretching was subjected to final cleaning again through an auxiliary cleaning tank, and after applying an oil agent, it was dried in a drying process and sent to a finishing process such as the next heat relaxation treatment. An acrylic fiber raw cotton was obtained from this tow through the steps of crimping and cutting.
The acrylic fiber was a fiber composed of a synthetic polymer on a straight chain having an acrylonitrile group repeating unit of 99% or more by mass ratio.

[Production of raw cotton of meta-aramid fiber]
20.0 parts by mass of polymetaphenylene isophthalamide powder having an intrinsic viscosity (IV) of 1.9 produced by an interfacial polymerization method in accordance with the method described in Japanese Patent Publication No. 47-10863 is placed at −10 ° C. It was suspended in 80.0 parts by mass of cooled N-methyl-2-pyrrolidone (NMP) to form a slurry. Subsequently, the suspension was heated to 60 ° C. and dissolved to obtain a transparent polymer solution. To the polymer solution, 3.0% by mass of 2- [2H-benzotriazol-2-yl] -4-6-bis (1-methyl-1-phenylethyl) phenol powder (solubility in water: 0) .01 mg / L) was mixed and dissolved, and depressurized under reduced pressure to obtain a spinning solution (spinning dope).
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 / NMP = 45/55 (parts by mass), and was spun by discharging into the coagulation bath at a yarn speed of 7 m / min.

Subsequently, the film was stretched at a stretching ratio of 3.7 times in a plastic stretching bath having a composition of water / NMP = 45/55 at a temperature of 40 ° C.
After stretching, the film was washed with a 20 ° C. water / NMP = 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.
The washed fiber was subjected to a dry heat treatment with a heat roller having a surface temperature of 280 ° C. to obtain a meta-type wholly aromatic aramid fiber.
The physical properties of the obtained meta-aramid fiber were a fineness of 1.7 dtex, a residual solvent amount of 0.08% by mass, and a crystallinity of 19%. Also, carrier staining was possible.

[Manufacture of other fibers]
The following raw fiber cotton was used.
Polyester fiber; Teijin Limited polyethylene terephthalate fiber "Tetron"
Flame retardant rayon fiber; “LenzingFR (registered trademark)” manufactured by Lenzing
Para-aramid fiber; “Twaron (registered trademark)” manufactured by Teijin Aramid
Antistatic fiber: Nylon “NO SHOCK (registered trademark)” kneaded with conductive carbon fine particles manufactured by Solcia

[Example 1]
Meta-aramid fiber (MA) raw cotton (length 51 mm, acrylic fiber (AN) raw cotton (length 51 mm), para-aramid fiber (PA) raw cotton (length 51 mm), antistatic fiber (length 51 mm) (AS) MA / AN / PA / AS = 36 / twisted yarn blended at a ratio of 75/15/8/2, and weaved at a weaving density of 100 yarns / 25.4 mm and weft yarns 56 / 25.4 mm A fabric made of a twill woven fabric having a basis weight of 230 g / m ² was obtained, dyed by the above-described method, and evaluated for the arc resistance performance, flame retardancy, and dyeing fastness. Is shown in Table 1.
Next, when a fire fighting garment was obtained using the fabric, it had a protection performance from flame, heat, arc, etc., had high dyeing fastness, and hardly yellowed over time.

[Examples 2 to 4, Comparative Examples 1 and 2]
In Example 1, the spun yarn was made of raw material of meta-aramid fiber (MA) (length: 51 mm, raw material of acrylic fiber (AN) (length: 51 mm), raw material of para-aramid fiber (PA) (length: 51 mm), antistatic fiber (Length 51 mm) (AS) was changed to a spun yarn as the blending rate shown in Table 1, and the other operations and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 3]
In Example 1, the acrylic fiber was changed to Kanekalon made of Modacrylic fiber (MO) Kaneka, and the same operations and evaluations as in Example 1 were performed except that. The results are shown in Table 1.

[Example 5]
In Example 1, the acrylic fiber was changed to a product in which 3% by weight of the flame retardant Nikkafinon HF-2200 (manufactured by Nikka Chemical Co., Ltd.) with respect to the polymer weight was added at the spinning solution stage. The same operation and evaluation as in Example 1 were performed. The results are shown in Table 1.

[Examples 6 to 9]
In Example 5, in the meta-aramid fiber (MA), the acrylic fiber (FRAN) to which the flame retardant is added, and the para-aramid fiber (PA), one, two, or three of the constituent fibers are reduced, and the polyester fiber ( PE) and / or flame retardant rayon fiber (RY) was added, and the same operation and evaluation as in Example 1 were performed except that. The results are shown in Table 1.

[Examples 10 to 13]
In Example 5, in the meta-aramid fiber (MA), the acrylic fiber (AN), and the para-aramid fiber (PA), one, two, or three of the constituent fibers are reduced, and the polyester fiber (PE) and / or Flame retardant rayon fiber (RY) was added, and the other operations and evaluations were the same as in Example 1. The results are shown in Table 1.

  According to the present invention, there are provided a spun yarn having a protection performance from flame, heat, arc, etc., having a high dyeing fastness and hardly yellowing with time, and a fabric and clothing using the spun yarn. The industrial value is extremely large.

Claims (17)

  A spun yarn comprising 50 to 80% by weight of meta-aramid fiber, 10 to 30% by weight of acrylic fiber, 5 to 20% by weight of para-aramid fiber, and 1 to 3% by weight of antistatic fiber.   The spun yarn of claim 1, comprising 65-75% by weight of meta-aramid fibers and 15-25% by weight of acrylic fibers and 5-15% by weight of para-aramid fibers and 2-3% by weight of antistatic fibers.   The antistatic fiber according to claim 1 or 2, wherein the antistatic fiber is any one selected from the group consisting of carbon fiber, metal fiber, metal fiber-plated organic fiber, and organic fiber containing conductive particles. Spun yarn.   The spun yarn according to any one of claims 1 to 3, wherein the meta-aramid fiber contains an organic dye.   The spun yarn according to any one of claims 1 to 4, wherein the meta-aramid fiber has a crystallinity within a range of 15 to 50%.   The spun yarn according to any one of claims 1 to 5, wherein the meta-aramid fiber is capable of carrier dyeing.   The spun yarn according to any one of claims 1 to 6, wherein the meta-aramid fiber has a residual solvent amount of 0.1% by mass or less.   The spun yarn according to any one of claims 1 to 7, wherein the acrylic fiber is a fiber made of a synthetic polymer on a straight chain containing 85% or more of a repeating unit of an acrylonitrile group.   The spun yarn according to any one of claims 1 to 8, wherein in the acrylic fiber, the repeating unit of acrylonitrile group is 85% or more by mass ratio, and the halogenated monomer unit is less than 15% by mass ratio.   The spun yarn according to any one of claims 1 to 9, wherein cellulose fiber, polyester fiber or polyamide fiber is further contained in the spun yarn.   The spun yarn according to claim 10, wherein the cellulose fiber is rayon.   The spun yarn according to any one of claims 1 to 11, wherein at least one of the fibers constituting the spun yarn contains a flame retardant.   A fabric comprising the spun yarn according to any one of claims 1 to 12. Basis weight of the fabric is in the range of 120~300g / ^{m 2,} the fabric of claim 13.   The fabric according to claim 13 or 14, wherein a shrinkage rate after 10 washing cycles is 5% or less.   The fabric according to any one of claims 13 to 15, which maintains a category 2 arc rating in an arc resistance test according to ASTM F-1959-99.   The clothing which uses the fabric described in any one of Claims 13-16.