JP2008038274A - Flame retardant aramid fiber containing inorganic carbonate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame retardant aramid fiber having flame retardancy economically imparted by an easy method. <P>SOLUTION: The aramid fiber comprises 3-50 mass% of inorganic carbonate having an average particle size of ≤2 μm and including at least one kind of metal selected from a group consisting of alkali metals and alkali earth metals based on total weight. Calcium carbonate is preferable as the inorganic carbonate and a copolyparaphenylene-3,4'-oxydiphenylene-terephthalamide is preferable as the aromatic polyamide. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an aromatic polyamide fiber containing an inorganic carbonate. More specifically, the present invention relates to a flame retardant aromatic polyamide fiber imparted with a flame retardant economically by a simple method.

  Conventionally, aromatic polyamide fibers are widely used in various fields such as automobile parts, electric / electronic parts, and machine parts because they are excellent in heat resistance, mechanical properties, and chemical resistance. In addition, recently, further improvements are required for the characteristics required for special applications, and improvement of flame retardancy is one of them.

  As a method for making an aromatic polyamide fiber flame-retardant, there is known a method in which a fiber swollen with water is impregnated with a flame retardant and then dried (see Patent Documents 1 to 3). Patent Documents 1 and 2 disclose phosphate ester-based flame retardants as flame retardants impregnated in fibers. In Patent Document 3, antimony oxide, a high bromine compound, a phosphorus compound, and a high chlorine compound are exemplified as flame retardants that impregnate fibers.

Further, as another method for making an aromatic polyamide fiber flame retardant, a method of impregnating a fiber swollen with water with a flame retardant and then treating with a supercritical fluid is also known (see Patent Document 4).
As another method, when high heat is applied to the fiber, the compound layer of the particles forms a protective film that inhibits combustion, thereby providing flame retardancy-imparting particles to which flame retardancy is imparted, A method of forming a composite on the fiber surface has also been proposed (see Patent Document 5).

JP-A 63-145416 Japanese Patent Laid-Open No. 05-230711 Japanese Patent Laid-Open No. 07-197317 JP 2001-348785 A JP 2001-131863 A

  However, in Patent Documents 1 to 3, since the aromatic polyamide fiber must be impregnated with a flame retardant, the fiber manufacturing process becomes complicated and the problem of lack of fastness has arisen.

Further, in Patent Document 4, since supercritical processing has to be performed, an expensive apparatus is required, and it is difficult to carry out easily.
Furthermore, in patent document 5, the flame retardance provision particle | grains of a special structure were required, and it was necessary to implement the process of compounding to a fiber separately.

  The present invention has been made against the background of such a conventional technique, and an object of the present invention is to provide a flame-retardant aromatic polyamide fiber imparted with flame retardancy economically by a simple method. It is in.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, the aromatic polyamide fiber contains an inorganic carbonate containing at least one metal selected from the group consisting of alkali metals and alkaline earth metals in an amount of 3% by mass to 50% by mass with respect to the entire fiber. The inventors have found that flame retardancy can be imparted economically by a simple method, and have completed the present invention.

  That is, the present invention is an aromatic polyamide fiber containing an inorganic carbonate containing at least one metal selected from the group consisting of alkali metals and alkaline earth metals in an amount of 3% by mass or more and 50% by mass or less based on the entire fiber. .

  In addition, the present inventors further have a content of an inorganic carbonate containing at least one metal selected from the group consisting of an alkali metal and an alkaline earth metal in the aromatic polyamide fiber, and an average of the inorganic carbonate fiber in the fiber It has been found that by appropriately controlling the particle size, the mechanical strength such as the tensile strength and tensile modulus inherent in the aromatic polyamide can be maintained and the production stability in the spinning process can be improved.

  The aromatic polyamide fiber of the present invention is a fiber imparted with flame retardancy economically by a simple method. Furthermore, by appropriately controlling the content of the inorganic carbonate and the average particle diameter in the fiber of the inorganic carbonate, the mechanical strength such as the tensile strength and tensile modulus inherent in the aromatic polyamide is maintained, and the spinning step The production stability in can be improved.

Hereinafter, embodiments of the present invention will be described in detail.
<Aromatic polyamide fiber>
The aromatic polyamide fiber of the present invention contains an inorganic carbonate. Below, the structural component of the aromatic polyamide fiber of this invention, a raw material, a manufacturing method, a physical property, etc. are demonstrated.

[Aromatic polyamide]
The aromatic polyamide constituting the fiber of the present invention is a polymer in which one or more divalent aromatic groups are directly linked by an amide bond. In addition, the aromatic group includes a group in which two aromatic rings are bonded via oxygen, sulfur, or an alkylene group, or a group in which two or more aromatic rings are directly bonded. Further, these divalent aromatic groups may include a lower alkyl group such as a methyl group or an ethyl group, a halogen group such as a methoxy group, or a chloro group. In addition, the position of the amide bond that directly links the divalent aromatic group is not limited, and may be either a para type or a meta type.

Examples of such aromatic polyamides include polyparaphenylene terephthalamide, polymetaphenylene isophthalamide, copolyparaphenylene in which a terephthalic acid component is copolymerized with a 3,4′-diaminodiphenyl ether component and a paraphenylenediamine component.・ Copolyparaphenylene, phenylbenzimidazole, terephthalamide copolymerized with 3,4'-oxydiphenylene terephthalamide, terephthalic acid component, aromatic diamine component having phenylbenzimidazole skeleton and paraphenidylenediamine component And so on.
Moreover, as aromatic polyamide used for this invention, it may be used individually by 1 type, or may use 2 or more types together.

  As the aromatic polyamide constituting the fiber of the present invention, those having a para type aromatic polyamide as a main component are preferred from the viewpoint of excellent mechanical properties. Here, the “main component” means that it is in the range of 50% by mass to 100% by mass with respect to the entire aromatic polyamide constituting the fiber. In the present invention, the para-type aromatic polyamide is particularly preferably 100% by mass.

Furthermore, in the present invention, since the mechanical strength is particularly excellent, it is preferable to use polyparaphenylene terephthalamide or copolyparaphenylene 3,4'-oxydiphenylene terephthalamide. From the viewpoint, it is most preferable to use copolyparaphenylene · 3,4′-oxydiphenylene · terephthalamide .

[Raw material for aromatic polyamide]
The aromatic polyamide constituting the fiber of the present invention can be obtained by using an aromatic dicarboxylic acid chloride component and an aromatic diamine component as raw materials and reacting them.

(Aromatic dicarboxylic acid chloride)
The aromatic dicarboxylic acid chloride component used as the raw material for the aromatic polyamide is not particularly limited, and generally known ones can be used. Examples of the aromatic dicarboxylic acid chloride component include isophthalic acid dichloride, terephthalic acid dichloride, 2-chloroterephthalic acid dichloride, 2,5-dichloroterephthalic acid dichloride, 2,6-dichloroterephthalic acid dichloride, and 3-methylterephthalic acid. Examples include acid dichloride, 4,4′-biphenyldicarboxylic acid dichloride, and 2,6-naphthalenedicarboxylic acid dichloride. Among these, terephthalic acid dichloride or isophthalic acid dichloride is preferably used from the viewpoint of versatility of raw materials and heat resistance of the obtained fiber. Furthermore, it is particularly preferable to use terephthalic acid dichloride from which para-type aromatic polyamide can be obtained from the viewpoint of heat resistance and mechanical properties of the obtained fiber.

(Aromatic diamine)
The aromatic diamine component used as the raw material for the aromatic polyamide is not particularly limited, and generally known ones can be used. Further, the aromatic ring of the aromatic diamine component may be substituted or unsubstituted.

Examples of such aromatic diamine components include p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dichloro-p-phenylenediamine, 2,6-dichloro-p-phenylenediamine, m- Examples include phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 3,3'-diaminodiphenyl sulfone. .
In addition, the aromatic polyamide constituting the fiber of the present invention may be one in which the aromatic diamine component is used alone, or two or more in combination.

  In these, it is preferable to use m-phenylenediamine from the viewpoint of the versatility of a raw material and the heat resistance of the fiber obtained. From the viewpoint of heat resistance and mechanical properties of the resulting fiber, it is preferable to use at least one selected from para-type aromatic diamines such as para-type phenylene diamine and para-type biphenylene diamine. Phenylenediamine alone or a combination of p-phenylenediamine and 3,4'-diaminodiphenyl ether is particularly preferred.

[Method for producing aromatic polyamide]
The aromatic polyamide which is a constituent component of the fiber of the present invention can be produced according to a conventionally known method. Specifically, it can be obtained, for example, by subjecting the aromatic dicarboxylic acid chloride component and the aromatic diamine component to low temperature solution polymerization or interfacial polymerization in a solvent.

  Here, examples of the solvent used for the polymerization include organic polar amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, and dimethylimidazolidinone. Solvents, water-soluble ether compounds such as tetrahydrofuran and dioxane, water-soluble alcohol compounds such as methanol, ethanol and ethylene glycol, water-soluble ketone compounds such as acetone and methyl ethyl ketone, water-soluble nitrile compounds such as acetonitrile and propionitrile, etc. Can be mentioned. These solvents can be used alone or as a mixed solvent of two or more. Note that the solvent used is preferably dehydrated.

  In addition, for the purpose of improving the solubility of the obtained aromatic polyamide in a solvent, it is generally preferable to add an appropriate amount of a known inorganic salt. The addition time of the inorganic salt is not particularly limited, and can be added at any time, such as before or during the start of polymerization or at the end of the polymerization. Examples of inorganic salts that can be added include lithium chloride and calcium chloride.

  The ratio of the aromatic dicarboxylic acid chloride component to the aromatic diamine component, which is the raw material of the aromatic polyamide, is 0.90 or more and 1.10 or less as the molar ratio of the aromatic dicarboxylic acid chloride component to the aromatic diamine component. The range is preferable, and the range of 0.95 to 1.05 is more preferable.

  The aromatic polyamide used in the present invention may be an aromatic polyamide having at least one end sealed. The end-capping of the aromatic polyamide can be carried out using an end-capping agent, and examples of the end-capping agent include phthalic acid chloride and substituted products thereof, aniline and substituted products thereof, and the like. .

Furthermore, in general, in the reaction between an acid chloride and a diamine, an aliphatic or aromatic amine or a quaternary ammonium salt can be used in combination in order to capture an acid such as hydrogen chloride to be generated.
After completion of the reaction, it is preferable to carry out a neutralization reaction by adding a basic inorganic compound such as sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide or the like as necessary.

  The reaction conditions for the aromatic dicarboxylic acid chloride component and the aromatic diamine component are not particularly limited. The reaction between acid chloride and diamine is generally rapid, and the reaction temperature is preferably in the range of −25 ° C. or higher and 100 ° C. or lower, and more preferably in the range of −10 ° C. or higher and 80 ° C. or lower.

  The aromatic polyamide obtained by polymerization as described above can be put into a non-solvent such as alcohol or water, precipitated, and taken out as a pulp. The taken-out aromatic polyamide can be dissolved again in another solvent and thereafter subjected to molding. However, the polymer solution obtained by the polymerization reaction can be used as it is prepared as a molding solution. The solvent used for once taking out and then dissolving again is not particularly limited as long as it dissolves the aromatic polyamide, but is preferably a solvent used for the polymerization of the aromatic polyamide described above.

[Inorganic carbonate]
The inorganic carbonate used in the present invention contains at least one metal selected from the group consisting of alkali metals and alkaline earth metals. The inorganic carbonate used in the present invention is non-toxic, and preferably has a low fuming property without generating toxic gas or corrosive gas in the event of a fire. , Calcium carbonate, magnesium carbonate, beryllium carbonate and the like. In addition, the inorganic carbonate can be used alone or in combination of two or more. Among these, it is preferable to use calcium carbonate from the viewpoint of easy handling and finer particles.

[Content of inorganic carbonate]
The content of the inorganic carbonate in the aromatic polyamide fiber of the present invention is in the range of 3% by mass to 50% by mass with respect to the entire fiber. When the content is less than 3% by mass, sufficient flame retardancy is not improved. On the other hand, when the content exceeds 50% by mass, production stability is maintained in the spinning process. It becomes difficult. The content of the inorganic carbonate is preferably in the range of 10% by mass to 50% by mass and more preferably in the range of 20% by mass to 50% by mass with respect to the entire fiber.

[Average particle size of inorganic carbonate]
The average particle size of the inorganic carbonate in the aromatic polyamide fiber of the present invention is preferably 2.0 μm or less. When the average particle diameter in the fiber is 2.0 μm or less, even if a small amount is added, sufficient flame retardancy is improved, and production stability in the spinning process is also improved. The average particle size of the inorganic carbonate in the aromatic polyamide fiber is more preferably 1.5 μm or less, and particularly preferably 1.0 μm or less.

  The aromatic polyamide fiber of the present invention exhibits high flame retardancy because of the endothermic decomposition reaction caused by heating of the inorganic carbonate contained in the fiber. In the present invention, if the average particle diameter of the inorganic carbonate contained in the fiber is reduced, the surface area of the particles increases, and therefore the limiting oxygen index (LOI value) is considered to be greatly improved. By controlling the average particle size of the inorganic carbonate contained in the aromatic polyamide fiber to 2.0 μm or less, high flame retardancy can be obtained with a small addition amount, and stable production in the spinning process can be realized. Furthermore, even when the amount of inorganic carbonate added is increased, it is possible to maintain good spinning properties and further improve the limit oxygen index (LOI value).

  The method for controlling the average particle size of the inorganic carbonate in the aromatic polyamide fiber to 2.0 μm or less is not particularly limited. For example, a method for preparing a spinning solution (dope) by adding an inorganic carbonate having a sufficiently small particle size to an aromatic polyamide solution, or using a bead mill or the like as a solvent for the spinning solution (dope) Examples include a method of preparing a spinning solution (dope) by previously pulverizing and dispersing inorganic carbonate so that the particle diameter is sufficiently small, and mixing the obtained slurry (dispersion) and an aromatic polyamide solution. it can.

  The average particle size of the inorganic carbonate contained in the aromatic polyamide fiber of the present invention is determined by cutting the aromatic polyamide fiber in a direction perpendicular to the fiber axis and using a transmission electron microscope (TEM). Can be obtained by observing.

[Other ingredients]
In the aromatic polyamide fiber of the present invention, for the purpose of imparting functionality and the like to the fiber, other optional components such as additives other than inorganic carbonates may be appropriately contained within a range not exceeding the gist of the present invention. it can. Examples of the optional component used in the present invention include fillers having a fibrous shape or a non-fibrous shape such as a plate shape, a scale shape, a granular shape, an indefinite shape, and a crushed product. Glass fibers, PAN and pitch carbon fibers, stainless fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as wholly aromatic polyamide fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia fibers, silica fibers, Titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, mica, talc, kaolin, silica, glass beads, glass flakes, glass microballoon, clay, two Molybdenum sulfide, wollastonite, titanium oxide, suboxide , Calcium polyphosphate, graphite, metal powders, metal flakes, metal ribbons, metal oxides, mention may be made of carbon nanotube, carbon powder, graphite, carbon flake, and scaly carbon. Moreover, in the aromatic polyamide fiber of this invention, the above other components can also be used not only individually by 1 type but in combination of 2 or more types.

  Further, the filler as the other component is one whose surface has been treated with a known coupling agent (for example, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agent. Also good.

[Method for producing aromatic polyamide fiber]
The method for producing the aromatic polyamide fiber of the present invention is not particularly limited, and can be produced using a known method. For example, a spinning solution containing an aromatic polyamide, an inorganic carbonate, and a solvent ( There is a method of preparing a dope) and discharging the obtained spinning solution (dope) from a nozzle.

  A method for preparing a spinning solution (dope) containing an aromatic polyamide, an inorganic carbonate, and a solvent is not particularly limited. For example, a method of adding an inorganic carbonate to an aromatic polyamide solution, an aromatic polyamide A method of mixing a solution of the above and an inorganic carbonate dispersion (slurry), a method of adding an aromatic polyamide to an inorganic carbonate dispersion (slurry) and dissolving it, an aromatic polyamide to which an inorganic carbonate was added during polymerization And the like.

  As a solvent used for the preparation of the spinning solution (dope), a solvent that can be used for the polymerization of the aromatic polyamide and that can dissolve and disperse the aromatic polyamide and the inorganic carbonate is used. Is preferred. Moreover, the solvent used may be a single solvent or a mixed solvent obtained by mixing two or more solvents.

  In addition, for the purpose of imparting functionality and the like to the fiber, when other optional components such as additives are blended within the range not exceeding the gist of the present invention, it can be introduced in the adjustment of the dope. Examples of other optional components include the above-described optional components, antioxidants, weathering agents, dyes, antistatic agents, conductive polymers, and other polymers. The introduction method is not particularly limited, and for example, the dope can be introduced using a ruder, a mixer, or the like.

  The polymer concentration in the spinning solution (dope), that is, the concentration of the aromatic polyamide is preferably in the range of 0.5% by mass to 30% by mass, and preferably in the range of 1% by mass to 25% by mass. It is more preferable. When the polymer concentration in the spinning solution (dope) is less than 0.5% by mass, the viscosity necessary for spinning cannot be obtained because the polymer is less entangled. On the other hand, when the polymer concentration exceeds 30% by mass, unstable flow tends to occur when discharging from the nozzle, and it becomes difficult to perform stable spinning.

  From the adjusted spinning solution (dope), the aromatic polyamide fiber of the present invention can be obtained by shaping the fiber by a wet method, a semi-dry semi-wet method, etc., removing the solvent and then drying. For example, in the semi-dry and semi-wet method, a spinning solution (dope) is discharged from a nozzle and solidified in a coagulation bath made of a poor solvent to obtain an undrawn yarn, and then the obtained undrawn yarn is An oriented yarn can be obtained by drawing as necessary, and then a fiber can be obtained through a washing and drying process.

  As a stretching method, not only water-washed stretching and boiling water stretching in a coagulated yarn state but also heat stretching in a dry yarn state can be performed. Although there is no restriction | limiting in particular about a draw ratio, It is preferable that it is 1.05 times or more, and it is further more preferable that it is 1.1 times or more. By controlling the draw ratio, the elongation and strength of the resulting aromatic polyamide fiber can be controlled.

[Physical properties of aromatic polyamide fiber]
The aromatic polyamide fiber of the present invention has flame retardancy, and appropriately controls the tensile strength and tensile elasticity inherent in the aromatic polyamide by appropriately controlling the content of inorganic carbonate and the average particle size of the inorganic carbonate fiber. The mechanical strength such as the rate is maintained, and the production stability in the spinning process is improved. The aromatic polyamide fiber of the present invention preferably has the following physical properties.

[Limited oxygen index (LOI value)]
The aromatic polyamide fiber of the present invention can improve the critical oxygen index (LOI value) by 5% or more as compared with a fiber not containing an inorganic carbonate. The limiting oxygen index (LOI value) of the aromatic polyamide fiber of the present invention is preferably 26 or more, and more preferably 28 or more. When the limiting oxygen index (LOI value) is less than 26, the characteristics of the aromatic polyamide fiber as the flame-retardant fiber are lost, which is not preferable.

The “limit oxygen index (LOI value)” in the present invention is an index indicating the combustibility of a textile product, and is a value obtained by measurement under the following conditions based on the JIS L 1091 E method.
(Measurement condition)
Specimen classification: No. E-2 Fabric creation method: Circular knitted fabric (23 wales / inch, 18 courses / inch)
Type of igniter heat source: JIS K2240 Type 1 No. 1 (LP gas)
The critical oxygen index is determined earlier in the following (a) or (b). (A) Combustion length when determining the critical oxygen index: 50 mm
(B) Combustion time when determining the critical oxygen index: 180 seconds

[Tensile strength]
The aromatic polyamide fiber of the present invention maintains the same tensile strength as that of a fiber not containing inorganic carbonate by appropriately controlling the content of inorganic carbonate and the average particle diameter of the inorganic carbonate fiber. Can do. The tensile strength of the aromatic polyamide fiber of the present invention is preferably 15.0 cN / dtex or more, and more preferably 20.0 cN / dtex or more. When the tensile strength is less than 15.0 cN / dtex, the characteristics as an aromatic polyamide as a high-strength fiber are lost, which is not preferable.

The “tensile strength” in the present invention refers to a value obtained by measurement under the following conditions based on ASTM method D885.
(Measurement condition)
Measurement sample length: 500 mm
Chuck pulling speed: 250mm / min
Initial load: 0.2 cN / dtex
Test start method: Slack start method

[Production stability in the spinning process]
The aromatic polyamide fiber of the present invention can improve the production stability in the spinning process by appropriately controlling the content of the inorganic carbonate and the average particle size of the inorganic carbonate fiber. The “production stability in the spinning process” in the present invention means that the frequency of yarn breakage when discharging a spinning solution (dope) from a nozzle is low in a 24-hour continuous spinning test. The aromatic polyamide fiber of the present invention can be continuously produced with almost no thread breakage.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, unless the range of this invention exceeds the summary, it is not limited to these at all.

<Measurement and evaluation method>
In Examples and Comparative Examples, the following items were measured and evaluated by the following methods.

[Tensile strength (cN / dtex)]
Using a tensile tester (Orientec Co., Ltd., trade name: Tensilon universal tester, model: RTC-1210A), measurement was performed under the following conditions based on the procedure of ASTM D885.
(Measurement condition)
Measurement sample length: 500 mm
Chuck pulling speed: 250mm / min
Initial load: 0.2 cN / dtex
Test start method: Slack start method

[Limited oxygen index (LOI value)]
Based on the JIS L 1091 E method, the measurement was performed under the following conditions.
(Measurement condition)
Specimen classification: No. E-2 Fabric creation method: Circular knitted fabric (23 wales / inch, 18 courses / inch)
Type of igniter heat source: JIS K2240 Type 1 No. 1 (LP gas)
The critical oxygen index is determined earlier in the following (a) or (b). (A) Combustion length when determining the critical oxygen index: 50 mm
(B) Combustion time when determining the critical oxygen index: 180 seconds

[Production stability in the spinning process]
In the 24-hour continuous spinning test, the frequency of yarn breakage when the spinning solution (dope) was discharged from the nozzle was evaluated according to the following criteria.
(Evaluation criteria)
◎: 0 to 1 time ○: 2 to 4 times △: 5 times or more ×: Cannot be spun

[Average particle size of inorganic carbonate in fiber]
An aromatic polyamide fiber is cut in a direction perpendicular to the fiber axis to prepare a section having a thickness of 90 nm, and the section obtained using a transmission electron microscope (TEM) is observed, and a range of 10 μm × 10 μm is randomly selected. The location was selected, the particle size of the existing particles was measured, and the average value was determined.

<Example 1>
As the inorganic carbonate, calcium carbonate (manufactured by Ube Material Co., Ltd., trade name: CS · 3N-A) was used.

[Adjustment of calcium carbonate dispersion]
Using a bead mill (trade name: Nano Grain Mill) manufactured by Asada Tekko Co., Ltd., an NMP dispersion (slurry) of calcium carbonate was prepared so as to be 6% by mass in N-methyl-2-pyrrolidone (NMP). At this time, 0.3 mm zirconia beads were used as media.

[Preparation of spinning solution (dope)]
The obtained calcium carbonate dispersion and NMP were placed in an NMP solution having a concentration of 6% by mass of copolyparaphenylene 3,4'-oxydiphenylene terephthalamide (aromatic polyamide having a copolymerization molar ratio of 1: 1). For the spinning, the content of calcium carbonate in the obtained spinning solution (dope) is 5% by mass based on the total mass of the aromatic polyamide, and stirred and mixed at a temperature of 80 ° C. for 4 hours. A solution (dope) was obtained.

[Production of aromatic polyamide fiber]
The obtained spinning solution (dope) is discharged from a spinneret with 667 holes and spun into an aqueous solution having an NMP concentration of 30% by mass through an air gap of about 10 mm to solidify the undrawn yarn. Obtained (semi-dry semi-wet spinning method). Subsequently, the obtained undrawn yarn was washed with water, dried, then drawn 10 times at a temperature of 500 ° C., and then wound up to obtain an aromatic polyamide fiber in which calcium carbonate was well dispersed.
The obtained aromatic polyamide fiber had a total fineness of 1100 dtex, a filament number of 667 filaments, and a single yarn fineness of 1.65 dtex / filament.

[Measurement / Evaluation]
Using the obtained fibers, the tensile strength, tensile modulus, critical oxygen index (LOI value), and average particle diameter of calcium carbonate were measured by the above measurement method. The results are shown in Table 1. Table 1 also shows the evaluation results of the production stability in the fiber spinning process.

<Example 2>
A calcium carbonate-containing aromatic polyamide fiber was obtained in the same manner as in Example 1 except that the calcium carbonate content was added at a ratio of 10% by mass with respect to the total mass of the aromatic polyamide. Various measurements and evaluations were performed on the obtained fibers in the same manner as in Example 1. The results are shown in Table 1.

<Example 3>
A calcium carbonate-containing aromatic polyamide fiber was obtained in the same manner as in Example 1 except that the content of calcium carbonate was added at a ratio of 45% by mass with respect to the total mass of the aromatic polyamide. Various measurements and evaluations were performed on the obtained fibers in the same manner as in Example 1. The results are shown in Table 1.

<Example 4>
The content of calcium carbonate was added in a proportion of 10% by mass with respect to the total mass of the aromatic polyamide, and the same procedure as in Example 1 was conducted except that a bead mill was not used when adjusting the calcium carbonate dispersion. Thus, an aromatic polyamide fiber containing calcium carbonate was obtained. Various measurements and evaluations were performed on the obtained fibers in the same manner as in Example 1. The results are shown in Table 1.

<Comparative Example 1>
A calcium carbonate-containing aromatic polyamide fiber was obtained in the same manner as in Example 1 except that calcium carbonate was not added. Various measurements and evaluations were performed on the obtained fibers in the same manner as in Example 1. The results are shown in Table 1.

<Comparative example 2>
A calcium carbonate-containing aromatic polyamide fiber was obtained in the same manner as in Example 1 except that the calcium carbonate content was added at a ratio of 0.1% by mass with respect to the total mass of the aromatic polyamide. Various measurements and evaluations were performed on the obtained fibers in the same manner as in Example 1. The results are shown in Table 1.

<Comparative Example 3>
Spinning was carried out in the same manner as in Example 1 except that the content of calcium carbonate was added at a ratio of 55% by weight with respect to the total mass of the aromatic polyamide, but yarn breakage at the nozzle occurred frequently. A calcium carbonate-containing aromatic polyamide fiber could not be obtained.

  The aromatic polyamide fiber of the present invention retains mechanical strength such as tensile strength and tensile elastic modulus inherent in aromatic polyamide while having flame retardancy, and is excellent in production stability in the spinning process. Therefore, in addition to the various properties of the aromatic polyamide, it can be suitably used in fields where flame retardancy is required. The aromatic polyamide fiber of the present invention can be suitably used in fields (uses) such as fire fighting clothes, fire wall reinforcing agents, automobile-related reinforcing agents, and the like.

Claims (6)

  An aromatic polyamide fiber comprising 3% by mass or more and 50% by mass or less of an inorganic carbonate containing at least one metal selected from the group consisting of alkali metals and alkaline earth metals with respect to the entire fiber.   The aromatic polyamide fiber according to claim 1, wherein an average particle size of the inorganic carbonate in the aromatic polyamide fiber is 2.0 µm or less.   The aromatic polyamide fiber according to claim 1 or 2, wherein the inorganic carbonate is calcium carbonate.   The aromatic polyamide fiber according to any one of claims 1 to 3, wherein the aromatic polyamide is mainly composed of para-type aromatic polyamide.   The aromatic polyamide fiber according to claim 4, wherein the para type aromatic polyamide is copolyparaphenylene 3,4'-oxydiphenylene terephthalamide.   The aromatic polyamide fiber according to any one of claims 1 to 5, wherein a LOI value which is a limiting oxygen index is 26 or more.