JP2971338B2 - Easily dyeable meta-type aromatic polyamide fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a meta-type aromatic polyamide fiber which can be dyed with a cationic dye.

[0002]

2. Description of the Related Art Meta-type aromatic polyamide fibers have excellent heat resistance, flame retardancy and flame resistance because most of the molecular skeleton is composed of aromatic rings. Therefore, this fiber is suitable for use in industrial materials where heat resistance is required, clothing and interior use where flame retardancy and flame resistance are important, and especially clothing and bedding that make use of flame retardancy and flame resistance. Applications for the interior and interior fields are rapidly expanding. In these fields, it is common to use colored fibers, while meta-type aromatic polyamide fibers have excellent physical properties,
Since the polymer molecular chain is rigid, it is difficult to dye it by a usual method.

Conventionally, various improvements have been proposed for using meta-type aromatic polyamide fibers in these fields. For example, Japanese Patent Application Laid-Open No. 50-59522 proposes a colored fiber in which a specific pigment is contained in a meta-type aromatic polyamide fiber. At the time of replacement), it is difficult to cope with small lot production, and it is difficult to obtain fibers of various required hues. As means for improving the dyeing properties, Japanese Patent Application Laid-Open
Japanese Patent Publication No. -21406 proposes a method of mixing a polymer obtained by copolymerizing xylylenediamine, but the use of a polymer obtained by copolymerizing a polymer chain with a third component is intended to produce easily dyeable fibers. Therefore, there is a problem of an increase in cost such as a decrease in the operation rate of the polymerization apparatus. Furthermore, Japanese Patent Publication No. 52-43930 proposes a porous aromatic polyamide fiber having a specific range of pore diameter, void volume and density and improved dyeability, but the dyeability of this fiber is insufficient. In addition, it is difficult to set dyeing conditions, for example, a dyeing aid is required together with the dye at the time of dyeing, and it is difficult to treat a waste liquid after dyeing. Japanese Patent Application Laid-Open No. 62-78285 proposes a substantially amorphous aromatic polyamide fiber containing a surfactant, but this fiber falls off from the fiber during dyeing. There is a problem that sufficient dyeability cannot be obtained.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the conventional meta-type aromatic polyamide fibers and to reduce the cost of colored fibers which can be used in the fields of bedding, clothing and interior decoration. Another object of the present invention is to provide a meta-type aromatic polyamide fiber which can be provided quickly and has excellent dyeability.

[0005]

Means for Solving the Problems The present inventors have studied various additives in order to improve the dyeability of the meta-type aromatic polyamide fiber. As a result, the dyeability can be improved by adding onium alkylbenzenesulfonate. It has been found that the dyeability is further improved by adding a halogen-containing alkyl (phenyl) phosphate, and the present invention has been achieved.

Thus, according to the present invention, "an onium alkylbenzenesulfonate is used in an amount of 2.8 to 7.0 mol%, preferably further halogen-containing alkyl (phenyl) phosphate, based on the repeating units of the meta-type aromatic polyamide. Is composed of a meta-type aromatic polyamide composition containing 0.5 to 5.0% by weight based on the weight of the meta-type aromatic polyamide, and is subjected to hot drawing. Is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The meta-type aromatic polyamide to which the present invention is directed is one in which the aromatic ring constituting the main skeleton is substantially meta-linked by an amide bond. The third component may be copolymerized in a range of less than 15 mol% of the unit. Among them, a meta-type aromatic polyamide in which 85 mol% or more of all the repeating units are metaphenylene isophthalamide units, particularly polymetaphenylene isophthalamide is preferred.

[0008] Such a meta-type aromatic polyamide can be produced by a conventionally known interfacial polymerization method. The degree of polymerization of the polymer is 1.3 to 1.9 dl as an intrinsic viscosity (IV) measured using N-methyl-2-pyrrolidone as a solvent.
/ G is preferable.

In the present invention, it is essential that the above-mentioned meta-type aromatic polyamide contains an onium salt of alkylbenzene sulfonate. The content of the alkylbenzene sulfonate onium salt is 2.8 to 7.0 mol%, preferably 3.5, based on the unit.
モ ル 7.0 mol%. When the content is less than 2.8 mol%, a sufficient effect of improving the dyeing properties cannot be obtained in many cases. On the other hand, when the content exceeds 7.0 mol%, single yarn breakage increases in the spinning process.

The onium alkylbenzenesulfonate which is preferably used includes tetrabutylphosphonium hexylbenzenesulfonate, tributylbenzylphosphonium hexylbenzenesulfonate, tetraphenylphosphonium dodecylbenzenesulfonate, and dodecylbenzenesulfonate. Examples thereof include compounds such as tributyltetradecylphosphonate, tetrabutylphosphonium dodecylbenzenesulfonate, and tributylbenzylammonium dodecylbenzenesulfonate. Among them, tetrabutylphosphonium dodecylbenzenesulfonate or tributylbenzylammonium dodecylbenzenesulfonate is easily available, has good thermal stability, and has high solubility in N-methyl-2-pyrrolidone. Therefore, it is particularly preferable.

The meta-type aromatic polyamide composition containing the onium alkylbenzenesulfonate according to the present invention preferably further contains a halogen-containing alkyl (phenyl) phosphate. The meta-type aromatic polyamide fiber comprising such a composition has further excellent dyeability.

The halogen-containing alkyl (phenyl) phosphate referred to in the present invention is a halogenated alkyl phosphate, a halogenated alkyl phenyl phosphate, a halogenated phenyl phosphate, or the like. (Β-chloropropyl)
Phosphate, tris (2,3-dichloropropyl)
Compounds such as phosphate, trichloroethyl phosphate, phenyldichloropropyl phosphate, and tris (dichlorophenyl) phosphate can be mentioned. Among them, tris (β-chloropropyl) phosphate and tris (dichlorophenyl) phosphate are particularly preferable. preferable. These compounds have little effect of improving dyeability when blended alone with the meta-type aromatic polyamide, but have a unique effect of improving dyeability when used in combination with onium alkylbenzene sulfonate. Bring.

[0013] The content of the halogen-containing alkyl (phenyl) phosphate in the composition is 0.5 to 5.0% by weight, preferably 1.8 to 5.0% by weight, based on the weight of the meta-type aromatic polyamide. %, More preferably 3.0%
The range of about 5.0% by weight is desirable. If the amount is less than 0.5% by weight, a unique effect of improving dyeability cannot be obtained, while 5.0% by weight.
Exceeds, the effect of improving the dyeability does not increase so much,
Spots during dyeing become noticeable.

When mixing the meta-type aromatic polyamide with the onium alkylbenzene sulfonate and the halogen-containing alkyl (phenyl) phosphate, the meta-type aromatic polyamide is dissolved in a solvent to form a solution, and the onium alkylbenzene sulfonate is added thereto. A method in which a salt and a halogen-containing alkyl (phenyl) phosphate are added or mixed as a solution in an appropriate solvent or as it is without forming a solution, or a meta-type aromatic polyamide, an onium alkylbenzene sulfonate and a halogen-containing salt A method of mixing alkyl (phenyl) phosphate and then dissolving this mixture in a solvent can be used. The dope thus obtained is
Next, it is spun and heat drawn by a known method to form a fiber.

For example, as an example of a typical molding method, onium N-methyl-2-pyrrolidone (NMP) solution of polymetaphenylene isophthalamide is added with an onium salt of alkyl benzene sulfonate and a halogen-containing alkyl (phenyl) phosphate. To prepare a dope. The dope is extruded from a nozzle into an inorganic aqueous solution containing calcium chloride as a main component, coagulated, washed, stretched in boiling water, and further stretched on a hot plate at 300 to 325 ° C.
Perform oiling to obtain fibers. In the case of short fibers, the fibers are further crimped, cut and then spun to obtain easily dyeable spun yarns.

[0016]

The present invention will be described below with reference to examples. In addition, each characteristic value in an Example and a comparative example was measured by the following method.

<Dyeability> The crimped fiber is cut into a length of about 50 mm,
Estrol navy blue N-2RL (Sumitomo Chemical) 8
% Owf, acetic acid 0.3 g / l, sodium nitrate 2
Using a dye liquor consisting of 5 g / liter, the ratio of fiber to dye liquor was 1:40 and dyeing was carried out at 130 ° C. for 90 minutes. After staining
Hydrosulfite 1g / liter, Amilazine D1
g / L and 1 g / L of sodium hydroxide in a bath ratio of 1:40 at 80 ° C. for 30 minutes, followed by washing with water and drying. 1.3 g of this fiber is 31 m inside diameter
m, packed into a 13 mm deep cell, Minolta Spectrophotometer C
Using M-2002, the color was measured under the conditions of a 10-degree visual field, a D76 light source, and regular reflection removal, and the L * value was used as an index of staining.

<Intrinsic Viscosity (IV)> The polymer was dissolved in NMP at a concentration of 0.5 g / 100 ml and measured at 30 ° C. using an Ostwald viscometer. <Fineness> The fineness of the fiber was measured according to JIS-L-1015. <Strength and elongation> Fiber strength and elongation are based on JIS-L-1074, test length 20 mm, initial load 1/20 g / de, elongation speed 20 m
It was measured in m / min.

<Content of Onium Alkylbenzenesulfonate in Fiber> (NH ₄ ) ₂ S at a known concentration as a standard sample of sulfur
0.1 cc of an O ₄ aqueous solution is dropped on a filter paper for analysis, dried under vacuum, and a calibration curve is prepared by fluorescent X-ray quantitative analysis. About 5 fibers
0mg and about 20mg of calcium chloride
The solution is heated at 110 ° C. for 1 hour to dissolve the solution, and a certain amount (0.1 cc) is dropped on the filter paper for analysis, and then dried under vacuum. This sample was quantified by X-ray fluorescence analysis, and the sulfur concentration in the fiber was determined from the calibration curve previously determined, and this sulfur was converted to the content assuming that all of the sulfur was derived from onium alkylbenzenesulfonate.

<Halogen-Containing Alkyl (phenyl) phosphate Content in Fiber> A calibration curve was prepared by a fluorescent X-ray analysis from a standard sample of phosphorus having a known concentration in the same manner as described above, and the phosphorus concentration in the fiber was determined. This phosphorus is all halogen-containing alkyl (phenyl)
It is converted to the content as derived from phosphate.

Example 1 30 g of polymetaphenylene isophthalamide having an intrinsic viscosity (IV) of 1.35 dl / g was dissolved in 110 g of N-methyl-2-pyrrolidone (NMP), and 3.6 g of dodecylbenzenesulfone was further dissolved. A tetrabutylphosphonium acid salt was mixed, dissolved, and defoamed under reduced pressure to obtain a spinning dope.

The dope was heated to 85 ° C.
Wet spinning was performed in a coagulation bath from a spinneret having a diameter of 7 mm and 200 holes. The composition of the coagulation bath is 40% by weight of calcium chloride, NM
P5% by weight and water 55% by weight;
5 ° C. The yarn was run about 10 cm in a coagulation bath and pulled out at a speed of 6.2 m / min. Next, the yarn was washed with water, stretched 2.4 times in hot water at 95 ° C.
After drying on rolls at 1.degree. C., 1.75 on a hot plate at 320.degree.
It was doubled to obtain a 400 de / 200 filament drawn yarn. The total stretching ratio was 4.2.

Example 2 30 g of polymetaphenylene isophthalamide having an IV of 1.35 dl / g was dissolved in 110 g of NMP.
A solution prepared by dissolving 6 g of tributylbenzylammonium dodecylbenzenesulfonate in 2 g of NMP was mixed, dissolved, and defoamed under reduced pressure to obtain a spinning dope. Using this dope, spinning and drawing were performed in the same manner as in Example 1,
A drawn yarn of 00 de / 200 filament was obtained.

Example 3 5.7 g of tetrabutylphosphonium dodecylbenzenesulfonate was dissolved in 110 g of NMP.
30 g of polymetaphenylene isophthalamide having a V of 1.35 dl / g was dissolved therein, and defoamed under reduced pressure to obtain a spinning dope. Using this dope, it was spun and drawn in the same manner as in Example 1 to obtain a drawn yarn of 400 de / 200 filament.

Example 4 2.7 g of tetrabutylphosphonium dodecylbenzenesulfonate were dissolved in 110 g of NMP.
30 g of polymetaphenylene isophthalamide having a V of 1.35 dl / g was dissolved therein, and defoamed under reduced pressure to obtain a spinning dope. Using this dope, it was spun and drawn in the same manner as in Example 1 to obtain a drawn yarn of 400 de / 200 filament.

Comparative Example 1 6.0 g of tetrabutylphosphonium dodecylbenzenesulfonate was dissolved in 110 g of NMP.
30 g of polymetaphenylene isophthalamide having a V of 1.35 dl / g was dissolved therein, and defoamed under reduced pressure to obtain a spinning dope. Using this dope, it was spun and drawn in the same manner as in Example 1 to obtain a drawn yarn of 400 de / 200 filament.

Table 1 shows the results of Examples 1 to 4 and Comparative Example 1. In each of the examples to which the onium alkylbenzenesulfonate was added, the dyeability was improved. However, the effect of improving the dyeability of Example 4 was slightly small, while the improvement of the dyeability of Comparative Example 1 was sufficient, but the fiber strength was reduced and single yarn breakage during yarn production was increased.

[0028]

[Table 1]

Example 5 30 g of polymetaphenylene isophthalamide having an IV of 1.35 dl / g was dissolved in 110 g of NMP.
6 g of tetrabutylphosphonium dodecylbenzenesulfonate and 1.5 g of tris (β-chloropropyl) phosphate were mixed and dissolved, and defoamed under reduced pressure to obtain a spin dope. Using this dope, it was spun and drawn in the same manner as in Example 1 to obtain a drawn yarn of 400 de / 200 filament.

Example 6 30 g of polymetaphenylene isophthalamide having an IV of 1.35 dl / g was dissolved in 110 g of NMP.
A solution prepared by dissolving 6 g of tributylbenzylammonium dodecylbenzenesulfonate and 1.5 g of tris (β-chloropropyl) phosphate in 2 g of N-methyl-2-pyrrolidone was mixed with this, dissolved and degassed under reduced pressure. To obtain a spinning dope. Using this dope, it was spun and drawn in the same manner as in Example 1 to obtain a drawn yarn of 400 de / 200 filament.

Example 7 3.6 g of tetrabutylphosphonium dodecylbenzenesulfonate and 1.5 g of tris (dichlorophenyl) phosphate were dissolved in 110 g of NMP, and the polymetaphenylene isophthalate having an IV of 1.35 dl / g was further dissolved. 30 g of amide was dissolved in this, and defoamed under reduced pressure to obtain a spinning dope. Using this dope, it was spun and drawn in the same manner as in Example 1 to obtain a drawn yarn of 400 de / 200 filament.

Example 8 2.25 g of tetrabutylphosphonium dodecylbenzenesulfonate and tris (β-chloropropyl)
2.4 g of phosphate was dissolved in 110 g of NMP, and 30 g of polymetaphenylene isophthalamide having an IV of 1.35 dl / g was dissolved therein, followed by defoaming under reduced pressure to obtain a spinning dope. Using this dope, it was spun and drawn in the same manner as in Example 1 to obtain a drawn yarn of 400 de / 200 filament.

Comparative Example 2 3.6 g of tris (β-chloropropyl) phosphate
Was dissolved in 110 g of NMP, and IV was 1.35 dl.
/ G of polymetaphenylene isophthalamide / g was dissolved therein and defoamed under reduced pressure to obtain a spinning dope. Using this dope, spinning and drawing was performed in the same manner as in Example 1, and 400 d
A drawn yarn of e / 200 filament was obtained.

Example 9 Tetrabutylphosphonium dodecylbenzenesulfonate (2.25 g) and tris (β-chloropropyl)
Dissolve 0.45 g of phosphate in 110 g of NMP,
Further, 30 g of polymetaphenylene isophthalamide having an IV of 1.35 dl / g was dissolved therein and defoamed under reduced pressure to obtain a spinning dope. Using this dope, it was spun and drawn in the same manner as in Example 1 to obtain a drawn yarn of 400 de / 200 filament.

Example 10 3.6 g of tetrabutylphosphonium dodecylbenzenesulfonate and 0.9 g of tris (β-chloropropyl) phosphate were dissolved in 110 g of NMP, and the IV was 1.35 dl / g. 30 g of metaphenylene isophthalamide was dissolved therein, and defoamed under reduced pressure to obtain a spinning dope. Using this dope, it was spun and drawn in the same manner as in Example 1 to obtain a drawn yarn of 400 de / 200 filament.

Table 2 shows the measurement results of physical properties of the fibers obtained in Examples 5 to 10 and Comparative Example 2. In these examples using an alkylbenzene sulfonate onium salt and a halogen-containing alkyl (phenyl) phosphate in combination,
In each case, the dyeability is significantly improved. However, in Comparative Example 2, the dyeability was extremely poor, and it can be seen that tris (β-chloropropyl) phosphate itself has no effect of improving the dyeability. In Example 9, where the amount of the halogen-containing alkyl (phenyl) phosphate used was small,
Example 1 in which the effect of improving the dyeability was rather small, while the amount of the halogen-containing alkyl (phenyl) phosphate was large.
At 0, although the dyeability is sufficiently improved, the spots are large and the quality of the final product is likely to deteriorate.

[0037]

[Table 2]

[0038]

The heat-stretched easily dyeable meta-type aromatic polyamide fiber of the present invention described above impairs the excellent heat resistance, flame retardancy and flame resistance inherent in the meta-type aromatic polyamide fiber. It also has excellent dyeing properties and can be effectively used in the fields of bedding, clothing, and interiors that require coloring. In particular, the addition of halogen-containing alkyl (phenyl) phosphate not only improves the flame retardancy, but also dramatically improves the dyeability compared to the case where only the alkylbenzene sulfonate onium salt is added. This has the advantage that the dyeing cost can be reduced.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) D01F 6/90 331 D01F 6/90 301 D01F 6/60 371 C08G 69/32

Claims (6)

(57) [Claims] 1. A composition comprising a meta-type aromatic polyamide composition containing 2.8-7.0 mol% of an alkylbenzene sulfonate onium salt based on the repeating units of the meta-type aromatic polyamide, and subjected to hot stretching. Easily dyeable meta-type aromatic polyamide fiber. 2. The easily dyeable meta-type aromatic polyamide fiber according to claim 1, wherein the content of the halogen-containing alkyl (phenyl) phosphate is 0.5 to 5.0% by weight based on the weight of the meta-type aromatic polyamide. . 3. The easily dyeable meta-type aromatic polyamide fiber according to claim 1, wherein 85% by mole or more of the repeating unit of the meta-type aromatic polyamide is a metaphenylene isophthalamide unit. 4. The easily dyeable meta-type aromatic polyamide fiber according to claim 1, wherein the onium alkylbenzenesulfonate is an onium dodecylbenzenesulfonate. 5. The easily dyeable meta-type aromatic polyamide fiber according to claim 1, wherein the onium alkylbenzenesulfonate is tetrabutylphosphonium alkylbenzenesulfonate or tributylbenzylammonium alkylbenzenesulfonate. 6. The easily dyeable meta-type aromatic polyamide fiber according to claim 2, wherein the halogen-containing alkyl (phenyl) phosphate is tris (β-chloropropyl) phosphate or tris (dichlorophenyl) phosphate.