JPS6134731B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a novel aromatic copolyamide having improved dyeability and excellent heat resistance. [Prior art] Aromatic polyamide, in which both the acid component and the diamine component are aromatic compounds, has a higher softening point and melting point than aliphatic polyamide, and has improved strength retention at high temperatures, morphological stability, and thermal decomposition. It not only has excellent heat resistance, flame resistance, flame retardance, etc., but also has extremely desirable physical and chemical properties such as chemical resistance, electrical properties, and mechanical properties such as strength and Young's modulus. This makes it suitable for use as heat-resistant, flame-retardant, flame-retardant fibers, high-strength, high-Young's-modulus fibers, and film molding materials. However, when fibers are made from this aromatic polyamide, there is a drawback that it cannot be easily dyed by ordinary dyeing methods due to its high degree of orientation and crystallinity. Therefore, aromatic polyamide fibers are widely used as electrical insulation materials in motors, transformers, etc., in industrial applications such as filter packs and heating tubes, and in other textiles that do not require coloring, and in the clothing and interior fields. Solution colored fibers are used (Special Publication No. 45688, Showa 51). However, as textile fibers for which fashionable colors are considered important, it is strongly desired to provide easily dyeable aromatic polyamide fibers. [Object of the Invention] The object of the present invention is to provide a polymer that maintains as much of the excellent properties of aromatic polyamide as possible while improving its poor dyeability. [Structure of the Invention] The present invention provides a dicarboxylic acid repeating unit consisting of at least one of the following formulas (A) and (B); At least one of the following formulas (C), (D), (E) and (F), (G)
consisting essentially of a diamine repeating unit consisting of at least one type of An aromatic copolyamide having an intrinsic viscosity of 1 to 4,
The total number of moles of the dicarboxylic acid repeating units is substantially equal to the total number of moles of the diamine repeating units, and the total number of moles of the diamine repeating units (F) and (G) is equal to the total number of moles of the diamine repeating units. 2-20% of the number
An aromatic copolyamide capable of forming fibers or films with improved dyeability, characterized by: The aromatic copolyamide of the present invention has the above formula (A) or (B) as a dicarboxylic acid repeating unit (acid component).
Contains one or both of the following. Further, the aromatic copolyamide of the present invention has at least one of the above formulas (C), (D), and (E) as a diamine repeating unit (diamine component).
It is a copolymer that necessarily contains at least one of the above formulas (F) and (G). The copolymerization ratio of the xylene diamine units of the above formulas (F) and (G) is 2 to 20 mol% of the total diamine repeating units.
It is necessary that If the total amount of xylene diamine units (F) and (G) is less than 2 mol %, the thermal properties will be excellent but the dyeability will be poor. If the total content of (F) and (G) is more than 20 mol%, the dyeability is excellent, but the thermal properties are poor and the properties as an aromatic polyamide are degraded.
The copolymerization ratio of (F) and (G) is 4 to 20 of the total repeating units.
Mol% is preferred. In addition, the copolyamide of the present invention can be prepared by dissolving 0.5 g of the copolyamide in 100 ml of 98% concentrated sulfuric acid at 30°C.
The intrinsic viscosity (ηinh) based on the value measured at
4, and those of 1 to 3 are particularly preferred. As mentioned above, the aromatic copolyamide of the present invention comprises:
At least one of isophthalic acid chloride and terephthalic acid chloride, metaphenylenediamine,
2 to 20 moles of at least one of 2,5-toluylene diamine, 2,4-toluylene diamine, para-xylylene diamine, and metaxylylene diamine to the total diamine. It can be produced by reacting at least two types of diamines selected to contain % with each other such that the number of moles of total acid chloride and the number of moles of total diamine are substantially equal. . Examples of combinations of the diamine and dicarboxylic acid chloride used to produce the aromatic polyamide of the present invention are shown in Table 1 below.

【table】

[Explanation of measured values]

(i) Intrinsic viscosity In the present invention, the degree of polymerization of aromatic copolyamide is expressed using intrinsic viscosity IV as a guideline. IV is determined by measuring the viscosity of a solution of a polymer dissolved in concentrated sulfuric acid at 30°C and using the formula below. IV=1nη/C C=polymer concentration (polymer g/concentrated sulfuric acid d) (ii) Dyeability As a guideline for dyeability, it is expressed as a K/S value. The sample was dyed using an acid dye at a temperature and time of 130°C x 90
After dyeing at a high temperature for 30 minutes, wash thoroughly with water, and dye with an aqueous solution of 0.5 g of sodium carbonate in 300 ml of water.
The K/S of the dried fiber sample was measured by soaping at ℃ for 20 minutes. The K/S value is determined by the following formula by packing a certain amount of well-opened fibers into a cell of a certain size and measuring the reflectance (R) of light at a wavelength of 500 mμ using a spectrophotometer. K/S=(1-R) ² /2R The staining conditions in Examples and Comparative Examples are as follows. Fiber sample 10.0g Dye Spranople-GL 0.6g Ammonium sulfate 22.5g Acetic acid 6.0g Dye paraphenylphenol 2.0g Water 300ml (iii) Heat resistance Thermal shrinkage rate was taken as a representative measure of the heat resistance of fibers. Also, temperature is a practical measure.
The temperature was 300℃. The heat shrinkage rate values in the Examples and Comparative Examples described below are based on a fiber with a constant length (l ₀ ) of 300
Length after relaxation treatment for 30 minutes in °C atmosphere
(l) is measured and defined by the following formula. Heat shrinkage rate at 300°C (S300) =l ₀ -l/l ₀ ×100 (%) [Effects of the invention] The aromatic copolyamide of the present invention as described above has better dyeability than conventional aromatic copolyamides. A dramatically improved fiber made of the aromatic copolyamide,
Molded products such as tapes and films can be dyed to a practical level with various dyes. Moreover, it maintains the excellent heat resistance and flame retardancy of an aromatic polyamide, making it useful in the clothing and interior fields that require heat resistance and flame retardancy. [Example] Next, Examples and Comparative Examples of the present invention will be described in detail. Comparative Example 1 and Examples 1 to 4 A solution of 32.485 g of isophthaloyl chloride (IPC) dissolved in 200 c.c. of tetrahydrofuran (THF)
(a) was cooled to 0°C. In addition, a solution (b) in which metaphenylenediamine (MPD) and/or metaxylylenediamine (MXD) is dissolved in THF200c.c. in the molar ratio and weight listed in Table 2, is cooled and vigorously stirred. It was slowly dripped onto (a). The obtained solution or slurry liquid (c) was added to anhydrous sodium carbonate.
A solution of 32.5 g dissolved in 400 c.c. of water and cooled to 5°C.
(d) while stirring vigorously. The precipitated polymer was taken, thoroughly washed with water, and dried. The intrinsic viscosity (IV) of the obtained aromatic copolyamide polymer is shown in Table 2. The polymer thus obtained was N-methyl-
It was dissolved in 2-pyrrolidone at the concentration shown in Table 2 to prepare a spinning stock solution. The spinning stock solution was extruded from a spinneret with a pore diameter of 0.08 mm and a number of holes of 100 at a speed of 4 m/min into an aqueous solution of inorganic salts mainly composed of calcium chloride, solidified, washed with water, and stretched in boiling water at the boiling water draw ratio listed in Table 2. After stretching and drying at (DR ₁ ), the film was further stretched at the hot stretching temperature listed in Table 2 and at the hot stretching ratio (DR ₂ ) listed in Table 2, and then wound onto a bobbin. The strength, elongation, heat shrinkage rate at 300°C (S ₃₀₀ ), and K/S of the obtained fibers are summarized in Table 2. It was confirmed that the aromatic copolyamide fibers according to the present invention (Examples 1 to 4) had a larger K/S value than the polymetaphenylene isophthalamide (Comparative Example 1), and had excellent dyeability. .

【table】

[Table] Examples 5 to 6 In Comparative Example 1 and Examples 1 to 4, terephthaloyl chloride (TPC) was used instead of isophthaloyl chloride (IPC) as the acid chloride,
Furthermore, as diamines shown in Table 3, metaphenylenediamine (MPD), 2,4-tolylenediamine (2,4-TDA) and/or 2,6-
Comparative Example 1 and Example 1 except that toluylene diamine (2,6-TDA) and meta-xylylene diamine (MXD) and/or para-xylylene diamine (PXD) were used and the molar ratios and weights listed in Table 3 were followed. Aromatic polyamides were polymerized in the same manner as in Examples 1-4. Then, a spinning stock solution was prepared in the same manner and fibers were obtained by spinning. The strength, elongation, heat shrinkage rate at 300°C (S ₃₀₀ ), and K/S of the obtained fibers are summarized in Table 3.

【table】

Claims (1)

[Claims] 1. A dicarboxylic acid repeating unit consisting of at least one of the following (A) and (B); At least one of the following (C), (D) and (E) and the following (F) and
A diamine repeating unit consisting of at least one type of (G), an aromatic copolyamide having an intrinsic viscosity of 1 to 4, the total number of moles of the dicarboxylic acid repeating units being substantially equal to the total number of moles of the diamine repeating units, and , wherein the total number of moles of the diamine repeating units (F) and (G) is 2 to 20 mol% of the total number of moles of the diamine repeating units, and is capable of forming a fiber or film with improved dyeability. Aromatic copolyamide.