JPS6157864B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aromatic polyamide fiber composition having improved dyeability and excellent heat resistance. Fully aromatic polyamides are known to be suitable for a wide range of applications. It has a higher softening point and melting point than aliphatic polyamide, and not only has excellent heat resistance such as strength retention at high temperatures, morphological stability, and decomposition resistance, flame resistance, and flame retardancy, but also chemical resistance. It has extremely desirable physical and chemical properties such as electrical properties, mechanical properties such as strength and Young's modulus, and is heat resistant, flame retardant, flame retardant fiber, high strength, high Young's modulus fiber, film, and molding material. Suitable for uses such as. However, when this wholly aromatic polyamide is used as fiber, it has the disadvantage that it cannot be easily dyed by ordinary dyeing methods due to its high degree of orientation and crystallinity. Therefore, for applications that require its excellent properties, uncolored wholly aromatic polyamide fibers are used as electrical insulating materials for motors, transformers, etc., industrial applications such as filter bags, heating tubes, and other applications. It is strongly desired to provide easily dyeable aromatic polyamide fibers for textile fibers where widely accepted and fashionable colors are considered important in textiles where aesthetic elements are not required. The object of the present invention is to improve the poor dyeability of aromatic polyamides while maintaining their excellent properties as much as possible. Conventionally, one of the methods for improving the dyeability of aromatic polyamides is to use polyamide copolymers that have functional groups that have an affinity for dyes, such as sulfone groups, tertiary amino groups, or quaternary ammonium groups in their polymer chains. Method of obtaining fibers (Special Publication No. 45-34777, Special Publication No. 52
-43930) and a method of obtaining fibers from a composition comprising such a polyamide copolymer and a wholly aromatic polyamide is known (Japanese Patent Publication No. 49-43930).
32658, Special Publication No. 49-32659, Special Publication No. 49-33594, Publication No. 8106 of No. 50-8). However, although the fibers obtained by these methods have improved dyeability, they are significantly inferior in thermal properties, which are most required for the use of these types of fibers. In order to improve the above-mentioned drawbacks, the inventors of the present invention aimed to improve the poor dyeability of wholly aromatic polyamide fibers to a practical level, and to achieve the excellent thermal properties of wholly aromatic polyamide fibers. As a result of extensive research into compositions that can obtain fibers that retain their properties and methods for producing the fibers, the present invention has been achieved. That is, the present invention is a composition comprising 95 to 50% by weight of polymetaphenylene isophthalamide (A) and 5 to 50% by weight of polyamide (B). (However, polyamide
In (B), the amine component consists of 40 to 100 mol % of phenylene diamine having at least one halogen nucleus substituent and 60 to 0 mol % of aromatic diamine, and the acid component consists of aromatic dicarboxylic acid. ) The composition of the present invention is a composition of polymetaphenylene isophthalamide (A) and polyamide (B) consisting of halogen-substituted phenylene diamine, aromatic diamine, and aromatic dicarboxylic acid, but the proportion of the former is (A) is preferably 95 to 50% by weight, and the latter (B) is preferably 5 to 50% by weight. In compositions in which the proportion of the latter (B) is less than 5% by weight, the fibers obtained therefrom may be heated at 300°C.
Even if the thermal properties such as the heat shrinkage rate are satisfied, the dyeability is significantly reduced. Also, the ratio of the latter (B) is 50
Even if the composition is larger than % by weight, the dyeability of the resulting fiber is satisfactory;
Its thermal properties such as heat shrinkage rate at 300°C are significantly reduced. A more preferable proportion of the composition varies depending on the composition of the latter polyamide (B), but generally the proportion of the latter (B) is 5 to 30% by weight, most preferably
10-25% by weight. One of the components of the composition of the present invention is a polyamide (B) containing 35 to 100 mol% of halogen substituted phenylene diamine and 65 to 0 mol% of aromatic diamine as an amine component and an aromatic dicarboxylic acid as an acid component. Yes, but
The number of halogen substituents in the halogen nucleus-substituted phenylenediamine, which is the amine component of the polyamide (B), is 4.
The number is at least 1, preferably 2 or less, and more preferably 1. Examples of the halogen substituent include chlorine, bromine, iodine, and fluorine, with chlorine and bromine being preferred, and chlorine being more preferred. Specific examples include 2,4-diaminochlorobenzene, 2,6-diaminochlorobenzene, 3,5-
Diaminochlorobenzene, 2,6-diamino-
Examples include 1,4-dichlorobenzene, chlorparaphenylenediamine, 2,5-diamino-1,4-dichlorobenzene, and mixtures thereof. Most preferred is 2,4-diaminochlorobenzene. The aromatic diamine which is another amine component of the polyamide (B) includes phenylene diamine,
Examples include naphthylene diamine, biphenylene diamine, diphenylthioether diamine, diphenyl ether diamine, diphenylmethane diamine, and diphenyl sulfone diamine. Specific examples of such aromatic diamines include paraphenylenediamine, metaphenylenediamine, 2.4
-tolylenediamine, 2,6-tolylenediamine and mixtures thereof, 2,6-naphthylenediamine, 4,4'-biphenylenediamine, 4.
4'-diaminophenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, etc. . Preferably paraphenylenediamine, metaphenylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine and mixtures thereof, 4,4'-diaminodiphenylsulfone,
Examples include 3,3'-diaminophenyl sulfone and 4,4'-diaminodiphenyl ether. More preferred are metaphenylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, and mixtures thereof. Further, examples of the aromatic dicarboxylic acid which is the acid component of the polyamide (B) include phenylene dicarboxylic acid, naphthalene dicarboxylic acid, and mixtures thereof. The hydrogen atom of the benzene nucleus of these aromatic dicarboxylic acids may be replaced by a substituent that does not react with the acid halide group or amino group. Such substituents include lower alkyl, phenyl, carbalkoxy, nitro, thioalkyl, and the like. Specific examples of such aromatic dicarboxylic acids include terephthalic acid, monochloroterephthalic acid, dichloroterephthalic acid, tetrachloroterephthalic acid,
These include methyl terephthalic acid, isophthalic acid, and 2,6-naphthalene dicarboxylic acid. Preferred are terephthalic acid, isophthalic acid, and 2,6-naphthalene dicarboxylic acid, and more preferred are terephthalic acid and isophthalic acid. The amine component of the polyamide (B) preferably has a ratio of 35 to 100 mol% of halogen substituted phenylene diamine and 65 to 0 mol% of aromatic diamine. If the amount of phenylenediamine substituted with a halogen nucleus is less than 35 mol %, the stainability will be significantly reduced. The proportion of halogen-substituted phenylenediamine varies depending on the type and proportion of other aromatic diamines and aromatic dicarboxylic acids constituting the polyamide (B), but generally 40
More preferably 100% by mole, most preferably 70% to 100% by mole. Logarithmic viscosity IV is used as a measure of the degree of polymerization of a polymer. IV is determined by measuring a solution of a polymer dissolved in concentrated sulfuric acid at 30°C and using the formula below. IV=In ηr/c c=polymer concentration polymer g/concentrated sulfuric acid dl The IV of the polyamide (B) is preferably 0.1 or more.
The polyamide (B) can be obtained by conventional methods for synthesizing polyamides, such as solution polymerization, interfacial polymerization, melt polymerization, and solid phase polymerization. Preferred methods are solution polymerization and interfacial polymerization. Further, the aromatic dicarboxylic acid constituting the polyamide (B) is used in the polymerization as a dicarboxylic acid or as an active derivative such as an ester or an acid halide. Preferred are acid halides, more preferred are acid chlorides. Polymetaphenylene isophthalamide (A), which is one component of the composition of the present invention, may be copolymerized with another diamine or dicarboxylic acid as a copolymerization component of up to 10 mol% of the total diamine and dicarboxylic acid components. . Furthermore, the composition of the present invention may contain various polymeric additives such as light stabilizers, flame retardants, crosslinking agents, etc. for the purpose of improving its properties. Any method may be used to produce the composition of the present invention, but a polymer solvent such as N.N'-dimethylformamide, N.N'-
It is preferable to mix and dissolve the required amount in a basic amide solvent such as dimethylacetamide or N-methyl-2-pyrrolidone to prepare a molding solution to obtain molded compositions such as fibers, films, and fibrids. The mixed solution may also be prepared by any method. Any method may be used, such as mixing mutually dissolved polymer solutions, dissolving and mixing one polymer in one solution, or mixing polymers in powder form and then dissolving them at the same time. The mixed solution can also be obtained by mixing and dissolving in a solution obtained from solution polymerization, or by previously dissolving one of the polymers in a polymerization solvent before solution polymerization. The method for producing fibers of the composition of the present invention includes 95 to 50% by weight of polymetaphenylene isophthalamide (A) and 40 to 100 mol% of halogen substituted phenylenediamine.
Polyamide (B) containing 60 to 0 mol% of aromatic diamine as the amine component and aromatic dicarboxylic acid as the acid component
5 to 50% by weight of the composition to form a fiber, the fiber is drawn to 1.5 to 5.0 times the original extrusion length, and the fiber is then subjected to tension heat treatment or It consists of hot stretching. The step of extruding the fiber to form a fiber may be carried out by any of a dry spinning method, a wet spinning method, or a semi-dry semi-wet spinning method using a solution of the composition,
It is preferable to undergo a water washing process before stretching. The fiber is then stretched to 1.5 to 5.0 times its original extrusion length, preferably in water or an aqueous solution containing a solvent or salt, or in steam at room temperature to 100°C. Furthermore, after drying, the fiber is subjected to tension heat treatment or hot stretching at a temperature of 280° C. or higher. In many cases, hot stretching is preferable here, and the preferred hot stretching ratio is 1.05 to 5.00.
It's double. The composition of the present invention can be manufactured as described above depending on the proportion of the polyamide (B) containing a halogen nucleus-substituted phenylene diamine as a diamine component and the composition of the polyamide (B), which is one component in the composition. By appropriately selecting conditions, improved dyeing properties and
The fiber can have a preferable heat shrinkage rate of 300°C. Thermal shrinkage rate at 300℃ was taken as a measure of the heat resistance of fibers. The value of the heat shrinkage rate in the examples and comparative examples is defined by the following formula by measuring a certain length (l ₀ ) of the fiber and measuring the length (l) after relaxing treatment for 30 minutes in an atmosphere of 300 ° C. It is. Heat shrinkage rate at 300°C (S ₃₀₀ ) = l ₀ - l/l ₀ × 100 (%) In addition, in order to show the difference in dyeability of fibers, after dyeing under the following dyeing conditions, wash thoroughly with water, and dye with sodium carbonate. The K/S of the dried fiber sample was measured by soaping with an aqueous solution of 0.5 g dissolved in 300 ml of water at 80° C. for 30 minutes, and the K/S values are described in the Examples and Comparative Examples. Fiber sample 10.0g Dye Supranol Blue GL 0.6g Ammonium sulfate 22.5g Acetic acid 6.0g Dyeing aid paraphenylphenol 2.0g Water 300ml Dyeing temperature and time 130℃ x 90 minutes K/S value is constant for well-opened fibers The reflectance (R) of light with a wavelength of 500 mμ was measured using a spectrophotometer by packing the amount into a cell of a certain size and using the following formula. K/S=(1-R) ² /2R Fibers made of the composition of the present invention are not limited to the above-mentioned acid dyes, but can also be practically used with dyes of other colors and various other dyes (such as cationic dyes). It has improved dyeability that allows it to be dyed to a high level. Examples and comparative examples of the present invention will be described below. Example 1 A solution of 17.824 g of 4-chloro-metaphenylenediamine (DACB) dissolved in 125 ml of tetrahydrofuran was added to 25.379 g of isophthalic acid chloride.
was dissolved in 125 ml of tetrahydrofuran and slowly added dropwise to the solution cooled to 0°C while stirring.
Subsequently, this slurry solution was added to an aqueous solution in which 21.2 g of anhydrous sodium carbonate was dissolved in 250 ml of water and cooled to 3° C. with vigorous stirring. Approximately after 3 minutes
After adding 300 ml of water and further stirring for 5 minutes, the polymer was taken out, washed three times with about 500 ml of water each time, and dried under reduced pressure at 100°C. The obtained polymer had an IV of 0.24. A spinning solution was prepared by dissolving 4.0 g of the polymer thus obtained and 20.0 g of polymer powder (IV1.80) of polymetaphenylene isophthalamide in 80 ml of N-methyl-2-pyrrolidone. Next, this spinning solution was passed through a nozzle with a hole diameter of 0.08 mm and a number of holes of 20.
Coagulation is performed by extrusion into an inorganic salt bath mainly composed of calcium chloride at 4.0 m/min, and after washing with water, the solidification is performed in boiling water.
It was stretched 230 times, then 1.80 times on a hot plate at 350°C, and wound up with a winder. The fiber thus obtained has a strength of 4.1 g/de,
It had an elongation of 53%, a heat shrinkage rate of 7.5% at 300°C, and a K/S of 11.5. Comparative Example 1 Polymetaphenylene isophthalamide (I.
V.1.80) 21.0g of N-methyl-2-pyrrolidone
A spinning solution was prepared by dissolving in 79.0 g. Subsequently, this spinning solution was used in the same manner as in Example 1 to form a yarn with a hole diameter of 0.08 mm and a hole number of 20.
The nozzle was extruded at a speed of 4.0 m/min into an inorganic salt bath mainly composed of calcium chloride to coagulate it, and after washing with water, it was heated 2.30 times in boiling water and then heated on a hot plate at 350°C.
It was stretched to 1.80 times and rolled up with a winder. The fiber thus obtained has a strength of 4.9 g/de and an elongation of 45
%, heat shrinkage rate at 300°C was 4.0%, and K/S was 0.8. Examples 2 to 3, Comparative Example 2 A solution of 4-chloro-metaphenylenediamine (DACB) and metaphenylenediamine (MPD) as amine components dissolved in 125 ml of tetrahydrofuran according to the weights listed in the table was used as an acid component. The weight of isophthalic acid chloride listed in the table was dissolved in 125 ml of tetrahydrofuran and slowly added dropwise to the solution cooled to 0° C. while stirring. Subsequently, the obtained slurry liquid was added to an aqueous solution in which 21.2 g of anhydrous sodium carbonate was dissolved in 250 ml of water and cooled to 3° C. with vigorous stirring. After stirring for 3 minutes, about 250 ml of water was added and stirring was continued for an additional 5 minutes. Subsequently, the obtained polymer was washed three times with about 500 ml of water each time, and the washing process was repeated and dried at 100° C. under reduced pressure. The IV of the obtained polymer was as shown in the table. A spinning solution was prepared by dissolving 4.0 g of the polymer thus obtained and 20.0 g of polymer powder (IV1.80) of polymetaphenylene isophthalamide in 80 ml of N-methyl-2-pyrrolidone. Next, this spinning solution was passed through a nozzle with a hole diameter of 0.08 mm and a number of holes of 20 at a high speed.
Coagulation was carried out by extrusion into an inorganic salt bath mainly containing calcium chloride at 4.0 m/min, and after washing with water, the surface was immersed in boiling water.
Stretched to the stretching ratio described in (boiling water stretching ratio),
Subsequently, it was stretched on a hot plate at the temperature (hot plate temperature) listed in the table to the stretching ratio (hot plate stretching ratio) listed in the table, and wound up with a winder. The strength, elongation, and
The heat shrinkage rate at 300°C, K/S, is shown in the table.

[Table] Examples 4 to 8 Using the combinations and weights of the amine component and acid component monomers as described in Table 1, polymers were synthesized in the same manner as in Examples, and the obtained polymer 4.0
g and polymetaphenylene isophthalamide 20.0 g
A spinning solution was prepared in the same manner as in Example 1 from 80 ml of N-methyl-2-pyrrolidone, and yarn was spun in the same manner as in Example 1. The boiling water draw ratio, hot plate draw ratio, hot plate temperature, strength (g/d), elongation (%), heat shrinkage rate at 300°C (%), and K/S of the obtained fibers are shown in the table. . DACB: 4-chloro-metaphenylenediamine MPD: metaphenylenediamine TDA: toluylenediamine mixture (2,4-toluylenediamine/2,6-toluylenediamine = 20/80) TPC: terephthalic acid chloride IPC: Isophthalic acid chloride

【table】

[Table] Example 9 Poly-4-chloro-metaphenylene isophthalamide (I.
V.0.24) and polymetaphenylene isophthalamide
(A) (IV2.00) and the total polymer concentration is 20.5% by weight, and the blend ratio of the former polymer is shown below.
A spinning solution was prepared by dissolving it in N-methyl-2-pyrrolidone as described above. The spinning solution with each blend ratio was passed through a nozzle with a hole diameter of 0.09 mm and a number of holes of 100.
Coagulation is performed by extrusion into an inorganic salt bath mainly composed of calcium chloride at 11.3 m/min, and after washing with water, the solidification is performed in boiling water.
It was stretched 2.83 times, then 1.56 times on a hot plate at 350°C, and wound up with a winder. Strength, elongation, shrinkage rate at 300℃ of the obtained fibers,
K/S is shown in the table.

[Table] Example 10 A fiber obtained in exactly the same manner as in Example 1 (blending ratio 16.7%) is referred to as fiber sample A. Further, a fiber obtained in exactly the same manner as in Comparative Example 1 (blend ratio 0%) is referred to as fiber sample B. The results of dyeing fiber samples A and B with various dyes in the same bath are shown. It is clear that the dyeing properties of the fibers made of the composition of the present invention are excellent.

【table】

【table】

[Table] Example 11 178.24 g of 4-chloro-metaphenylenediamine (DACB) was added to 1250 ml of tetrahydrofuran.
Terephthalic acid chloride solution dissolved in 253.79
g was dissolved in 1250 ml of tetrahydrofuran and slowly added dropwise to the solution cooled to 0° C. while stirring. Subsequently, the obtained slurry solution was added to an aqueous solution in which 212 g of anhydrous sodium carbonate was dissolved in 2500 ml of water and cooled to 3° C. with vigorous stirring. After 3 minutes, add about 3.0% water and stir for about 2 minutes, then remove the polymer and add about 3.0% water each.
Washing was repeated several times and dried at 100°C under reduced pressure. The obtained polymer had an IV of 0.31. The polymer thus obtained and the polymer powder of polymetaphenylene isophthalamide (I.
V.1.80) was dissolved in N-methyl-2-pyrrolidone at each blend ratio listed in the table to prepare a spinning solution. Next, apply this spinning solution to a pore size of 0.08 mm and a number of pores.
It is extruded from a nozzle of 100 at a speed of 4 m/min into an inorganic salt bath mainly composed of calcium chloride, and coagulated.
After washing with water, it was stretched in boiling water to the boiling water draw ratio (DR ¹ ) listed in the table, then stretched to the draw ratio (DR ₂ ) listed in the table on a hot plate at the temperature listed in the table, and then stretched in a winder. I rolled it up. The K/S, heat shrinkage rate at 300°C (S ₃₀₀ ), strength, and elongation of each of the obtained fibers are shown in the table.

[Table] Examples 12 to 15 Polyamides were synthesized in exactly the same manner as in Example 1 except that 17.824 g of 4-chlormethphenylenediamine was replaced with the diamine shown in the table in the amount described. A spinning solution was prepared in exactly the same manner as in Example 1, and the results are shown in Table 1.

【table】

Claims (1)

[Claims] 1 Polymetaphenylene isophthalamide (A) 95~
50% by weight, and the amine component consists of 40 to 100 mol% of phenylenediamine having 1 to 4 halogen nuclear substituents and 60 to 0 mol% of other aromatic diamines, and the acid component consists of aromatic dicarboxylic acid. An aromatic polyamide composition comprising an aromatic polyamide (B).