JPS595124B2 - Axolonitrile fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention uses acrylonitrile fibers, more specifically, acrylonitrile as a main component, and copolymerization components of maiconic acid or butenetricarboxylic acid and a compound represented by the following formula (hereinafter referred to as compound A) of 0.3% each. The present invention relates to an acrylonitrile fiber containing a polymer in an amount ranging from 3 to 3 mol%, and having a crosslinked structure.

CH2=C-C 101N0CH2CH20H (However, in the above formula, R is H or an alkyl group having 1 to 4 carbon atoms.

)15-In general, acrylonitrile (AN) fibers have lower crystallinity than other synthetic fibers, such as polyamide or polyester fibers, so they have poor thermal stability and are prone to mechanical changes at high temperatures, resulting in poor heat resistance. A shortage has been pointed out.

C0 Various proposals have been made in the past to improve this drawback.

As one of these, a series of attempts have been made to improve the heat resistance of the fiber itself by introducing crosslinking bonds into □ type fibers, and in this case copolymerization of crosslinkable monomers is commonly used. However, when cross-linking monomers are copolymerized, the cross-linking reaction usually progresses easily during the polymerization and spinning process, and when cross-linking progresses during the polymerization process, the spinning stock solution gels and becomes difficult to spin, and when cross-linking progresses during the spinning process, stretching becomes difficult. There was a problem. Therefore, it is desirable to use a method in which the crosslinking reaction does not proceed during the polymerization and spinning process, but instead occurs during the drying or heat treatment process after yarn formation. For this purpose, for example, Japanese Patent Publication No. 46-33132 discloses that after wet-spinning an AN-based polymer containing the compound A used in the present invention in an amount ranging from 1 to 6 mol%, it is swollen in water and then spun with a strong acid. It has been proposed to treat with an aqueous solution containing , followed by drying at a temperature in the range of 100 to 200°C.

However, in the fiber yarn obtained by this method, a small amount of processing acid remains, which not only affects the subsequent yarn processing, but also causes the processing container to be corroded by the acid in the process using a strong acid aqueous solution. There is a problem with touching. Therefore, the present inventors proposed a method in which the crosslinking reaction does not proceed during the polymerization/forming process, but easily proceeds during the drying or heat treatment process after yarn formation, thereby imparting suitable heat resistance. The present invention was achieved as a result of intensive research into fiber films based on the above-mentioned fibers.

That is, an object of the present invention is to provide an AN-based fiber having a crosslinked structure with extremely excellent heat resistance. What is the AN-based fiber of the present invention? is the main component, itaconic acid or putentricarboxylic acid and Compound A are used as copolymerization components, and in Compound A, R is H or has 1 to 1 carbon atoms.
A preferred compound A is 2-hydroxyethyl methacrylate.

The amount of copolymerization in the total monomers of such copolymerization components is 0.3 to 3 mol%, preferably 0.5 to 2.0 mol%, and more preferably the amount (mol) of itaconic acid or butenetricarboxylic acid. should not exceed the amount (mol) of Compound A used. If the amount of each copolymer component is less than 0.3 mol%, crosslinking will be insufficient even if heat treatment is sufficient, and fibers with excellent thermal stability will not be obtained.On the other hand, if the amount is more than 3 mol%, crosslinking will occur before fiber formation. This is unsuitable because it progresses to the point where molding becomes difficult.

The AN-based fiber of the present invention may be prepared by copolymerizing the above-mentioned itaconic acid or butenetricarboxylic acid and Compound A with a small amount of an ionic monomer for imparting dyeability and an appropriate amount of another vinyl monomer for the purpose of changing physical properties, or by copolymerizing an appropriate amount of other vinyl monomers for the purpose of changing physical properties. It is also possible to blend polymers of

As a polymerization method for the polymer of the AN-based fiber of the present invention, either normal solution polymerization or water-based polymerization can be applied, but in the case of water-based polymerization, crosslinking reaction occurs because heat is added during the drying process of the polymer cake. In this respect, the solution polymerization method is advantageous because it can directly obtain a spinning stock solution.

Further, as the method for spinning and forming the polymer, any conventionally known method can be applied, regardless of whether it is a dry or wet method, but a wet method using a coagulation solution of the polymer in a solvent and water is particularly desirable.

The obtained coagulated yarn is subjected to treatments such as stretching and washing with water, and then dried at 100 to 200°C.

A high drying temperature is preferable, but if the drying temperature is too high, the fibers will become colored. The crosslinking reaction proceeds during this high temperature treatment, but in order to further advance the crosslinking reaction, it is preferable to perform a dry heat treatment step after drying. It goes without saying that various other methods well known to those skilled in the art may be employed in such spinning, molding, drying, and drying treatment steps. The fact that the fibers of the present invention are insoluble in common solvents such as dimethyl sulfoxide and dimethyl formamide indicates that they have a crosslinked structure.

The characteristic that this crosslinked structure is formed during the drying or heat treatment process after yarn formation is unique to the polymer of the present invention. Characteristics cannot be obtained, and itaconic acid or butenetricarboxylic acid alone,
Alternatively, this feature cannot be obtained even if Compound A is copolymerized alone, and this feature is obtained by using a system copolymer containing AN of the present invention as a main component, itaconic acid or butenetricarboxylic acid, and Compound A as copolymerization components. It is recognized only in

Moreover, the AN fiber obtained by the present invention has extremely excellent thermal stability, so even when a product using the AN fiber according to the present invention is heat-set, the texture does not change, and the product has a low Its effects are remarkable in terms of its elongation properties and anti-pilling properties.

The present invention will be specifically explained below with reference to Examples.

In this example, the creep curve was calculated by accurately weighing the sample to 60D using the usual method, pulling the fibers together, gripping one end, applying a load of 10y to the other end, and creeping in a heating bath kept at a predetermined temperature for 60 minutes. , which also shows creep recovery 30 minutes after weight removal. In addition, the creep rate (60 minutes) and creep recovery rate (30 minutes) were determined by the following equations. [In formula 1.

is the sample length (20 mm), 11 is the sample length after 60 minutes of creep, and 12 is the sample length after 30 minutes of creep recovery. [Reference Example 1] Acrylonitrile (AN)-itaconic acid (IA)-2-hydroxyethyl acrylate (HEA) was prepared by a solution polymerization method using azobisisobutyronitrile (AIBN) as a polymerization catalyst in dimethyl sulfoxide (DMSO).
), AN-butenetricarboxylic acid (BTCA)-2-hydroxyethyl methacrylate (HEMA), AN-A
、． AN-HEMAI and AN-acrylic acid (AH)
Each copolymer stock solution partially consisting of MA was prepared.

In polymerizing these stock solutions, the copolymerization amount of each of the copolymerization compositions other than AN based on the total monomers is 1 mol%.
And so. No gelation phenomenon was observed in any of these five stock solutions.

These polymerization stock solutions were precipitated into filaments in water, and the reprecipitated polymers were absolutely dried at about 120° C. in a hot air dryer, and the solubility of the dried polymers in DMSO was examined.

As shown in Table 1 below, the results showed that only the dry copolymerized polymers of AN-1AHEA and AN-BTCA-HEMA were insoluble in DMSO.

Example 1 A copolymer stock solution consisting of AN-HEMA-1A-sodium allylsulfonate (SAS) was prepared by a solution polymerization method using AIBN as a polymerization catalyst in DMSO.

In polymerizing this stock solution, the monomer charging ratio was AN97.
7 mol%, HEMA1. O mol%, IAl. O mol%,
SASO. 3 mol%, and the obtained polymer concentration was 22
．． The viscosity at 3% and 40° C. was 229 poise.
Similarly, AN94.7 mol%, methyl acrylate (M
EH) 5.0 mol%, SASO. A normal AN-based copolymer stock solution containing 3 mol % was prepared as a comparative product.

The polymer concentration at this time was 22.8%, and the viscosity at 40°C was 251 poise. These stock solutions have a pore size of 0.08
DMSO5 at 30℃ using a φMm, 400-hole cap.
After discharging and solidifying a 5% aqueous solution at a speed of 5 m/Mi, 9
Stretched 6 times in a DMSO3O% aqueous solution at 8°C, then stretched at 50°C.
The DMSO was removed by washing thoroughly with warm water. These fibers were subjected to drying heat treatment in a hot air dryer under predetermined conditions, ie, 140° C. for 20 minutes and 160° C. for 30 minutes while giving 10% relaxation, to obtain dry fibers of 2.9 d each.

When these dry fibers were subjected to a dissolution test in heated DMSO, AN/HEMA/IA/SA according to the present invention was found.
The AN-based fibers consisting of S were no longer dissolved and remained in almost perfect fiber form.

In contrast, the usual A-based polymer consisting of AN/MEA/SAS was easily dissolved. Also, the temperature of the dry fiber at 90°C
The creep line, creep rate (60 minutes) and creep recovery rate (30 minutes) in water and silicone oil at 140°C were investigated, and the results were shown in Figures 1 and 2 and Table 2.

Figure 1 shows the creep curve in water at 90°C.
140 AN/HEMA/IA/SAS copolymer fibers
°C, dry heat treated for 20 minutes (product of the present invention), 2 is A
N/HEMA/IA/SAS copolymer fiber at 160℃,
Those subjected to dry heat treatment for 30 minutes (product of the present invention), 3 is AN/M
EA/SAS copolymer fiber was dry heat treated at 140° C. for 20 minutes (comparative product).

FIG. 2 is a creep curve in silicone oil at 140° C., and 1 to 3 are the same as in FIG. 1.

As is clear from these results, the AN-based fibers according to the present invention are less deformed at high temperatures than normal AN-based fibers.

Furthermore, when the dry fibers were steam-treated at 110°C for 30 minutes, the strength properties were investigated using a strength and elongation measuring device manufactured by Toyo Sokki Co., Ltd., and the results were as shown in Figures 3 and 4 and Table 3. The results were shown.

Figure 3 shows the strength and elongation curve of dry fibers (before steam treatment).
1 contains 14 AN/HEMA/IA/SAS copolymer fibers
Dry heat treated at 0℃ for 20 minutes, 2 is AN/HEMA
/ IA/SAS copolymer fiber subjected to dry heat treatment at 16'C for 30 minutes (product of the present invention), 3 is AN/MEA/SA
This is an S copolymer fiber subjected to dry heat treatment at 140° C. for 20 minutes (comparative product).

FIG. 4 is a strength and elongation curve obtained when dry fibers are steam-treated at 110° C. for 30 minutes, and 1 to 3 are the same as in FIG. 3. As is clear from these results, A according to the present invention
N-based fibers are relatively unaffected by steaming treatment,
In particular, it can be seen that the low elongation properties of these fibers are maintained as they are.

Example 2 In the same manner as in Example 1, the concentrations of IA and HEMA were changed as shown in Table 4 to prepare polymerization solutions, and these were mixed with DMSO using a nozzle with a hole diameter of 0.08 mmφ and 400 holes. - After spinning in an aqueous spinning bath and stretching 6 times, washing with water and heating at 160°C while giving 10% relaxation in a hot air dryer.
Dry fibers were obtained by dry heat treatment for 30 minutes.

The solubility of these dry fibers in DMSO was investigated, and the gel fraction was determined as shown in Table 4.

Furthermore, AN93. O mol%-IA3.5 mol%-HEM
In the case of A3.5 mol % preparation conditions, crosslinking progressed slightly in the stock solution, making it difficult to spin, and the resulting fibers also became sticky, making them impractical as fibers. Example 3 In the same manner as in Example 1, AN97.7 mol% 2-hydroxyethyl acrylate (HEA) 1.0 mol%-1
A1.0 mol%-SASO. A copolymer stock solution containing 3 mol % was prepared.

The resulting stock solution had a polymer concentration of 22.5% and a viscosity of 269 poise at 40°C. This has a hole diameter of 0.08mm.
The fibers were spun in a DMSO monoaqueous spinning bath using a nozzle with φ and 400 holes, stretched 6 times, washed with water, and subjected to 10% relaxation in a hot air dryer under predetermined conditions: 140°C, 30 minutes, 150°C.
Dry heat treatment was performed at 160° C. for 30 minutes and at 160° C. for 30 minutes to obtain dry fibers. When the creep curve, creep rate (60 minutes) and creep recovery rate (30 minutes) of these dry fibers in water at 90°C were investigated, the results were shown in FIG. 5 and Table 5. Figure 5 shows the creep curve of dry fibers in 90°C water;
No. 3 is the same copolymer fiber that was dry heat treated at 40° C. for 30 minutes.

As is clear from these results, it was found that the AN-based fiber according to the present invention has extremely excellent stability in the heating process, and as the heat treatment temperature increases, this property is further accentuated.

Example 4 In the same manner as in Example 1, AN97.7 mol% butenetricarboxylic acid (BTCA) 0.5 mol%-SASO. A copolymer stock solution containing 3 mol % was prepared.

The polymer concentration of the obtained stock solution was 21.4%, and the viscosity at 40°C was 216 poise. This hole diameter is 0.08m.
77! Spun in a DMSO monoaqueous spinning bath using a nozzle with φ and 400 holes, stretched 6 times, washed with water, and heated to 10% in a hot air dryer.
Dry heat treatment was carried out under predetermined conditions, namely, 140° C. for 30 minutes, 150° C. for 30 minutes, and 160° C. for 30 minutes, while providing relaxation, to obtain dry fibers.

The solubility of these fibers in DMSO was investigated, and the percentage of the fibers that did not dissolve in DMSO was determined as the gel fraction, and the results were shown in Table 6.

[Brief explanation of drawings]

Figure 1 shows the creep curve of dry fibers in water at 90°C, and 1 shows the AN/HEMA/IA/SAS copolymer fibers subjected to dry heat treatment at 140°C for 20 minutes (product of the present invention).
, 2 is AN/HEMA/IA/SAS copolymer fiber 1
60°C, 30 minutes dry heat treatment (invention product), 3 is AN/ME) A/SAS copolymer fiber at 140°C, 20 minutes
This is a product subjected to dry heat treatment for a minute (comparative product). FIG. 2 shows the creep curve of dry fibers in silicone oil at 140° C., and 1 to 3 are the same as in FIG. 1. Figure 3 shows the strength and elongation curve of dry fibers (before steam treatment).
1 contains 14 AN/HEMA/IA/SAS copolymer fibers
0°C, dry heat treated for 20 minutes (product of the present invention), 2 is A
N/HEMA/IA/SAS comonopolymer fiber at 160℃
, 30 minutes dry heat treated (product of the present invention), 3 is AN/
'MEA/SAS copolymer fibers were subjected to dry heat treatment at 140° C. for 20 minutes (comparative product). FIG. 4 is a strength and elongation curve obtained when dry fibers are steam-treated at 110° C. for 30 minutes, and 1 to 3 are the same as in FIG. 3. Figure 5 shows the creep curves of dry fibers in 90°C water; 1 is the AN/HEA/IA/SAS copolymer fiber treated with dry heat at 140°C for 30 minutes, and 2 is the same copolymer fiber at 150°C. , 30 minutes dry heat treatment, and 3 is the same copolymer fiber treated at 160° C. for 30 minutes dry heat treatment.

Claims (1)

[Scope of Claims] 1 Consisting of a polymer containing acrylonitrile as a main component and containing itaconic acid or butenetricarboxylic acid as copolymerization components and a compound represented by the following formula in an amount ranging from 0.3 to 3 mol%, respectively, Acrylonitrile fiber that also has a crosslinked structure. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the above formula, R is H or an alkyl group having 1 to 4 carbon atoms.)