JPH0153395B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an oil agent suitable for acrylic synthetic fibers, particularly porous acrylic synthetic fibers. When spinning porous acrylic synthetic fibers,
The first obstacle is the reduction in operability due to the generation of static electricity during the carding process. This is presumed to be because the fibers are porous, so the oil agent that adheres to the surface immediately penetrates into the porous structure, reducing the amount of oil agent that adheres to the surface, which contributes to antistatic properties.
In JP-A-55-40829, the water retention rate is 0.033 to 0.1 based on the water retention rate of porous acrylic synthetic fibers.
We suggest applying double the amount. However, in this method, the tendency of excessive winding of the top rubber roller during drawing and spinning during high temperature and high humidity cannot be avoided, and operability is seriously impaired. In addition, air spinning requires a large amount of oil, so there is a drawback that a large amount of oil residue accumulates on the combing roller, which requires periodic cleaning. That is, the second obstacle in spinning porous acrylic synthetic fibers is the above-mentioned drawback caused by excessive use of oil. In addition, it is uneconomical because a large amount of oil is deposited, and the oil is removed during the dyeing process, which is not only wasteful in terms of resource conservation, but also causes problems in that the COD in the wastewater increases significantly, which is undesirable. The present inventors have completed the present invention as a result of intensive study and research in order to eliminate the conventional defects. An object of the present invention is to provide a spinning oil agent particularly suitable for porous acrylic synthetic fibers. That is, the present invention is based on the general formula (In the formula, R ₁ is an alkyl group having a straight chain or side chain having 8 to 22 carbon atoms, an alkylcarbonyl group, and a carbon number 2
In the alkylamidoalkylene group to which ~3 alkylene is added, R ₂ and R ₃ are alkyl groups having 1 to 3 carbon atoms, and R ₂ and R ₃ may be the same or different. R ₄ is H or an alkyl group having 1 to 8 carbon atoms,
Alkoxyalkyl group or aromatic alkyl group.
X represents a monovalent negative group selected from C ₂ H ₅ SO ₄ , C ₃ H ₇ SO ₄ , C ₄ H ₉ SO ₄ ) Quaternary ammonium salt cation activator (A), anion activity Agent (B)
and a nonionic activator (C) in a manner that satisfies the following formulas (1) to (4) (indicated by weight %). 2≦A≦50 (1) 20≦B (2) 40≦A+B≦90 (3) 10≦C (4) The cation activator applicable to the present invention is a quaternary ammonium salt cation represented by the above general formula. It is essential that the active agent (A) is a water-soluble compound. If a cationic activator that is not water-soluble is used, it will react with the sulfonic acid groups of the porous acrylic synthetic fiber and remain on the fiber surface, significantly reducing the water absorption performance, which is undesirable. If the amount of the cationic activator (A) is less than 2% by weight based on the total amount (purity) of the oil agent, the antistatic effect will not be sufficient and the amount of the oil agent attached to the porous acrylic synthetic fibers cannot be reduced. In addition, if the cationic activator (A) exceeds 50% by weight based on the total amount (pure content) of the oil, not only will its antistatic effect become saturated, but it will also react with the sulfonic acid group that is the dye-seating agent of porous acrylic synthetic fibers. This is undesirable as the proportion increases and it acts like a slowing agent during dyeing, prolonging the dyeing time. Further, as the anionic activator (B) applied to the present invention, any ordinary anionic activator may be used, but preferably the general formula and/or general _{formula R5} -O-( _CH2CH2O ) _l-
SO ₂ M (wherein R ₅ is an alkyl group or alkylene group having 7 to 22 carbon atoms, M is H, Na, K, and l is an integer of 0 to 30.
m and n are 1 or 2, and m+n=3). Anionic activator (B) is also commonly used as an antistatic agent for acrylic synthetic fibers, but when used for porous acrylic synthetic fibers, if the amount is less than 20% by weight, the antistatic effect will not be sufficient. However, as a lubricant for porous acrylic synthetic fibers, the antistatic effect of either the cationic activator (A) alone or the anionic activator (B) alone is insufficient and the amount of adhering oil cannot be reduced. When it is wet, there is a tendency for the sliver to stick to the top rubber roller of the spinning process or the top rubber roller of the spinning process, the sliver is disturbed due to the adhesion of oil to the coiler tube, and a large amount of oil residue accumulates on the combing roller during air spinning. This is undesirable as it reduces operability. However, by using a cationic activator (A) and an anionic activator (B) together, the antistatic effect was significantly improved even in porous acrylic synthetic fibers, and it was found that the amount of oil used could be significantly reduced. did. When a cationic activator (A) and an anionic activator (B) are used together, a synergistic effect appears, but the reason for this is that a certain type of complex exists between the quaternary ammonium salt cationic activator (A) and the anionic activator (B). It is thought that the rate of penetration into the porous structure decreases, and the amount of oil adhering to the surface, which contributes to antistatic properties, increases. In other words, it is essential to use the quaternary ammonium salt cation activator (A) and anion activator (B) together, and the sum of (A) and (B) must be 40% by weight or more based on the total amount of oil (purity). It needs to be 90% by weight or less. If (A) + (B) is less than 40% by weight, the antistatic effect will be insufficient, and if it exceeds 90% by weight, the antistatic effect will be satisfactory, but the convergence and smoothness will be insufficient, so avoid it. There must be. In addition, the nonionic activator (C) may be a compound whose main purpose is to improve convergence and smoothness, and it is necessary to contain it in an amount of 10% by weight or more based on the total amount of oil (purity). If the content of the nonionic activator (C) is less than 10% by weight, the cohesiveness or smoothness will be insufficient, leading to clogging of the coiler tube during the carding process and filament process during spinning, and the capacity of the can will be reduced, which is undesirable. . Nonionic activator C is not particularly limited, but generally polyethylene glycol (molecular weight 400-1000)
lauric acid ester, myristic acid ester,
Examples include palmitic acid ester, oleic acid ester, lauryl ether of polyoxyethylene (the number of moles is at most 30), cetyl ether, oleyl ether, castor oil ether, Brulonik type polyether, block type polyether, random type polyether, etc. One or more of these may be used. The amount of the oil agent used in the present invention is not particularly limited. In other words, the amount of oil is not particularly limited as long as there is no disturbance due to static electricity generated during the carding process during spinning, rolling of rollers during the drawing process or spinning process, but the oil of the present invention may also be used as a general oil. Similarly, if the amount of oil is too small, the antistatic properties will be lacking, and if the amount of oil is too large, problems with rolling will occur frequently, which is not preferable. The amount of the mixed oil agent for the porous acrylic synthetic fiber is preferably 0.3 to 1.5% by weight based on the weight of the porous acrylic synthetic fiber, and 0.01 to 0.032 times the water retention rate. Particularly preferably, the amount of oil is 0.02 to 0.03 times the water retention rate. Furthermore, in the case of porous acrylic synthetic fibers for air spinning applications, it is particularly preferable that the amount of oil agent be 0.02 to 0.025 times the water retention rate. That is, if an oil agent containing formulas (1) to (4) is applied to porous acrylic synthetic fiber according to the method of the present invention, the water retention rate of the porous acrylic synthetic fiber is It is surprising that it is possible to spin with the same spinnability as regular acrylic synthetic fibers simply by attaching an oil agent with a water retention rate of 0.01 to 0.032 times. The present invention will be explained in detail through Examples below.
Note that in the middle part of the examples, all % means parts by weight and weight %, and the water retention rate and the amount of oil adhesion were measured by the following methods, respectively. (Method for measuring water retention rate) DIN-53814 (Method for measuring oil amount) Weigh 5 g of the sample, place it in a Soxhlet extractor, add 120 ml of ethanol, and repeat extraction under boiling for 6 hours under reflux. The amount of oil attached to the fibers is determined from the amount of oil obtained. Example 1 90 parts of acrylonitrile:methyl acrylate:sodium allylsulfonate = 90.3:9.0:0.7
(%) of an acrylic polymer and 10 parts of cellulose acetate to form a polymer with a polymer concentration of 27%.
The spinning stock solution dissolved in dimethylformamide was dimethylformamide:water = 50:41.
(%), spun in a coagulation bath at 15°C, subjected to primary stretching 5 times, dried in a heated roller dryer at 130°C,
Next, the second stretching was carried out by 1.2 times at 110°C with moist heat.
As shown in the table, 0.6% oil was applied. Thereafter, crimping was applied, and a fiber of 1.5 de was obtained after crimping.
The water retention rate of the fiber was 30%. In addition, the fiber is 51
The amount of electricity generated was measured by cutting the sample into 20°C x 50% RH and applying it to a card at 25rpm under humidity control. In addition, the top clearer of the 30°C x 80% RH humidity-controlled premixed strip material was removed and the number of times it was rolled around the roller was measured.

【table】

[Table] Example 2 Polymers with different ratios of acrylic polymer and cellulose acetate having a composition of acrylonitrile: methyl acrylate: 2 acrylamide 2 methyl propane sulfonate sodium = 90:9:1 (%) as shown in Table 2. A dimethylformamide solution with a combined concentration of 27% was used as the spinning stock solution, dimethylformamide:water = 55:45
(%), spun out during coagulation and melting at 18°C, first stretched 5 times, dried in a hot roller dryer at 130°C, then second stretched 1.2 times at 110°C with wet heat, octyldimethylbenzylisopropyl Sulfate:
Potassium cetyl phosphate salt: (POE) 15 Potassium lauryl phosphate salt: (POE) 3 cetyl ether = 15:40:30:15 (%) oil was deposited as shown in Table 2. Thereafter, crimping was applied, and a 1.5 d fiber was obtained after crimping. The static electricity generated in the carding process and the winding test in the drawing process were conducted in the same manner as in Example 1.

【table】

【table】

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ is an alkyl group having a straight chain or side chain having 8 to 22 carbon atoms, an alkylcarbonyl group, and a carbon number 2
In the alkylamidoalkylene group to which -3 alkylene is added, R ₂ and R ₃ are alkyl groups having 1 to 3 carbon atoms, and R ₂ and R ₃ may be the same or different. R ₄ is H or an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group, an aromatic alkyl group, and X is
1 selected from C ₂ H ₅ SO ₄ , C ₃ H ₇ SO ₄ , C ₄ H ₉ SO ₄
A quaternary ammonium salt cationic activator represented by
(A), general formula and/or R ₅ -O-(CH ₂ CH ₂ O) _l -SO ₃ M (wherein R ₅ is an alkyl group or alkylene group having 7 to 22 carbon atoms. M is H, Na, K, l is 0 to 30 integers.
m and n are 1 or 2, and m+n=3. An oil agent for acrylic synthetic fibers containing an anionic activator (B) and a nonionic activator (C) represented by: 2. The oil agent according to claim 1, which contains at most 10% by weight of a cationic activator and/or an amphoteric activator other than the cationic activator (A).