JPS5834561B2 - Production method of animal hair-like acrylic synthetic fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing acrylic synthetic fibers that have animal hair-like texture and texture, and in particular, are easily crimped.

Acrylic synthetic fibers have excellent processability, dyeability, and texture, and in the field of short fibers in particular, we have developed unique materials and products as spun yarn with a wool-like texture, and our applications are expanding. I came.

However, in the field of acrylic fibers such as high pile, boa, seal, raised products, wigs, etc., if minute crimps or "wavy" remain in the fibers, the product value will be significantly impaired, so crimps must be completely removed. However, acrylic fibers are prone to crimping and ``waving'', and even if this is temporarily removed, crimping and ``undulation'' will occur if they are subjected to hot water treatment such as dyeing or mechanical entanglement. It has the property of causing the undulation to recur.

The purpose of the present invention is, first, to make the hair easy to remove crimps and "undulations" during hot water dyeing treatment, and second, to make the hair easy to remove crimps and "undulations" even during mechanical stretching treatments such as raising and polysoaring. Our goal is to provide acrylic fibers that are flexible and have a texture that closely resembles animal hair.

Up to now, the following methods have been known as techniques for achieving the above objectives.

That is, this is a method in which an acrylic polymer is spun by a conventional method, the resulting fibers are stretched, heat treated, and then subjected to secondary stretching at high temperature and high pressure to achieve crimping.

However, this method involves equipment and operational difficulties due to high temperatures and high pressures, and heat discoloration may occur due to high temperatures, and it is not very effective at removing crimps or "undulations" from the resulting fibers themselves. However, small creases and ``undulations'' remained.

Furthermore, since secondary stretching is performed at a high temperature, shrinkage during dyeing hot water treatment, etc. is large, which cancels out the effect of crimping, making it unsuitable for use as non-shrinkable spun yarn other than bulky yarn.

In order to achieve the above object, the inventors of the present invention have conducted various studies, and in particular, as a result of detailed examination of fiber drawing and heat treatment conditions, etc.
To find a method for producing the acrylic fiber of the present invention, which is easy to remove crimps and waviness during hot water treatment or mechanical stretching treatment, has no shrinkage, has good hair handling, and has an animal hair-like texture. It's arrived.

That is, the present invention provides at least 60% by weight (% means % by weight unless otherwise specified below).

) A polymer containing acrylonitrile of
The fibers are stretched 1.0 to 1.5 times under steam or dry heat at 0°C or higher, and then stretched between a pair of rollers at 50 to 120°C.
This is a method in which the material is heated and pressurized to 11 to 10 kg/crA, and then mechanically crimped after shrinkage heat treatment in a straight line.

The acrylonitrile polymer of the present invention contains polyacrylonitrile or at least 60% acrylonitrile, and other components are not particularly limited, but usually contain less than 40% methyl acrylate, vinyl acetate, acrylamide, or vinyl chloride. , a copolymer or a mixed polymer containing a monomer imparting thermoplasticity such as vinylidene chloride, or a monomer imparting dyeability.

In particular, in order to match the dyeability with animal hair, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dibutylaminoethyl methacrylate, methacryloxyethyltrimethylammonium chloride, methacryloxyethyltrimethylammonium sulfate, 2-hydroxy-3-methacryloxypropyl Strongly basic monomers such as trimethylammonium chloride are particularly preferred as dye-imparting monomers because they can be used with the same type of dye as animal hair.

Of course, in order to prevent thermal coloring due to the introduction of strong basic monomers,
For example, a heat stabilizer such as hydroxyurea may be used.

The spinning dope used in the present invention is prepared by dissolving the acrylonitrile polymer in a known organic or inorganic solvent using a conventional method.

In the present invention, spinning requires wet spinning using an aerial traveling system.

That is, without directly discharging the stock solution into the coagulation bath, it is once heated to about 0.
If it is placed in a coagulation bath after running in the air at about 1 to 10 CrfL, it will have properties that meet the purpose of the present invention.

When ordinary wet spinning is used instead of this aerial spinning method, it is insufficient to impart to the fiber the properties that make it easy to remove crimps and "undulations," which is the objective of the present invention, and It is also impossible to impart a soft hair-like texture or gloss.

There are no particular restrictions on the detailed conditions for washing with water, stretching, and drying after coagulation, but it is necessary to sufficiently dry and densify the film before entering the secondary stretching.

So-called raw silk that is not dried has no crimping effect.

Further, drying is preferably carried out in a straight line with less tension, and the drying temperature is also preferably 150°C or lower.

Although this may be preferable in terms of preventing heat coloring, drying at high temperatures is not preferable because it has the same effect as heat treatment.

Next, the second essential requirement for the post-drying treatment is to perform secondary stretching and heating and pressurization without performing heat treatment.

As shown in the examples below, it is surprising that even if heat-treated fibers are subjected to the secondary stretching and subsequent treatments of the present invention, no crimp-free effect can be obtained.

Furthermore, it also has the disadvantage of increasing shrinkage during dyeing hot water treatment.

The non-crimping effect of using non-heat treated fibers is due to the non-relaxed fibers being more strongly oriented, crystallized, and densified by secondary stretching, and the final mechanical crimping is not strong enough. It is thought that it is not fixed and becomes easy to remove.

The above-mentioned secondary stretching of the present invention may be performed by stretching 1.0 to 1.5 times under steam or dry heat at 100°C or higher.

If the temperature is lower than the above, the effect is weak; if the temperature is higher than the above, the effect is good, but it is not preferable in terms of thermal coloring or deterioration of physical properties, and is unnecessary.

Further, in the case of steam stretching, normal pressure or heated steam may be used.

It is necessary that the stretching ratio is greater than 1.0 times, but 1.
If it is larger than 5 times, it is not desirable because it causes deterioration of physical properties such as brittleness and elongation.

Furthermore, an effect other than the non-crimping effect of the secondary drawing is that the texture of the fiber becomes extremely soft, which is particularly noticeable during dry heat drawing.

Next, by pressing the second-stretched fibers with a heating roller, structural changes caused by the second-stretching are fixed, and crimps and undulations after dyeing hot water treatment and mechanical treatment can be easily removed.

The pressure roller may be heated by internal heating using a heating wire or heating by infrared ray irradiation, and any method may be used as long as the roller surface temperature can be maintained at 50 to 120°C.

Any pressure applied by a roller in the range of 1 to 10 kg/crA is effective, but the roller surface temperature is 50°C.
In this case, a range of 2 to 3 kg/crA is preferable.

If the fibers that have been subjected to the secondary drawing and heat/pressure treatment are mechanically crimped and made into spun yarn, they will shrink due to stretching strain during the dyeing hot water treatment later, resulting in so-called bulky spinning. It becomes a thread and no crimping effect can be obtained.

To remove this residual shrinkage, mechanical crimping is applied to the fibers that have been subjected to secondary drawing, heating, and pressure, and then a relaxing heat treatment is applied to fix the crimps, and the crimps do not come off during dyeing with hot water, resulting in a crimping-free effect. cannot be obtained.

If this relaxation heat treatment is performed in a non-linear state even before mechanical treatment, the crimp-free effect will be drastically reduced, leaving wrinkles and "waviness" in the fibers.

Therefore, the third essential condition of the present invention is to perform a relaxing heat treatment in a linear state after the secondary stretching, heating, and pressing, and then to apply mechanical crimp necessary for the spinning process.

The purpose of this relaxation heat treatment is to remove the residual strain caused by the secondary stretching, and it may be carried out using normal pressure steam, drying, or a combination of both. For example, the supply side may be fed between two rollers at a predetermined excess rate.

From the perspective of the purpose of the present invention, the subsequent mechanical crimp is preferably weaker, and is preferably applied using a stuffing box type crimp under steam or dry heat.

Next, examples of the present invention will be shown.

Example 1 Acrylonitrile 88%, methyl acrylate 3%, acrylamide 4%, dimethylaminoethyl methacrylate 5%, and ammonium persulfate and acidic sodium sulfite were used as polymerization catalysts at 0.3% and 0.3%, respectively, based on the total monomers.
Polymerization was carried out using a suspension polymerization method using 5%.

The obtained polymer was dissolved at 70% in nitric acid at 0° C., and at this time, 0.5% titanium oxide was added to the polymer to obtain a stock solution with a polymer concentration of 15%.

600 with a space of 5 mm from the surface of the coagulation bath.
After running through the air through the 0 hole nozzle, the 0
The fibers were introduced into a 30% nitric acid coagulation bath at 0.degree. C. to obtain a coagulated fiber, which was washed with water and then stretched 8 times in hot water to obtain a single fiber bundle of 15 denier.

Next, the fiber bundle was dried in a straight line in dry hot air at 120°C, then passed through hot water at 80°C containing a spinning oil, and immediately crimped with an average of 13.5 fibers/inch. It was crimped and dried in dry hot air at 80°C.

The fibers thus obtained were used as samples, and each of the seven samples was subjected to the following treatments.

(1) Sample 1 A blank was prepared by applying relaxation treatment using high-pressure steam at 105°C.

Sample 2 After 1.2 times secondary stretching in steam at 102°C, and then pressurized heat treatment using a heated roller with a surface temperature of loO'c at a press pressure of 2 kg/crA, the fiber was Steaming at 103℃ while keeping it straight 10
．． 9% shrinkage followed by an average crimp of 7.6 crimps/inch.

Sample 3 After secondary stretching and pressure heat treatment under the same conditions as sample 2,
An average of 7.6 crimps/inch was applied.

Sample 4 Second stretching was performed by 1.2 times in dry hot air at 160°C, and then secondary stretching and pressure heat treatment were performed under the same conditions as Sample 2, and the fibers were stretched in 11. 5% shrinkage followed by an average of 7.6 crimps/inch.

Sample 5 After being subjected to a relaxation treatment using high-pressure steam at 105°C, it was subjected to secondary stretching and pressure heat treatment under the same conditions as Sample 2, and then crimped at an average of 7.6 crimps/inch.

Sample 6 Secondary stretching was performed under the same conditions as Sample 2, and the fibers were then shrunk by 9.5% while keeping them in a straight shape.
Added inch crimps.

Sample 7 The sample was subjected to secondary stretching and pressurized heat treatment under the same conditions as Sample 2, and then crimped at an average of 7.5 crimps/inch, and then subjected to relaxation treatment using high pressure steam at 105°C.

These samples 1 to 7 were boiled at 100° C. for 30 minutes.

Through the above treatment, the degree of crimp removal and boil shrinkage rate were examined, and the results shown in Table 1 and the attached drawing (representative photograph of the drawing) were obtained.

As is clear from Table 1 and the attached drawings, the method of processing sample 2.4, that is, the processing method according to the present invention, removes crimps by boiling, resulting in straight fibers, and is suitable for dyeing, etc. It can be seen that the contraction inside is also small.

As in sample 3.5, if either the pressure heat treatment or the steaming treatment is not performed after the secondary stretching, strong crimps can be obtained, but the fibers will not be straight and undulations will remain. The elongation is insufficient.

Furthermore, if relaxation treatment with high-pressure steam is performed after applying crimps as in sample 1.5.7, the crimps are firmly fixed, and the crimps do not become loose during boiling treatment.

Next, sample 2.3 was cut at 152 mm to make a staple.
After mixing a single 3-denier acrylic fiber into each sample, it was spun into a double yarn with a single yarn count of 15 meters, a number of first twists of 180 T/m, and a number of first twists of 260 T/m using Yoneni Worsted Spinning to create bulky yarn. made.

Here, the spun yarn made by mixing sample 2 is referred to as sample 2', and the spun yarn made by mixing sample 3 is referred to as sample 3'.

The two types of spun yarns thus obtained were dyed in whole form under the following conditions.

Dye Sumiacryl Navy Blue R (manufactured by Sumitomo Chemical) Concentration 0.6% owf Acid 0.5 CC/, i (90% acetic acid) Bath ratio 1:
25 Temperature: 100°C Time: 60 minutes Regarding the obtained spun yarn to be dyed, sample 3' had insufficient elongation of the crimps of sample 3, and also had a large boiling shrinkage rate, so it slipped into the spun yarn and caused the entire spun yarn to deteriorate. It was a rough and hard thing that didn't look good.

Sample 2' had better crimp elongation than Sample 2, and also had a smaller boiling shrinkage rate, so it did not sink in, and had extremely high commercial value.

Example 2 Fibers that had been polymerized, spun, dried, and crimped in the same manner as in Example 1 were treated according to the treatment method of the present invention while changing the secondary draw ratio.

That is, sample 8 is 1.1 times, sample 9 is 1.2 times, sample 1o is 13 times, sample 11 is 1.5 times, and sample 12 is 1.7 times.
Stretched in steam at 02°C, then stretched at a surface temperature of 10°C.
After applying pressure and heat treatment at a press pressure of 2 kg/crA using a heating roller at 0°C, steaming at 103°C was performed while keeping it in a straight line, and then an average of 7.5 crimps/inch was applied. .

When these samples 8 to 12 were boiled at 100'C for 30 minutes, the crimps were removed and straight fibers were obtained.

Next, Samples 8 to 2 were cut into 152 mm lengths to form staples, and blended with 3-denier acrylic fiber single yarns to produce bulky yarns.

At this time, the amount of fried food generated during the process was observed.

Table 2 shows the amount of fly generated and the physical properties of single yarns of Samples 8 to 12 used for spinning.

As is clear from the results, as the secondary draw ratio increases, the loop elongation particularly decreases markedly, the yarn becomes brittle, and the amount of fries in the spun yarn increases.

In particular, sample 12 with a secondary draw ratio of 1.7 times had low loop elongation and a large amount of fly generation, which caused frequent troubles due to yarn breakage and neps during spinning, making it difficult to spin stably. .

Example 3 90% acrylonitrile, 4% vinyl acetate, 6% diethylaminoethyl methacrylate, 0.6% hydroxylurea based on the total monomers, and ammonium persulfate and acidic sodium sulfite as polymerization catalysts, respectively. Polymerization was carried out using suspension polymerization using 0.35% and 0.45%.

70% of the obtained polymer was dissolved in nitric acid at 0° C., and 0.6% titanium oxide was added to the dissolved polymer to obtain a stock solution with a polymer concentration of 15.2%.

When spinning the stock solution, Sample 13 was introduced into a 3000-hole nozzle immersed in a 30% nitric acid coagulation bath at 0° C., and directly discharged into the coagulation bath for spinning.

The fiber bundle was then washed with water and stretched 8 times in hot water to obtain a single fiber bundle of 15 denier.

In addition, sample 14 was prepared using a 600-meter tube with a space of 4 m from the surface of the coagulation bath.
The stock solution was introduced into the nozzle of the 0-hole, and once discharged and run in the air, it was introduced into a 30% nitric acid coagulation bath at 0°C for spinning, and after washing with water, it was stretched 8 times in hot water to form a single yarn of 15 A denier fiber bundle was obtained.

Next, samples 13 and 14 were dried in a straight line in dry hot air at 125°C, then passed through hot water at 80°C containing a spinning oil, and immediately crimped with an average of 13.2 pieces/piece. It was given an inch of crimp and dried in dry hot air at 80°C.

Next, it was stretched 1.15 times in steam at 102°C, and then pressed at a pressure of 3 kg/1.
After the crrt pressure and heat treatment, the fibers were steamed at 103° C. while keeping them straight to shrink by 9.7%, and then crimped at an average of 7.7 crimps/inch.

Samples 13 and 14 treated as described above were boiled at 100° C. for 30 minutes, and as shown in the attached drawings, there was a difference in the degree of crimp removal before and after boiling.

In other words, sample 14 spun by the air running method is sufficiently crimped and has a straight shape, whereas sample 13 spun directly into a coagulation bath has insufficient crimps elongation and strong undulations remain. ing.

Example 4 □ A polymer obtained in the same manner as in Example 3 was melted and spun in the same manner as in Example 1, and stretched 8 times in hot water to obtain a single yarn of 15
A denier fiber bundle was obtained.

After drying this fiber bundle while keeping it in a straight line in hot dry air at 125°C, it was stretched to 1.26 times in steam at 103°C, and pressed at a pressure of 3 kg/cm using a heated roller with a surface temperature of 60°C. The fiber bundle was subjected to pressure and heat treatment using crrt, and then steamed at 103° C. while keeping the fiber bundle in a straight shape, to give an average of 7.7 crimps/inch.

As a result of boiling the folded fiber bundle at 100'C for 30 minutes, the crimps were removed and the fibers became straight, and the shrinkage rate during boiling was 1.5%, which is comparable to non-shrinkable yarn. The value was small, and the dyeability showed the same coloring as mohair.

[Brief explanation of drawings]

The drawings are photographs substituted for drawings showing the state of fibers obtained by the method of the present invention and a method for comparison. (4 times larger than the actual size).

Claims (1)

[Claims] 1. A polymer containing at least 60% by weight of acrylonitrile is spun using an air running method to obtain fibers, and after the fibers are subjected to a conventional stretching and drying treatment, the fibers are heated at 100°C.
The fibers are stretched 1.0 to 1.5 times under steam or dry heat, and then stretched between a pair of rollers at 50 to 120°C.
A method for producing animal hair-like acrylic synthetic fibers, which is characterized by heating and pressurizing the fibers to 1 to 10 kg/crA, then applying mechanical crimp after shrinkage heat treatment in a straight line.