KR101306233B1 - Cellulose filament fiber, preparation method thereof, and tire cord comprising the same - Google Patents

Abstract

The present invention relates to a cellulosic filament fiber comprising a HALS-based antioxidant, a method for producing the same, and a tire cord including the same.

The cellulose filament fiber exhibits improved heat or oxidation resistance as it comprises a Hals-based antioxidant. Therefore, the cellulose filament fibers can exhibit excellent shape stability and maintain excellent physical properties even when used at high temperatures.

Tire cord, cellulose filament fiber, antioxidant

Description

Cellulose-based filament fibers, a manufacturing method thereof, and a tire cord comprising the same {CELLULOSE FILAMENT FIBER, PREPARATION METHOD THEREOF, AND TIRE CORD COMPRISING THE SAME}

The present invention relates to a cellulosic filament fiber, a manufacturing method thereof and a tire cord comprising the same.

Generally, nylon or polyester is used as a material for tire cords. However, these materials are limited in size and use, etc. of the tires used due to their advantages and disadvantages.

Nylon fiber has high tensile elongation and high strength, and is mainly used for tires used on curved roads such as heavy trucks and unpaved roads. However, the nylon fiber is not suitable for a tire for a passenger car in which concentrated heat accumulation occurs inside the tire, and a low modulus is used to travel at high speed or require a ride comfort.

Polyester fiber has better shape stability and price competitiveness than nylon, and strength and adhesion are improved due to continuous research, and its usage is increasing in the tire cord field. However, it is not suitable for high-speed running tires because of limitations in heat resistance and adhesive strength.

Accordingly, recently, it has been considered that cellulose filament fibers such as rayon fibers or lyocells are used as materials for tire cords. Among these, rayon fibers are known to be preferably used as materials for tire cords because they exhibit relatively high strength retention and shape stability at high temperatures.

In addition, Korean Patent Laid-Open Publication No. 2002-0085188 discloses a tire cord using lyocell fibers having health, wet strength and modulus superior to rayon fibers.

However, these cellulose filament fibers, such as rayon fibers or lyocell fibers, also have limitations in heat resistance or oxidation resistance. Thus, when applied to ultra-high speed tires, cellulose filament fibers have insufficient shape stability at high temperatures and maintain high physical properties at high temperatures. There is also a lack of characteristics. For this reason, there is a need for improvement.

The present invention is to provide a cellulosic filament fiber and a method for producing the same exhibiting improved heat resistance or oxidation resistance.

The present invention also provides a tire cord having excellent physical properties by using the cellulose filament fibers.

The present invention is based on HLS (Hindered Amine Light Stabilizer) Provided is a cellulose filament fiber comprising an antioxidant.

Preferably, the Halis-based antioxidant comprises a compound of Formula 1, a compound of Formula 2, or a mixture thereof:

[Formula 1]

(2)

In addition, the cellulose filament fibers may be lyocell fibers or rayon fibers.

The present invention also comprises the steps of mixing a hals-based antioxidant in the cellulose spinning dope; Extruding the mixed solution; Solidifying the spun mixed solution to produce a multifilament; Washing the multifilament; And it provides a method for producing a cellulosic filament fiber comprising the step of drying the washed multi-filament.

The present invention also provides a tire cord comprising the cellulose filament fibers.

Hereinafter, the present invention will be described in more detail.

The cellulose filament fiber according to the present invention includes a Hals-based antioxidant.

Such a halogen-based antioxidant can inhibit the oxidation of the polymer chain of cellulose contained in the cellulose filament fibers. Therefore, the cellulose filament fibers including the same can be improved heat resistance or oxidation resistance, even if used at high temperatures can exhibit high morphological stability and also maintain high physical properties.

As the Halus-based antioxidant, any substance capable of inhibiting oxidation of the polymer chain of various fibers can be used without limitation. However, in order to more effectively inhibit the oxidation of the polymer chain of cellulose, one or a mixture thereof may be used as the Hals-based antioxidant.

In addition, the Halus-based antioxidant may be included in the 5 to 500 ppm in the cellulose filament fibers. As a result, the oxidation of the polymer chain of cellulose can be effectively suppressed, and the overall physical properties of the cellulose filament fibers can be further improved.

The cellulose filament fibers may be, for example, lyocell fibers or rayon fibers. These lyocell fibers or rayon fibers exhibit improved heat resistance or oxidation resistance compared to conventional fibers that do not contain Hals-based antioxidants, and thus may exhibit high morphological stability even at high temperatures and maintain high physical properties. It can be preferably used for the cord.

On the other hand, the cellulose filament fibers of the present invention comprises the steps of mixing a hals-based antioxidant in the cellulose spinning dope; Extruding the mixed solution; Solidifying the spun mixed solution to produce a multifilament; Washing the multifilament; And it may be produced by a manufacturing method comprising the step of drying the washed multi-filament. As the Hals-based antioxidant is mixed with the cellulose-based spinning dope during the manufacturing process, the cellulose filament fibers produced through this can exhibit high morphological stability even at high temperatures and maintain high physical properties.

In the above manufacturing method, the Hals-based antioxidant may be mixed with 0.05 to 5% by weight in the cellulose spinning dope. As such, through the above manufacturing method, a cellulose filament fiber exhibiting excellent physical properties with improved heat resistance or oxidation resistance can be produced.

In addition, the cellulose-based spinning dope includes cellulose (cellulose), N-methylmorpholine-N-oxide (NMMO) and water.

The cellulose may be conventional in the art to which the present invention pertains, but may be used in an amount of 96% or more of alpha-cellulose to improve physical properties of the fiber. In particular, southern pine pulp containing 96% alpha-cellulose can be used.

The cellulose-based spinning dope may be included in 5 to 35% by weight, in addition to 7 to 18% by weight in consideration of the spinning properties.

In addition, the solvent contained in the cellulose-based spinning dope is a mixed solvent containing N-methylmorpholine-N-oxide (NMMO) and water, the weight ratio of NMMO and water in the mixed solvent is increased or the melting point of the solvent It may be 93: 7 to 85:15 in order to prevent excessively high temperature and at the same time to ensure the minimum solubility and swelling of the cellulose.

The cellulose-based spinning dope is N-methylmorpholine-N-oxide (NMMO): N-methylmorpholine after swelling the cellulose in a mixed solvent containing a weight ratio of 90:10 to 50:50 -N-oxide (NMMO): water by weight ratio of 93: 7 to 85:15, the final content of cellulose is 5 to 35% by weight, more preferably 7 to 18% by weight according to the process for removing water Can be.

On the other hand, in the manufacturing method of the cellulose filament fibers, the extrusion spinning temperature can be maintained at 70 to 130 ℃.

Solidification of the spun filament is carried out in a coagulation bath, the coagulation temperature may be 45 ℃ or less. This means that the solidification temperature is 45 ° C. or lower so that the temperature is not too high than necessary so that the solidification rate is properly maintained. Herein, the coagulating bath is not particularly limited as it can be manufactured and used in a conventional composition in the technical field to which the present invention belongs.

Subsequently, the prepared multifilament is washed with water and dried.

According to the present invention, in consideration of the ease of recovery and reuse of the solvent after washing, the washing temperature in the step of washing and drying may be 35 ℃ or less, the drying temperature may be 100 ℃ to 200 ℃. Here, the water washing and drying may use the usual conditions in the technical field to which the present invention belongs, and are not particularly limited by the above conditions.

Cellulose-based filament fibers produced by the above-described manufacturing method has excellent physical properties such as strength, elongation and initial elastic modulus. In addition, since the cellulose filament fibers contain a Hals-based antioxidant, oxidation of the polymer chain of cellulose may be suppressed even at high temperatures, thereby exhibiting high form stability and maintaining high physical properties. Therefore, it can be preferably used for tire cords applied at high temperatures.

The present invention provides a tire cord made from the cellulose filament fibers.

An example of the manufacturing method of the tire cord is as follows. After the cellulose filament fibers prepared by the method described above are twisted with a twister to produce raw cords, weaving them with a weaving machine to immerse them in a dipping solution to produce tire cords. Can be. The manufacturing method of the tire cord is not limited to the above-described method, in addition, it may be manufactured using a manufacturing method commonly known in the art.

Cellulose-based filament fibers of the present invention shows more improved heat resistance or oxidation resistance, can exhibit a high form stability even at high temperature and can maintain excellent physical properties.

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to specific examples and comparative examples in order to help understanding of the present invention. However, the following examples are only intended to more clearly understand the present invention, and are not limited to the following examples of the present invention.

 [ Example  And Comparative example ]

Example  One

The cellulose sheet (buckeye V-81) was put into a grinder equipped with a 100 mesh filter to prepare a cellulose powder having a diameter of 1700 μm or less.

The cellulose powder was swollen in 50 wt% NMMO aqueous solution. At this time, the content of cellulose in the NMMO aqueous solution was 6.5% by weight.

The swelled cellulose slurry was maintained at an internal temperature of 90 ° C. and injected into a kneader maintained at an absolute pressure of 50 mmHg at a rate of 16 kg / hour using a rotary valve pump, while 50% by weight of NMMO aqueous solution was 89% by weight of NMMO aqueous solution. After dissolving the cellulose completely while removing excess moisture, the spinning dope was discharged through the discharge screw. At this time, the cellulose concentration of the spinning dope discharged was 11% by weight, and it was confirmed that it was in a homogeneous state containing no undissolved cellulose particles.

The cellulose-based spinning dope is mixed with the antioxidant of Formula 1 to be 0.1% by weight relative to the total dope, and the mixed solution is adjusted so that the final filament total fineness is 1,650 denier, and the number of nozzles is 1000, and the nozzle cross section is 0.047 mm2. Spinning was performed using a nozzle. At this time, an air layer was placed between the nozzle and the coagulation bath.

The discharged and solidified multifilament yarn was completely removed from the NMMO by the washing liquid, and dried on a drying roll to obtain a lyocell multifilament yarn. At this time, the temperature of each drying roll was adjusted to 100 degreeC, 130 degreeC, and 150 degreeC.

Example  2

A lyocell fiber was manufactured in the same manner as in Example 1, except that the antioxidant of Formula 1 was mixed so as to be 1% by weight based on the total dope.

Example  3

A lyocell fiber was prepared in the same manner as in Example 1, except that the antioxidant of Formula 1 was mixed to be 3 wt% based on the total dope.

Example  4

A lyocell fiber was manufactured in the same manner as in Example 1, except that the antioxidant of Formula 1 was mixed to be 5 wt% based on the total dope.

Example  5

A lyocell fiber was manufactured in the same manner as in Example 1, except that the antioxidant of Formula 2 was mixed to be 1 wt% based on the total dope.

Example  6

A lyocell fiber was prepared in the same manner as in Example 1, except that the antioxidant of Formula 2 was mixed to be 3 wt% based on the total dope.

Comparative example  One

A lyocell fiber was manufactured in the same manner as in Example 1, except that Hals-based antioxidant was not mixed with the cellulose spinning dope.

The lyocell filament fibers prepared according to Examples 1 to 6 and Comparative Example 1 were heat treated at 200 ° C., and the degree of yellowing over time was observed using a computer color matching system (CCM).

As a result, the present invention was observed that the lyocell filament fibers according to Examples 1 to 6 is slower than the lyocell filament fibers according to Comparative Example 1.

Cellulose-based filament fiber according to the present invention is a useful technology that can contribute to the industrial development by being able to produce high morphological stability and excellent physical properties even at high temperatures, and to produce a high-speed tire tire for high-speed driving .

Claims (9)

Cellulose filament fiber comprising a HLS (Hindered Amine Light Stabilizer) -based antioxidant comprising a compound of formula (1), a compound of formula (2) or a mixture thereof: [Formula 1]

(2)

. delete The method of claim 1, Cellulose-based filament fibers comprising the Halus-based antioxidant of 5 to 500 ppm. The method of claim 1, The cellulose filament fibers are cellulose filament fibers are lyocell fibers or rayon fibers. Mixing the cellulose-based dope with a Hals-based antioxidant comprising a compound of Formula 1, a compound of Formula 2, or a mixture thereof; Extruding the mixed solution between the cellulose spinning dope and the Halis antioxidant; Solidifying the spun mixed solution to produce a multifilament; Washing the multifilament; And Method for producing a cellulose-based filament fiber comprising the step of drying the washed multifilament: [Formula 1]

(2)

. delete The method for producing cellulose filament fibers according to claim 5, wherein the Halis-based antioxidant is mixed at 0.05 to 5% by weight in the cellulose spinning dope. 6. The method of claim 5, The cellulose-based spinning dope is 5 to 35 weight percent of cellulose, and 65 to 95% by weight of an NMMO aqueous solution containing NMMO and water in a weight ratio of 93: 7 to 85:15 Method for producing a cellulose filament fiber comprising a. A tire cord comprising the cellulose filament fibers according to claim 1.