KR20140075198A - Method for manufacturing Meta-aramid conjugated fiber having potentialcrimping and Meta-aramid conjugated fiber Produced thereof - Google Patents

Abstract

The present invention relates to a method for manufacturing a potentially crimped meat-aramid yarn and a potentially crimped meta-aramid yarn produced by the same which provide an excellent crimping ratio. Moreover, products manufactured with the potentially crimped meta-aramid yarn using the method for manufacturing a potentially crimped meta-aramid yarn have an excellent bulkiness, modulus, and crimp yield at the same time.

Description

TECHNICAL FIELD The present invention relates to a method for producing a meta-aramid conjugate fiber, and a meta-aramid conjugate fiber produced by the method,

The present invention relates to a method of producing a meta-aramid pottery and a meta-aramid pottery produced thereby, and more particularly, to a method for producing a meta-aramid pottery having different shrinkage ratios and a meta- It is about potential housing.

Generally, polyamide-based synthetic resins are classified into aliphatic polyamides and aromatic polyamides. Aliphatic polyamides are generally known under the trade name Nylon, and aromatic polyamides are known under the trade name Aramid. The aliphatic polyamide. Especially, nylon 6 and nylon 6,6 are the most common thermoplastic engineering plastics, and they are used not only as fibers but also as molding materials in various fields. The nylon resin used in the molding industry is made of reinforced plastics which is reinforced with mineral or glass fiber to improve mechanical properties such as elasticity and lowering the price to have improved flame retardancy and impact resistance.

In contrast to the molecular motion, the benzene ring of aromatic polyamide has a rigid molecular chain and does not easily move even when heat is applied. Therefore, the benzene ring of the aromatic polyamide shows a large difference in characteristics from the aliphatic polyamide because it is stable to heat and has a high elastic modulus.

The aromatic polyamide is classified into a para-aramid and a meta-aramid. The para-aramid is represented by Kevlar developed by DuPont. The para-aramid is the benzene ring bound to the amide group at the para position. Since the molecular chain is very stiff and has a linear structure, it has a very high strength and a particularly high elasticity, so that it has excellent shock absorbing performance. It is used for armor, bulletproof helmet, safety gloves, boots and fire extinguisher. It is used for sports equipment such as sticks, fishing rods and golf clubs, and also for industrial use such as FRP (Fiber Reinforced Plastics) and asbestos replacement fibers. The meta-aramid is a combination of benzene ring and amide group at the meta position. Its strength and elongation are similar to ordinary nylon, but it is very stable against heat. It is light and sweat-absorbing compared to other heat-resistant materials. Have. In the early days, the color was limited to a few, but recently it has been made in various colors including fluorescent colors. It is used as fire-resistant clothing, uniforms for racing motorists, astronaut uniforms, work clothes, etc., and for industrial use, it is used for high-temperature filters.

In the meantime, in the production of the fiber having the crimp performance, a method of separately radiating one type of polymer to different quenching speeds, and a method of selecting two different kinds of polymers for composite radiation . Compared with the composite spinning method of two kinds of polymers, the method of manufacturing the culvert yarn by dual cooling is insufficient in the crimp performance, and since there are many restrictions on the equipment to be equipped with a large scale production facility, It is most commonly commercialized.

In recent years, latent sheaves have been produced by composite spinning of two kinds of polymers having different heat shrinkability in a side-by-side manner or a sheath-core type, and then heat is applied in a spinning process or a stretching process It is a fiber that has a physical coil shape due to a difference in heat shrinkage, and imparts a high elasticity and a bell-like property to a spring similar to the principle. It is not different from conventional spandex fiber in elasticity, but it is excellent in resistance to chlorine and shape stability, which is a disadvantage of spandex fiber, and is easy to dye and post-process.

Examples of the two kinds of polymers used in the production of the polyester-based latent fiber housing include high viscosity polyethylene terephthalate and low viscosity polyethylene terephthalate or a method using high viscosity polypropylene terephthalate. In addition to polyethylene terephthalate, A method using methylene terephthalate or polybutylene terephthalate (PBT) is also proposed.

However, since the meta-aramid fiber is required to satisfy the high heat resistance and high strength by applying the solution spinning method, there is a problem that it is difficult to use the composite yarn by mixing with other kinds of polymers.

In addition, the existing meta-aramid composite fibers have a problem that it is difficult to realize various desired properties such as bulkiness and water repellency.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is to provide a method for producing a meta-aramid pottery having excellent elasticity and crimp ratio and a meta-aramid pottery manufactured thereby.

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a process for preparing a polymer composition comprising: (1) a first composition comprising a first meta-aramid polymer and a first solvent; And a second meta-aramid polymer identical to said first and meta-aramid and a second solvent identical to said first solvent; Preparing a second composition comprising a second composition having a different concentration of the meta-aramid polymer of the first composition; And (2) composite spinning the first composition and the second composition to produce a conjugate fiber. The present invention also provides a method for producing a latent meta-aramid fiber.

According to a preferred embodiment of the present invention, the first meta-aramid polymer and the second meta-aramid polymer may comprise a copolymer comprising an aromatic diamine and an aromatic diacid chloride, wherein the meta-aramid polymer And the concentration of the meta-aramid polymer relative to the second composition may be between 1 and 10%.

According to a preferred embodiment of the present invention, the composite spinning may be dry spinning, and the spinning and drawing process after the step (2) may be further performed.

According to a preferred embodiment of the present invention, the meta-aramid composite fiber may be of a side by side type.

Another aspect of the present invention provides a meta-aramid conjugate fiber having the shrinkage characteristics, the meta-aramid conjugate fiber comprising at least two meta-aramid components having different heat shrinkage ratios, wherein the difference in thermal contraction ratio between the two or more meta-aramid components can be between 1000 and 50,000 ppm , The meta-aramid component may comprise a copolymer comprising aromatic diamine and aromatic diacid chloride, wherein the meta-aramid component is selected from the group consisting of poly (metaphenylene isophthalamide), poly (m-benzamide), poly (m- (M, m'-phenylenebenzamide), and poly (1,6-naphthylene isophthalamide), and the composite fiber may be at least one selected from the group consisting of May be of the side by side type. Further, the fineness of the meta-aramid fiber may be 1 to 10 denier.

The process for producing the meta-aramid pottery of the present invention and the latent meta-aramid pot thus produced have different shrinkage properties, so that it is possible to produce a product to which a glue property is imparted, and a meta-aramid having a good elastic modulus and crimp ratio A method for producing a pottery barn and a meta-aramid pottery manufactured thereby can be provided.

1 is a cross-sectional view of a washing / stretching bath used in the present invention.
2 is a cross-sectional view of a side-by-side type composite fiber according to a preferred embodiment of the present invention.
3 is a graph according to Experimental Example 2 of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described in more detail with reference to the accompanying drawings.

As described above, conventionally, there has been a problem in that different shrinkage characteristics can not be exhibited with the same components.

Thus, according to one aspect of the present invention, there is provided a composition comprising: (1) a first composition comprising a first meta-aramid polymer and a first solvent; And a second meta-aramid polymer identical to said first and meta-aramid and a second solvent identical to said first solvent; Preparing a second composition having a different concentration of the meta-aramid polymer of the first composition, (2) combining the first composition and the second composition to prepare a conjugate fiber, and A method of making an aramid pottery housing is provided to provide a meta-aramid pottery housing with different shrinkage rates, thereby making it possible to produce products that can provide excellent modulus and crimp rates.

First, a first composition comprising the first meta-aramid polymer and the first solvent as the step (1); And a second meta-aramid polymer identical to said first and meta-aramid and a second solvent identical to said first solvent; The preparation of the second composition comprising the meta-aramid polymer of the first composition with a different concentration is described.

According to a preferred embodiment of the present invention, the first meta-aramid polymer and the second meta-aramid polymer may include those copolymerized with an aromatic diamine and an aromatic diacid chloride.

Specifically, the aromatic diamine can be generally used as metaphenylenediamine, and the aromatic diacid chloride can be polymerized by reacting isophthaloyl chloride as a raw material in the following reaction formula (1).

 [Reaction Scheme 1]

The polymerization process may be carried out by stirring the m-phenylenediamine and isophthaloyl chloride in an amide-based solvent to form a polymethenylene isophthaloyl chloride by a polymerization reaction. The m-phenylenediamine and isophthaloyl chloride are reacted at a similar molar ratio And more preferably, 5 to 15 parts by weight of metaphenylenediamine and 10 to 30 parts by weight of isophthaloyl chloride are mixed and polymerized in 100 parts by weight of the amide solvent. The amide-based solvent is preferably a polar amide-based solvent, and it is preferable to use dimethylacetamide, hexamethylphosphoramide, N-methylpyrrolidone, tetrahydrofuran, hexafluoroisopropanol, and dimethylsulfoxide will be.

In the present invention, the temperature at which the meta-aramid polymer is formed may be 0 to 70 ° C, and the meta-aramid polymer may be selected from the group consisting of poly (metaphenylene isophthalamide), poly (m-benzamide) (M, m'-phenylene benzamide), and poly (1,6-naphthylene isophthalamide).

Further, the meta-aramid polymer is subjected to a neutralization step. It is possible to neutralize hydrochloric acid (HCl) which is a by-product of the polymerized poly (meta-phenylene isophthalamide) by reacting metaphenylenediamine with isophthaloyl chloride. This is for the stability of the polymer composition.

A basic compound such as calcium hydroxide (Ca (OH) ₂ ) or lithium hydroxide (LiOH) may be added for the neutralization of hydrochloric acid produced by the reaction of metaphenylenediamine and isophthaloyl chloride, same.

[Reaction Scheme 2]

HCl + Ca (OH) _{2 -} > CaCl ₂ + 2H ₂ O

In the neutralization step, the amount added in the step of adding calcium hydroxide to neutralize hydrochloric acid, which is a by-product of the polymerization step, should be controlled according to the amount of metaphenylenediamine or isophthaloyl chloride used, and the amount of metaphenylenediamine or isophthaloyl It is desirable to add an amount equal to or 10% greater than the molar ratio of chloride.

According to a preferred embodiment of the present invention, the first composition and the second composition used in the present invention have different concentrations of the first meta-aramid polymer and the second meta-aramid polymer for each composition, The concentration of the aromatic amide and the aromatic diacid chloride may be adjusted according to the amount of the aromatic amide and the aromatic diacid chloride during the preparation of the first and second compositions, or the concentration of the meta-aramid polymer may be controlled according to the degree of removal of the solvent during the defoaming process.

Further, the difference in concentration of the first and second compositions is preferably such that the concentration of the meta-aramid polymer with respect to the first composition and the concentration of the meta-aramid polymer with respect to the second composition are between 1 and 10% If the concentration difference is less than 1%, the difference in the shrinkage ratio may be small and the occurrence of the crimp may be difficult. If the concentration difference is more than 10%, the difference in the solvent removal due to the difference in concentration may be large, Can be.

On the other hand, the composite fiber of the present invention may mean that the first composition and the second composition are not mixed with each other, and that the respective components are separately formed in the fibers. Since the first meta-aramid and the second meta-aramid are the same , It is possible to produce a composite fiber having a good elastic modulus and a crimp ratio due to the difference in the concentration of the first meta-aramid polymer with respect to the first composition and the concentration of the second meta-aramid polymer relative to the two compositions.

Next, the step of composite spinning the first composition and the second composition, which is the step (2), to produce a conjugate fiber will be described.

According to a preferred embodiment of the present invention, the composite spinning is any spinning method that can be used in general, and preferably it can be dry spinning.

Further, after the step (2), the water washing and drawing step can be further performed.

The wash and stretch process of the present invention is a process in which the unstretched first and second compositions 11 of Figure 1 pass through the wash / extend bath 10 while the concentration of the meta-aramid polymer in the first and second compositions is different The amount of the solvent to be eluted becomes different. At the same time, the stretching is performed by the roll 12, and the degree of molecular chain orientation between the first and second compositions is different. When passing through the heat treatment process in this state, natural contraction occurs due to the orientation difference between the first and second compositions, and the crimp is expressed.

Meanwhile, the present invention may further include the following additional steps after the spinning step. In general, the meta-aramid polymer may contain a salt, and the meta-aramid polymer solution containing the salt is extruded through the dry spinning process at elevated temperature, and then the fibers are sent downward through a column having a gaseous medium at an elevated temperature , And a portion of the solvent is evaporated. In general, subsequent treatment steps may be necessary to remove by-products and solvents generated by the residue during the meta-aramid polymerization process.

Wherein the preliminary conditioning step comprises adding to the spinning fiber at least one solvent selected from dimethylacetamide, hexamethylphosphoramide, N-methylpyrrolidone, tetrahydrofuran, hexafluoroisopropanol, and dimethylsulfoxide, and The solution is contacted with a preconditioning solution having a concentration of any one of salt selected from lithium chloride (LiCl), calcium chloride, preferably the solution may comprise from 4 to 40% by weight of solvent, 15% by weight. And in general the temperature of the pre-conditioning solution is significantly lower than the temperature of the fibers exiting the spinneret, and preferably the temperature of the pre-conditioning solution is 0 to 10 ° C. The pre-conditioning solution can further reduce the temperature of the fibers and create a polymer-rich phase at the surface of the fibers, which can extend the length of the fiber to several times its unit length to the desired diameter If the fibers are pricked in the stretching process, the individual fibers tend to break. To prevent this, in current practice, still wet fibers from the pre-conditioning process are placed in the tub for a period of time that can be from hours to days. The fibers may then be removed from the barrel and washed to remove the solvent and simultaneously stretched to a desired extent on a series of rolls in a number of aqueous baths. The bundle of fibers or filaments may then be further subjected to a conditioning step in which the fibers are conditioned prior to the subsequent stretching step to prevent breakage of the individual filaments in this continuous process. The additional conditioning step is most commonly the spraying of the conditioning solution onto the continuously traveling fibers.

The conditioning solution preferably comprises, at elevated temperature, at least one solvent selected from dimethylacetamide, hexamethylphosphoramide, N-methylpyrrolidone, tetrahydrofuran, hexafluoroisopropanol, and dimethylsulfoxide, (LiCl), calcium chloride, and the like. In particular, the conditioning solution may have a higher concentration of solvent than the pre-conditioning solution, and may have a temperature higher than the pre-conditioning solution temperature, and preferably the conditioning solution is in the solvent and salt, based on the total weight of the aqueous conditioning solution , The solvent may include 2 to 20 wt% and the salt may include 2 to 10 wt%, and the conditioning temperature may be 25 to 110 째 C.

Further, the present invention may further include a spinning process and a heat treatment process after spinning in a different form from the above. The spinning process of the present invention is a spinning process in which the first composition and the second composition are spinned at a spinning ratio of 30:70 to 70:30 at 230 to 290 ° C at a spinning speed of 800 to 1500 mpm into side by side type fibers And the stretching process may be preferably a process of stretching the spun fibers at a stretching ratio of 1.5 to 4.5 at 40 to 120 캜, preferably in a warm bath. The heat treatment may be performed in a dry heat process by heat treating the drawn fibers at 250 to 370 ° C. In the present invention, shrinkage difference occurs after passing through the stretching and heat treatment processes, and natural omega-shaped crimps are formed and the bulky property is expressed.

According to the method for producing a meta-aramid composite fiber, the meta-aramid composite fiber produced by the method of the present invention includes two or more meta-aramid components having different heat shrinkage ratios, Thereby making it possible to manufacture a product imparted with a bulky property.

According to another aspect of the present invention, there is provided a meta-aramid potting compost comprising two or more meta-aramid components having different heat shrinkage rates, wherein the difference in heat shrinkage of the two or more meta-aramid components may be between 1000 and 50,000 ppm, If the difference in the heat shrinkage ratio of the meta-aramid component is less than 1000 ppm, there may be a problem in the winding-up performance, and if the difference is more than 50,000 ppm, the phase separation due to the shrinkage may be separated.

In addition, the meta-aramid component may include one copolymerized with an aromatic diamine and an aromatic diacid chloride. Specifically, the aromatic diamine may be generally used as a metaphenylenediamine, and the aromatic diacid chloride may be an isophthaloyl chloride. Can be polymerized by reacting as a raw material in accordance with the following reaction formula (1).

 [Reaction Scheme 1]

The polymerization process may be carried out by stirring the m-phenylenediamine and isophthaloyl chloride in an amide-based solvent to form a polymethenylene isophthaloyl chloride by a polymerization reaction. The m-phenylenediamine and isophthaloyl chloride are reacted at a similar molar ratio And more preferably, 5 to 15 parts by weight of metaphenylenediamine and 10 to 30 parts by weight of isophthaloyl chloride are mixed and polymerized in 100 parts by weight of the amide solvent.

On the other hand, the composite fiber of the present invention may mean that the first composition and the second composition are not mixed with each other, and that the respective compositions are separately formed in the fibers. Specifically, the conjugate fiber of the present invention may be of the side by side type, and is not particularly limited thereto. It is preferable that the conjugate fiber is in the form of a composite fiber including the first composition and the second composition separately.

2 is a cross-sectional view of a side by side type composite fiber according to a preferred embodiment of the present invention.

According to a preferred embodiment of the present invention, the fineness of the meta-aramid conjugate fiber may be 1 to 10 denier, and if the fineness is less than 1 denier, there may be a problem with the elasticity of the meta- If it exceeds 10 denier, it may be difficult to extract the solvent present therein.

As a result, the meta-aramid pottery provided in the present invention imparts different shrinkage characteristics, making it possible to manufacture a product having a bulky property.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

[ Example ]

Preparation Example  One

(1) Preparation of first and second meta-aramid polymers

6 parts by weight of metaphenylenediamine and 20 parts by weight of isophthaloyl chloride were mixed with 100 parts by weight of dimethylacetamide to prepare a polymer. After the above-mentioned polymerization step, 8 parts by weight of calcium hydroxide was added to 100 parts by weight of dimethylacetamide, and the neutralization step was carried out. After neutralization, a 22% strength meta-aramid polymer was prepared by a defoaming process.

Preparation Example  2

Was prepared in the same manner as in Example 1, except that the concentration of the meta-aramid polymer was 20%.

Preparation Example  3

The procedure of Example 1 was repeated except that the concentration of the meta-aramid polymer was 18%.

Preparation Example  4

Was prepared in the same manner as in Example 1, except that the concentration of the meta-aramid polymer was 16%.

Example 1 Manufacture of meta-aramid composite fiber

Examples 1 and 2 were prepared by injecting gaseous nitrogen at a weight ratio of 50:50 by weight into the first composition and the second composition, spinning at a spinning temperature of 260 占 폚 at a spinning rate of 1000 mpm on a side by side basis, C and immediately proceeded to a conditioning step and after the drawn fibers were drawn at a draw ratio of 4.0 at 90 DEG C, the drawn fibers were immediately advanced to the washing process, where the fibers were stretched at 90 DEG C Lt; RTI ID = 0.0 > fiber < / RTI > surfaces to wash and remove residual solvent and salts from the fibers. After washing for 4 seconds, the washed fibers exited the washing process and proceeded to the drying step immediately, and heat treated at 350 ° C to produce a composite fiber having a uniaxiality of 2.2 and a single fiber fineness of 2 denier.

Example  2

Preparation Examples 2 and 3 were prepared in the same manner as in Example 1, except that the first composition and the second composition were used, respectively.

Example  3

The procedure of Example 1 was repeated except that Examples 2 and 4 were used as the first composition and the second composition, respectively.

Example  4

Preparation Examples 1 and 4 were prepared in the same manner as in Example 1, except that the first composition and the second composition were used, respectively.

Comparative Example  One

Preparation Example 1 was prepared in the same manner as in Example 1, except that only Example 1 was used.

Experimental Example  One

The amount of solvent elution over time was measured after spinning the meta-aramid composition prepared in Preparation Examples 1 to 4 and shown in FIG.

3, it can be seen that the meta-aramid compositions prepared in Preparation Examples 1 to 4 have different concentrations and thus, the elution amounts of the solvents are also different.

Experimental Example  2

The fibers prepared in Examples 1 to 4 and Comparative Example 1 were evaluated in the following 1 to 2.

1. Measurement of heat shrinkage difference

; ASTM-E881.

2. Measurement of River and Shinto

The tensile strength, the friction strength, and the flexural strength of the fibers are generally indicated by the tensile strength. Gangshin-do varies depending on the temperature and humidity of the atmosphere and moisture absorption of the fiber, so it is a general rule to measure it in the standard state (20 ℃ and 65% RH) of the atmosphere. As a measurement method, a constant descent type is applied. Constant decoration is to extend the sample at a constant speed.

The elongation is the percentage of the difference between the initial length of the fiber and the stretched length of the fiber just before it is broken.

The test equipment used is VIBROSKOP.

Heat shrinkage difference burglar
(g / de) Shindo
(%) The first meta-aramid component The second meta-aramid component Difference Example 1 12000 48000 36000 4.2 38.2 Example 2 13500 41000 27500 4.0 32.5 Example 3 18000 29000 11000 4.0 36.3 Comparative Example 1 20000 19000 1000 3.8 36.5

As a result of the measurement, it can be seen that the difference in heat shrinkage ratio in Example 1 is larger than that in Comparative Example 1. [

10: water / stretching bath 11: unstretched first and second compositions
12: roll

Claims (13)

(1) a first composition comprising a first meta-aramid polymer and a first solvent; And a second meta-aramid polymer identical to said first and meta-aramid and a second solvent identical to said first solvent; Preparing a second composition comprising a second composition having a different concentration of the meta-aramid polymer of the first composition;
(2) combining the first composition and the second composition to prepare a conjugate fiber.
The method according to claim 1,
Wherein the meta-aramid polymer comprises a copolymer comprising an aromatic diamine and an aromatic diacid chloride.
The method according to claim 1,
Wherein the difference between the concentration of the meta-aramid polymer in the first composition and the concentration of the meta-aramid polymer in the second composition is 1 to 10%.
The method according to claim 1,
Wherein the composite radiation is dry radiation.
The method according to claim 1,
Wherein the step (2) is followed by further washing and stretching steps.
6. The method of claim 5,
Wherein the first composition and the second composition differ in the amount of the solvent eluted from the first composition and the second composition during the water washing and the stretching process, and the degree of molecular chain orientation is different as the layer is elongated.
The method according to claim 1,
Wherein the meta-aramid conjugate fiber is a side by side meta-aramid conjugate fiber.
A meta-aramid pottery comprising two or more meta-aramid components differing in heat shrinkage.
9. The method of claim 8,
Wherein the difference in heat shrinkage of the two or more meta-aramid components is in the range of 1000 to 50,000 ppm.
9. The method of claim 8,
Wherein the meta-aramid component comprises a copolymer comprising an aromatic diamine and an aromatic diacid chloride.
9. The method of claim 8,
The meta-aramid component can be selected from the group consisting of poly (metaphenylene isophthalamide), poly (m-benzamide), poly (m-phenylene isophthalamide) 1,6-naphthylene isophthalamide); and a meta-aramid pottery barn.
9. The method of claim 8,
Wherein the meta-aramid conjugate fiber is a side by side type meta-aramid conjugate fiber.
9. The method of claim 8,
Wherein the meta-aramid composite fiber has a fineness of 1 to 10 denier.

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