WO2015102297A1 - Copolymerized aramid dope-dyed yarn and method for preparing same - Google Patents

Copolymerized aramid dope-dyed yarn and method for preparing same Download PDF

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Publication number
WO2015102297A1
WO2015102297A1 PCT/KR2014/012809 KR2014012809W WO2015102297A1 WO 2015102297 A1 WO2015102297 A1 WO 2015102297A1 KR 2014012809 W KR2014012809 W KR 2014012809W WO 2015102297 A1 WO2015102297 A1 WO 2015102297A1
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Prior art keywords
basic
blue
cation
copolymerized aramid
copolymerized
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PCT/KR2014/012809
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French (fr)
Korean (ko)
Inventor
이범훈
채유리
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코오롱인더스트리(주)
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Priority to CN201480071976.6A priority Critical patent/CN105899717B/en
Priority to US15/106,359 priority patent/US20180195207A1/en
Priority to JP2016544566A priority patent/JP6185184B2/en
Priority to BR112016015170-4A priority patent/BR112016015170B1/en
Priority to EP14877413.6A priority patent/EP3091107B1/en
Publication of WO2015102297A1 publication Critical patent/WO2015102297A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/04—Pigments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/06—Dyes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
    • D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/20—Physical properties optical

Definitions

  • the present invention relates to a copolymerized aramid primary yarn and a method for manufacturing the same, and specifically, when a polymerization solution containing a copolymerized aramid polymer is spun into spinneret without using sulfuric acid, a pigment having a cation is mixed with the polymerization solution.
  • the present invention relates to a method for producing a copolymerized aramid primary yarn having excellent color strength and fastness.
  • Aromatic polyamides collectively referred to as aramids, include para-aramids and meta-aramids having a structure in which benzene rings are linearly connected through an amide group (CONH).
  • Para-aramid has excellent properties such as high strength, high elasticity and low shrinkage.
  • the 5mm thick thread produced therefrom has a strong strength enough to lift 2 tons of automobiles and is used not only for bulletproof but also for various uses in high-tech industries in the aerospace field.
  • aramid is carbonized at 500 ° C or higher, and thus has been in the spotlight in fields requiring high heat resistance.
  • the method for producing aramid fibers is well described in the applicant's Korean Patent No. 10-0910537. According to this registered patent, an aromatic diamine is dissolved in a polymerization solvent to prepare a mixed solution, and aromatic dieside is added thereto to prepare an aramid polymer. Subsequently, the aramid fiber is finally finished by dissolving the aramid polymer in a sulfuric acid solvent to prepare a spinning dope and spinning it, followed by solidification, washing, and drying processes.
  • the sulfuric acid solvent used to dissolve aramid polymer having high chemical resistance and removed after spinning should be treated properly after use because it causes environmental pollution.
  • the cost of treating such waste sulfuric acid is economical of aramid fiber. Lowers.
  • Korean Patent No. 10-171994 discloses a method for producing aramid fibers without using a sulfuric acid solvent by using a copolymerized aramid polymerization solution directly spinning.
  • the polymerization solution including the copolymerized aramid polymer is polymerized, and then the polymerization is performed.
  • the solution was spun and coagulated to produce copolymerized aramid fibers.
  • the prior art has the advantage of not using a sulfuric acid solvent, the copolymerized aramid fibers produced has a problem of poor dyeability due to high crystallinity.
  • Korean Patent No. 10-067338 discloses copolymerization aramid polymer by adding and reacting terephthaloyl dichloride to an organic solvent in which paraphenylenediamine and cyano-para-phenylenediamine are dissolved.
  • the present invention discloses a method of adding polyvinylpyrrolidone, which is an amorphous polymer, to the polymerization solution when polymerizing the polymerization solution, followed by spinning and solidifying the polymerization solution to produce copolymerized aramid fibers.
  • the method can improve the dyeability of the prepared copolymer aramid fibers, there is a problem that the solubility and dyeing fastness of the polymerization solution is poor.
  • terephthaloyl dichloride is added and reacted with an organic solvent in which paraphenylenediamine and cyano-para-phenylenediamine are dissolved to polymerize a polymerization solution including a copolymerized aramid polymer.
  • a dye which cannot hydrogen bond with the cyano group (-CN) of the copolymerization aramid that is, a pigment not having cation is added to the polymerization solution.
  • the method of manufacturing the copolymer aramid primary yarn was also performed, the said conventional method has the problem that the degree of polymerization of a copolymerization aramid polymer falls, the solubility of a polymerization solution falls, and the fastness of the manufactured original yarn was inferior.
  • An object of the present invention is to provide a copolymerized aramid primary yarn having excellent color strength and color fastness and a method of manufacturing the same, while preventing a decrease in the polymerization degree of the copolymerized aramid and a decrease in the solubility of the polymerization solution.
  • terephthaloyl dichloride is added and reacted with an organic solvent in which an aromatic diamine containing a cyano group is dissolved, followed by polymerization to polymerize a polymerization solution containing a copolymerized aramid polymer.
  • a pigment having a cation is added to the copolymerized aramid polymer by weight.
  • the present invention can effectively prevent the polymerization degree of the copolymerized aramid polymer from being lowered or the solubility of the polymerization solution from being lowered by adding the dye to the polymerization solution.
  • the present invention is the copolymer aramid when the pigment having a cation is hydrogen-bonded during the process of polymerizing the copolymerization aramid polymer having a cyano group (-CN) and the dye having a cation polymerize a polymerization solution containing a copolymerized aramid polymer.
  • the ionic bond with the cyano group (-CN) located in the main chain of the polymer can be combined to improve the color strength, light fastness and wash fastness of the copolymer aramid primary.
  • an inorganic salt is dissolved in an organic solvent, and then an aromatic diamine containing a cyano group (CN-) is added thereto to dissolve it.
  • CN- aromatic diamine containing a cyano group
  • paraphenylenediamine and cyano-para-phenylenediamine may be dissolved in an aromatic diamine containing a cyano group (CN-) in a molar ratio of 1: 9 to 9: 1, and cyano-para-phenylenediamine May be dissolved alone.
  • CN- cyano group
  • organic solvent examples include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), hexamethylphosphoamide (HMPA), N, N, N ', N'- Tetramethyl urea (TMU), N, N-dimethylformamide (DMF), or mixtures thereof.
  • the inorganic salt is added to increase the degree of polymerization of the aromatic polyamide, and specific examples thereof include halogenated alkali metal salts or halogenated alkaline earth metal salts such as CaCl 2 , LiCl, NaCl, KCl, LiBr and KBr. These inorganic salts may be added alone or in the form of a mixture of two or more thereof.
  • the amount of the inorganic salt added is preferably about 2 to 5% by weight based on the weight of the organic solvent.
  • terephthaloyl dichloride is added in the same molar amount as the aromatic diamine containing the cyano group to the organic solvent in which the aromatic diamine containing the cyano group is added and dissolved as described above.
  • a dye having a cation is added to the organic solvent to prepare a polymerization solution containing a copolymerized aramid polymer.
  • the content of the dye having a cation is preferably 0.1 to 5% by weight based on the weight of the copolymer aramid polymer. If the input content is less than 0.1% by weight, the color strength is weak, and when the content exceeds 5% by weight, the physical properties of the fiber may decrease.
  • the polymerization solution prepared as described above is extruded through a spinneret using a spinning dope as it is, and then the extruded polymerization solution is coagulated with a coagulation solution to prepare a copolymerized aramid primary yarn on filament.
  • the cyano group (-CN) has a strong electronegative anion.
  • (Anion) Reacts with the anion sulfonic groups of the dyes, whereby the anion dyes do not deposit on the polymer and escape with the solvent, resulting in a color of contamination level rather than the level of pigmentation, which greatly reduces color intensity, light fastness and wash fastness. do.
  • the copolymerized aramid primary yarn according to the present invention may contain only one kind of the dye having the above cation or may contain two or more kinds together.
  • the dye having a cation is a pigment having a cation, a dye having a cation or a mixture of a pigment having a cation and a dye having a cation.
  • the copolymerized aramid primary yarn prepared by the method according to the present invention contains a pigment having a cation (coloration) is excellent in color strength of 50 or more, excellent light fastness and wash fastness of the fourth to fifth grade, There is no fall in polymerization degree and the strength is excellent at 28-35 g / d.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat-treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare copolymerized aramid fibers.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare copolymerized aramid fibers.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • NMP N-methyl-2-pyrrolidone
  • the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier.
  • the spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
  • the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
  • Example 1 Table 1 division Color intensity (K / S value) Daylight Fastness (Grade) Wash fastness (class) Example 1 50 Grade 4 Grade 5 Example 2 120 Grade 4 Grade 4 Example 3 180 Grade 4 Grade 4 Example 4 200 Grade 4 Grade 5 Example 5 60 Grade 4 Grade 4 Example 6 110 Grade 4 Grade 4 Example 7 170 Grade 4 Grade 5 Example 8 210 Grade 5 Grade 4 Example 9 100 Grade 4 Grade 4 Example 10 150 Grade 4 Grade 4 Example 11 180 Grade 5 Grade 4 Example 12 50 Grade 4 Grade 4 Example 13 60 Grade 4 Grade 4 Example 14 120 Grade 4 Grade 5 Comparative Example 1 5 2nd class 2nd class Comparative Example 2 40 2-3 grade Level 3 Comparative Example 3 10 2nd class 2nd class Comparative Example 4 30 2nd class 2nd class Comparative Example 5 25 2nd class 2nd class
  • KS K 0205 Color intensity was confirmed based on KS K 0205. Specifically, the aramid fibers were wound tightly on a small card 7.5 cm long and 6.5 cm wide, and then measured with a 10 degree field of view at a D65 light source using a spectrophotometer (Konica-Minolta CM-3600d spectrophotometer). At this time, the average value measured three times by changing the position was measured.
  • a spectrophotometer Konica-Minolta CM-3600d spectrophotometer
  • Copolymer aramid primary yarn according to the invention is useful as a protective glove or protective clothing material.

Abstract

The present invention relates to a copolymerized aramid dope-dyed yarn and a method for preparing the same, wherein when a copolymerized aramid yarn is prepared by adding terephthaloyl dichloride to an organic solvent in which an aromatic diamine having a cyano group is dissolved, followed by a reaction, to polymerize a polymerization solution containing a copolymerized aramid polymer, and then spinning and solidifying the polymerization solution, a copolymerized aramid dope-dyed yarn is prepared by adding a dye having a cation during the polymerization process of the polymerization solution containing the copolymerized aramid polymer. The present invention can effectively prevent deterioration in the polymerization degree of the copolymerized aramid polymer or deterioration in the dissolubility of the polymerization solution due to the addition of the dye to the polymerization solution. Further, according to the present invention, when a copolymerized aramid polymer having a cyano(-CN) group and a dye having a cation are bonded by a hydrogen bond to form a liquid crystal during the polymerization process of the polymerization solution containing the copolymerized aramid polymer, the behavior together with a main chain of the copolymerized aramid polymer is possible, thereby enhancing the color strength, color fastness to light, and color fastness to washing of the copolymerized aramid doped-dyed yarn.

Description

공중합 아라미드 원착사 및 그의 제조방법Copolymer Aramid Yarn and Manufacturing Method Thereof
본 발명은 공중합 아라미드 원착사 및 그의 제조방법에 관한 것으로서, 구체적으로는 공중합 아라미드 중합체를 포함하는 중합용액을 황산 사용 없이 방사구금으로 방사할 때 양이온(cation)을 가지는 색소를 상기 중합용액에 혼합하여 색강도 및 견뢰도가 우수한 공중합 아라미드 원착사를 제조하는 방법에 관한 것이다.The present invention relates to a copolymerized aramid primary yarn and a method for manufacturing the same, and specifically, when a polymerization solution containing a copolymerized aramid polymer is spun into spinneret without using sulfuric acid, a pigment having a cation is mixed with the polymerization solution. The present invention relates to a method for producing a copolymerized aramid primary yarn having excellent color strength and fastness.
아라미드로 통칭되는 방향족 폴리아미드는, 벤젠 고리들이 아미드기(CONH)를 통해 직선적으로 연결된 구조를 갖는 파라계 아라미드와 그렇지 않은 메타계 아라미드를 포함한다. Aromatic polyamides, collectively referred to as aramids, include para-aramids and meta-aramids having a structure in which benzene rings are linearly connected through an amide group (CONH).
파라계 아라미드는 고강도, 고탄성, 저수축 등의 우수한 특성을 가지고 있다. 이로부터 제조된 5㎜ 정도 굵기의 가느다란 실은 2톤의 자동차를 들어올릴 정도의 막강한 강도를 가지고 있어 방탄 용도로 사용될 뿐만 아니라, 우주항공 분야의 첨단 산업에서 다양한 용도로 사용되고 있다.Para-aramid has excellent properties such as high strength, high elasticity and low shrinkage. The 5mm thick thread produced therefrom has a strong strength enough to lift 2 tons of automobiles and is used not only for bulletproof but also for various uses in high-tech industries in the aerospace field.
또한, 아라미드는 500℃ 이상에서 검게 탄화하므로 고내열성이 요구되는 분야에서도 각광을 받고 있다.In addition, aramid is carbonized at 500 ° C or higher, and thus has been in the spotlight in fields requiring high heat resistance.
아라미드 섬유의 제조방법이 본 출원인의 대한민국 등록특허 제10-0910537호에 잘 설명되어 있다. 이 등록 특허에 의하면, 방향족 디아민을 중합용매에 녹여 혼합용액을 준비하고 이것에 방향족 디에시드를 첨가하여 아라미드 중합체를 제조한다. 이어서, 아라미드 중합체를 황산용매에 녹여 방사도프를 제조하고 이를 방사한 후 응고, 수세, 및 건조 공정들을 차례로 수행함으로써 아라미드 섬유가 최종적으로 완성된다.The method for producing aramid fibers is well described in the applicant's Korean Patent No. 10-0910537. According to this registered patent, an aromatic diamine is dissolved in a polymerization solvent to prepare a mixed solution, and aromatic dieside is added thereto to prepare an aramid polymer. Subsequently, the aramid fiber is finally finished by dissolving the aramid polymer in a sulfuric acid solvent to prepare a spinning dope and spinning it, followed by solidification, washing, and drying processes.
그러나, 이와 같은 공정을 통해 아라미드 섬유를 제조할 경우, 고체 상태의 아라미드 중합체를 제조한 후 이를 다시 황산용매에 녹여 방사도프를 제조하여 방사하기 때문에, 제조공정이 복잡해지고 인체에 유해할 뿐만 아니라 장치가 부식에 따른 내구성 저하 등의 문제점들이 있다.However, when the aramid fibers are manufactured through such a process, since the aramid polymer in the solid state is prepared and then dissolved in a sulfuric acid solvent to spin the dope, the manufacturing process is complicated and harmful to the human body. There are problems such as deterioration of durability due to corrosion.
더욱이, 높은 내화학성을 갖는 아라미드 중합체를 녹이기 위하여 사용되고 방사 후에는 제거되는 황산용매는 환경 오염을 유발하기 때문에 사용 후에 적절하게 처리되어야 하는데, 이와 같은 폐황산의 처리에 소요되는 비용은 아라미드 섬유의 경제성을 저하시킨다.Moreover, the sulfuric acid solvent used to dissolve aramid polymer having high chemical resistance and removed after spinning should be treated properly after use because it causes environmental pollution. The cost of treating such waste sulfuric acid is economical of aramid fiber. Lowers.
상기 문제점을 해결하기 위해서, 대한민국 등록특허 제10-171994호에서는 공중합된 아라미드 중합용액을 바로 방사도프로 이용함으로써 황산용매의 사용 없이도 아라미드 섬유를 제조하는 방법을 게재하고 있다.In order to solve the problem, Korean Patent No. 10-171994 discloses a method for producing aramid fibers without using a sulfuric acid solvent by using a copolymerized aramid polymerization solution directly spinning.
구체적으로 상기 종래기술에서는 파라페닐렌디아민과 시아노-파라-페닐렌디아민이 용해되어 있는 유기용매에 테레프탈로일 디클로라이드를 첨가, 반응시켜 공중합 아라미드 중합체를 포함하는 중합용액을 중합한 다음 상기 중합용액을 방사, 응고하여 공중합 아라미드 섬유를 제조하였다.Specifically, in the prior art, by adding and reacting terephthaloyl dichloride to an organic solvent in which paraphenylenediamine and cyano-para-phenylenediamine are dissolved, the polymerization solution including the copolymerized aramid polymer is polymerized, and then the polymerization is performed. The solution was spun and coagulated to produce copolymerized aramid fibers.
그러나, 상기 종래기술은 황산용매를 사용하지 않는 장점은 있으나, 제조된 공중합 아라미드 섬유는 높은 결정성으로 인해 염색성이 떨어지는 문제가 있었다.However, the prior art has the advantage of not using a sulfuric acid solvent, the copolymerized aramid fibers produced has a problem of poor dyeability due to high crystallinity.
이와 같은 문제점을 해결하기 위해서 대한민국 등록특허 제10-067338호에서는 파라페닐렌디아민과 시아노-파라-페닐렌디아민이 용해되어 있는 유기용매에 테레프탈로일 디클로라이드를 첨가, 반응시켜 공중합 아라미드 중합체를 포함하는 중합용액을 중합한 다음 상기 중합용액을 방사, 응고하여 공중합 아라미드 섬유를 제조할 때 상기 중합용액에 비결정 고분자인 폴리비닐피롤리돈을 첨가하는 방법을 게재하고 있다. 그러나 상기 방법은 제조된 공중합 아라미드 섬유의 염색성은 개선할 수 있으나, 상기 중합용액의 용해성과 염색견뢰도가 떨어지는 문제점이 있다. In order to solve this problem, Korean Patent No. 10-067338 discloses copolymerization aramid polymer by adding and reacting terephthaloyl dichloride to an organic solvent in which paraphenylenediamine and cyano-para-phenylenediamine are dissolved. The present invention discloses a method of adding polyvinylpyrrolidone, which is an amorphous polymer, to the polymerization solution when polymerizing the polymerization solution, followed by spinning and solidifying the polymerization solution to produce copolymerized aramid fibers. However, the method can improve the dyeability of the prepared copolymer aramid fibers, there is a problem that the solubility and dyeing fastness of the polymerization solution is poor.
또 다른 종래기술로는, 파라페닐렌디아민과 시아노-파라-페닐렌디아민이 용해되어 있는 유기용매에 테레프탈로일 디클로라이드를 첨가, 반응시켜 공중합 아라미드 중합체를 포함하는 중합용액을 중합한 다음 상기 중합용액을 방사, 응고하여 공중합 아라미드 섬유를 제조할 때 상기 중합용액에 공중합 아라미드의 시아노기(-CN)와 수소결합을 할 수 없는 색소, 다시 말해 양이온(cation)을 구비하지 않는 색소를 첨가하여 공중합 아라미드 원착사를 제조하는 방법도 실시되어 왔으나, 상기 종래방법은 공중합 아라미드 중합체의 중합도가 저하되고, 중합용액의 용해성이 저하되고, 제조된 원착사의 견뢰도가 떨어지는 문제가 있었다.In another conventional technique, terephthaloyl dichloride is added and reacted with an organic solvent in which paraphenylenediamine and cyano-para-phenylenediamine are dissolved to polymerize a polymerization solution including a copolymerized aramid polymer. When the copolymerization solution is spun and solidified to produce copolymerized aramid fibers, a dye which cannot hydrogen bond with the cyano group (-CN) of the copolymerization aramid, that is, a pigment not having cation is added to the polymerization solution. Although the method of manufacturing the copolymer aramid primary yarn was also performed, the said conventional method has the problem that the degree of polymerization of a copolymerization aramid polymer falls, the solubility of a polymerization solution falls, and the fastness of the manufactured original yarn was inferior.
본 발명의 과제는 공중합 아라미드의 중합도 저하 및 중합용액의 용해도 저하를 방지하면서 색강도 및 견뢰도가 우수한 공중합 아라미드 원착사 및 이를 제조하는 방법을 제공하는 것이다.SUMMARY OF THE INVENTION An object of the present invention is to provide a copolymerized aramid primary yarn having excellent color strength and color fastness and a method of manufacturing the same, while preventing a decrease in the polymerization degree of the copolymerized aramid and a decrease in the solubility of the polymerization solution.
이와 같은 과제를 달성하기 위해서, 본 발명에서는 시아노기를 포함하는 방향족 디아민이 용해되어 있는 유기용매에 테레프탈로일 디클로라이드를 첨가, 반응시켜 공중합 아라미드 중합체를 포함하는 중합용액을 중합한 다음 상기 중합용액을 방사, 응고하여 공중합 아라미드 원사를 제조할 때, 상기의 공중합 아라미드 중합체를 포함하는 중합용액을 중합하는 공정중에 양이온(cation)을 가지는 색소를 공중합 아라미드 중합체 중량대비 0.1~5중량% 첨가한다.In order to achieve the above object, in the present invention, terephthaloyl dichloride is added and reacted with an organic solvent in which an aromatic diamine containing a cyano group is dissolved, followed by polymerization to polymerize a polymerization solution containing a copolymerized aramid polymer. In the process of polymerizing the polymerization solution containing the copolymerized aramid polymer, 0.1 to 5% by weight of a pigment having a cation is added to the copolymerized aramid polymer by weight.
본 발명은 중합용액에 상기 색소를 첨가하는 것으로 인해서 공중합 아라미드 중합체의 중합도가 저하되거나 중합용액의 용해성이 저하되는 것을 효과적으로 방지할 수 있다.The present invention can effectively prevent the polymerization degree of the copolymerized aramid polymer from being lowered or the solubility of the polymerization solution from being lowered by adding the dye to the polymerization solution.
또한, 본 발명은 시아노기(-CN)를 가진 상기 공중합 아라미드 중합체와 양이온을 가지는 색소가 공중합 아라미드 중합체를 포함하는 중합용액을 중합하는 공정 중에 수소결합하여 상기 양이온을 가지는 색소가 액정 형성시 공중합 아라미드 중합체의 주쇄(main chain)에 위치한 시아노기(-CN)와 이온결합을 하여 함께 거동이 가능하여 공중합 아라미드 원착사의 색강도, 일광견뢰도 및 세탁견뢰도가 향상된다.In addition, the present invention is the copolymer aramid when the pigment having a cation is hydrogen-bonded during the process of polymerizing the copolymerization aramid polymer having a cyano group (-CN) and the dye having a cation polymerize a polymerization solution containing a copolymerized aramid polymer. The ionic bond with the cyano group (-CN) located in the main chain of the polymer can be combined to improve the color strength, light fastness and wash fastness of the copolymer aramid primary.
이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
아래에서 설명되는 본 발명의 실시예 들은 본 발명의 이해를 돕기 위한 예들에 불과한 것으로서 본 발명의 권리범위를 제한하지 않으며, 본 발명의 기술적 사상 및 범위를 벗어나지 않는 범위 내에서 본 발명의 다양한 변경 및 변형이 가능하다는 점은 당업자에게 자명할 것이다. 따라서, 본 발명은 특허청구범위에 기재된 발명 및 그 균등물의 범위 내에 드는 변경 및 변형을 모두 포함한다.Embodiments of the present invention described below are only examples to help understanding of the present invention, and do not limit the scope of the present invention, and various changes and modifications of the present invention without departing from the spirit and scope of the present invention. It will be apparent to those skilled in the art that variations are possible. Accordingly, the invention includes all modifications and variations that fall within the scope of the invention as set forth in the claims and their equivalents.
본 발명에서는 먼저, 유기용매에 무기염을 용해시킨 다음 여기에 시아노기(CN-)를 포함하는 방향족 디아민을 첨가하여 용해시킨다.In the present invention, first, an inorganic salt is dissolved in an organic solvent, and then an aromatic diamine containing a cyano group (CN-) is added thereto to dissolve it.
이때 시아노기(CN-)를 포함하는 방향족 디아민으로 파라페닐렌디아민과 시아노-파라-페닐렌디아민을 1:9~9:1의 몰비로 용해할 수도 있고, 시아노-파라-페닐렌디아민을 단독으로 용해할 수도 있다.At this time, paraphenylenediamine and cyano-para-phenylenediamine may be dissolved in an aromatic diamine containing a cyano group (CN-) in a molar ratio of 1: 9 to 9: 1, and cyano-para-phenylenediamine May be dissolved alone.
상기 유기용매의 구체적인 예로는 N-메틸-2-피롤리돈(NMP), N,N-디메틸아세트아미드(DMAc), 헥사메틸포스포아미드(HMPA), N,N,N',N'-테트라메틸 우레아(TMU), N,N-디메틸포름아미드(DMF), 또는 이들의 혼합물을 들 수 있다. Specific examples of the organic solvent include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), hexamethylphosphoamide (HMPA), N, N, N ', N'- Tetramethyl urea (TMU), N, N-dimethylformamide (DMF), or mixtures thereof.
상기 무기염은 방향족 폴리아미드의 중합도를 증가시키기 위하여 첨가하는 것으로서, 그 구체적인 예로는 CaCl2, LiCl, NaCl, KCl, LiBr 및 KBr 등과 같은 할로겐화 알칼리 금속염 또는 할로겐화 알칼리 토금속염을 들 수 있다. 이들 무기염은 단독으로 또는 2종 이상의 혼합물의 형태로 첨가될 수 있다. The inorganic salt is added to increase the degree of polymerization of the aromatic polyamide, and specific examples thereof include halogenated alkali metal salts or halogenated alkaline earth metal salts such as CaCl 2 , LiCl, NaCl, KCl, LiBr and KBr. These inorganic salts may be added alone or in the form of a mixture of two or more thereof.
상기 무기염의 첨가량은 유기용매 중량 대비 2~5중량% 정도인 것이 바람직하다.The amount of the inorganic salt added is preferably about 2 to 5% by weight based on the weight of the organic solvent.
다음으로는, 상기와 같이 시아노기를 포함하는 방향족 디아민이 첨가, 용해된 유기용매에 테레프탈로일 디클로라이드를 상기 시아노기를 포함하는 방향족 디아민과 동일한 몰량(Molar amount)으로 첨가하고, 아울러, 양이온(cation)을 가지는 색소를 상기 유기용매에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조한다.Next, terephthaloyl dichloride is added in the same molar amount as the aromatic diamine containing the cyano group to the organic solvent in which the aromatic diamine containing the cyano group is added and dissolved as described above. A dye having a cation is added to the organic solvent to prepare a polymerization solution containing a copolymerized aramid polymer.
다음은 대표적인 캐치온 색소의 구조이며 한정하지는 않는다.The following are the structures of representative catchon pigments and are not limiting.
색소모체가 아조(azo)인 씨.아이.베이직 블루 64(C.I.Basic Blue 64), 씨.아이.베이직 레드 22(C.I.Basic Red 22),C.I.Basic Blue 64, C.I.Basic Red 22, whose pigment is azo
Figure PCTKR2014012809-appb-I000001
Figure PCTKR2014012809-appb-I000001
씨.아이.베이직 블루 64(C.I.Basic Blue 64)C.I.Basic Blue 64
Figure PCTKR2014012809-appb-I000002
Figure PCTKR2014012809-appb-I000002
씨.아이.베이직 레드 22(C.I.Basic Red 22)C.I.Basic Red 22
색소모체가 아진(azine)과 아조(azo) 복합체인 씨.아이.베이직 블랙 2(C.I.Basic Black 2),C.I.Basic Black 2, in which the pigment matrix is a azine and azo complex,
Figure PCTKR2014012809-appb-I000003
Figure PCTKR2014012809-appb-I000003
씨.아이.베이직 블랙 2(C.I.Basic Black 2)C.I.Basic Black 2
색소모체가 아진(azine) 과 옥사진(oxazine) 복합체인 씨.아이.베이직 블랙 7(C.I.Basic Black 7),C.I. Basic Black 7, whose pigment is an azine and oxazine complex,
Figure PCTKR2014012809-appb-I000004
Figure PCTKR2014012809-appb-I000004
씨.아이.베이직 블랙 7(C.I.Basic Black 7)C.I.Basic Black 7
색소모체가 옥사진(oxazine)인 씨.아이.베이직 블루 10(C.I.Basic Blue 10), 씨.아이.베이직 블루 12(C.I.Basic Blue 12), 씨.아이.베이직 블루 74(C.I.Basic Blue 74),C.I.Basic Blue 10, CIBasic Blue 12, C.I.Basic Blue 74, whose pigment is oxazine. ,
Figure PCTKR2014012809-appb-I000005
Figure PCTKR2014012809-appb-I000005
씨.아이.베이직 블루 10(C.I.Basic Blue 10)C.I.Basic Blue 10
Figure PCTKR2014012809-appb-I000006
Figure PCTKR2014012809-appb-I000006
씨.아이.베이직 블루 12(C.I.Basic Blue 12)C.I.Basic Blue 12
Figure PCTKR2014012809-appb-I000007
Figure PCTKR2014012809-appb-I000007
씨.아이.베이직 블루 74(C.I.Basic Blue 74)C.I.Basic Blue 74
색소모체가 티아진(thiazine)인 씨.아이.베이직 블루 24(C.I.Basic Blue 24), 씨.아이.베이직 블루 25(C.I.Basic Blue 25),C.I.Basic Blue 24, C.I.Basic Blue 25, whose pigment is thiazine
Figure PCTKR2014012809-appb-I000008
Figure PCTKR2014012809-appb-I000008
씨.아이.베이직 블루 24(C.I.Basic Blue 24)C.I.Basic Blue 24
Figure PCTKR2014012809-appb-I000009
Figure PCTKR2014012809-appb-I000009
씨.아이.베이직 블루 25(C.I.Basic Blue 25)C.I.Basic Blue 25
색소모체가 안트라퀴논(anthraquinone)인 씨.아이.베이직 블루 47(C.I.Basic Blue 47), 씨.아이.베이직 블루 22(C.I.Basic Blue 22)C.I.Basic Blue 47, C.I.Basic Blue 22, whose pigment is anthraquinone
Figure PCTKR2014012809-appb-I000010
Figure PCTKR2014012809-appb-I000010
씨.아이.베이직 블루 47(C.I.Basic Blue 47)C.I.Basic Blue 47
Figure PCTKR2014012809-appb-I000011
Figure PCTKR2014012809-appb-I000011
씨.아이.베이직 블루 22(C.I.Basic Blue 22)C.I.Basic Blue 22
색소모체가 이중 아조(double azo)인 씨.아이.베이직 레드 32(C.I.Basic Red 32), 씨.아이.베이직 레드 111(C.I.Basic Red 111),C.I.Basic Red 32, C.I.Basic Red 111, whose pigment is double azo,
Figure PCTKR2014012809-appb-I000012
Figure PCTKR2014012809-appb-I000012
씨.아이.베이직 레드 32(C.I.Basic Red 32)C.I.Basic Red 32
Figure PCTKR2014012809-appb-I000013
Figure PCTKR2014012809-appb-I000013
씨.아이.베이직 레드 111(C.I.Basic Red 111)C.I.Basic Red 111
색소모체가 프탈로시아닌(phthalocyanine)인 씨.아이.베이직 블루 140(C.I.Basic Blue 140),C.I.Basic Blue 140, whose pigment is phthalocyanine,
Figure PCTKR2014012809-appb-I000014
Figure PCTKR2014012809-appb-I000014
씨.아이.베이직 블루 140(C.I.Basic Blue 140)C.I.Basic Blue 140
상기 양이온을 가지는 색소의 투입함량은 공중합 아라미드 중합체 중량대비 0.1~5중량%인 것이 바람직하다. 상기 투입 함량이 0.1중량% 미만이면 색강도가 약하고 5중량%를 초과하는 경우에는 섬유의 물성이 저하될 수 있다.The content of the dye having a cation is preferably 0.1 to 5% by weight based on the weight of the copolymer aramid polymer. If the input content is less than 0.1% by weight, the color strength is weak, and when the content exceeds 5% by weight, the physical properties of the fiber may decrease.
다음으로는, 상기와 같이 제조된 중합용액을 그대로 방사도프로 사용하여 방사구금을 통해 압출한 다음, 압출된 중합용액을 응고액으로 응고시켜 필라멘트 상의 공중합 아라미드 원착사를 제조한다.Next, the polymerization solution prepared as described above is extruded through a spinneret using a spinning dope as it is, and then the extruded polymerization solution is coagulated with a coagulation solution to prepare a copolymerized aramid primary yarn on filament.
상기의 공중합 아라미드 중합체를 포함하는 중합용액을 중합하는 공정 중에 양이온(Cation)을 가지는 색소 대신에 음이온(Anion)을 가지는 색소를 투입하는 경우에는 시아노 기(-CN)가 강한 전기 음성을 가져 음이온(Anion) 색소의 음이온 술폰기와 서로 반발하게 되고, 그로인해 음이온 색소가 폴리머에 침착되지 못하고 용매와 함께 빠져나와 착색 수준이 아니라 오염 수준의 색상을 띄게되고 색강도, 일광견뢰도 및 세탁견뢰도가 크게 저하된다.In the case of adding a dye having an anion instead of a dye having a cation during the process of polymerizing the polymerization solution containing the copolymerized aramid polymer, the cyano group (-CN) has a strong electronegative anion. (Anion) Reacts with the anion sulfonic groups of the dyes, whereby the anion dyes do not deposit on the polymer and escape with the solvent, resulting in a color of contamination level rather than the level of pigmentation, which greatly reduces color intensity, light fastness and wash fastness. do.
음이온(Anion)을 가지는 색소의 일례는 아래와 같다.An example of the pigment | dye which has anion is as follows.
씨.아이.액시드 블루 25(C.I.Basic Acid Blue 25)C.I.Basic Acid Blue 25
Figure PCTKR2014012809-appb-I000016
Figure PCTKR2014012809-appb-I000016
씨.아이.액시드 레드 138(C.I.Basic Acid Red 138)C.I.Basic Acid Red 138
Figure PCTKR2014012809-appb-I000017
Figure PCTKR2014012809-appb-I000017
씨.아이.액시드 블랙 60(C.I.Basic Acid Black 60)C.I. Basic Acid Black 60
본 발명에 따른 공중합 아라미드 원착사는 상기의 양이온을 가지는 색소중 1종만을 함유할 수도 있고 2종 이상을 함께 함유할 수도 있다.The copolymerized aramid primary yarn according to the present invention may contain only one kind of the dye having the above cation or may contain two or more kinds together.
상기 양이온을 가지는 색소는 양이온을 가지는 안료, 양이온을 가지는 염료 또는 양이온을 가지는 안료와 양이온을 가지는 염료의 혼합물이다.The dye having a cation is a pigment having a cation, a dye having a cation or a mixture of a pigment having a cation and a dye having a cation.
상기 본 발명에 따른 방법으로 제조된 공중합 아라미드 원착사는 양이온(cation)을 가지는 색소를 함유하여 색강도가 50 이상으로 우수하고 일광견뢰도 및 세탁견뢰도가 4급 내지 5급으로 우수하며, 공중합 아라미드 중합체의 중합도가 저하가 없어서 강도가 28~35g/d로 우수하다.The copolymerized aramid primary yarn prepared by the method according to the present invention contains a pigment having a cation (coloration) is excellent in color strength of 50 or more, excellent light fastness and wash fastness of the fourth to fifth grade, There is no fall in polymerization degree and the strength is excellent at 28-35 g / d.
이하, 실시예 및 비교실시예를 통하여 본 발명을 보다 구체적으로 살펴본다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
실시예 1Example 1
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Basic Black 2를 0.3중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. 0.3 wt% of Basic Black 2 (relative to the weight of the copolymerized aramid polymer) was added at the same time to prepare a polymerization solution including the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃ 에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat-treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
실시예 2Example 2
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 100몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 100 mol% of cyano-p-phenylenediamine was added. Into the reactor was dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Basic Blue 22을 1.5중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. Basic Blue 22 was added at the same time 1.5% by weight (based on the weight of the copolymerized aramid polymer) to prepare a polymerization solution containing the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
실시예 3Example 3
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Basic Blue 64를 3중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. 3 wt% of Basic Blue 64 (by weight of the copolymerized aramid polymer) was added at the same time to prepare a polymerization solution including the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
실시예 4Example 4
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 100몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 100 mol% of cyano-p-phenylenediamine was added. Into the reactor was dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Basic Red 22를 4.9중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. 4.9% by weight of Basic Red 22 (based on the weight of the copolymerized aramid polymer) was added at the same time to prepare a polymerization solution containing the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
실시예 5Example 5
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Basic Black 7을 0.3중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. 0.3 wt% of Basic Black 7 (by weight of the copolymerized aramid polymer) was added at the same time to prepare a polymerization solution including the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
실시예 6Example 6
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Basic Blue 74를 1.5중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. Basic Blue 74 was added at the same time 1.5% by weight (based on the weight of the co-polymer aramid polymer) to prepare a polymerization solution containing the copolymer aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
실시예 7Example 7
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Basic Blue 24를 3중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. 3% by weight of Basic Blue 24 (relative to the weight of the copolymerized aramid polymer) was simultaneously added to prepare a polymerization solution including the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
실시예 8Example 8
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Basic Blue 25를 4.9중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. 4.99% by weight of Basic Blue 25 (based on the weight of the copolymerized aramid polymer) was added at the same time to prepare a polymerization solution including the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
실시예 9Example 9
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Basic Blue 47을 1.5중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. Basic Blue 47 was added at the same time 1.5% by weight (based on the weight of the copolymerized aramid polymer) to prepare a polymerization solution containing the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
실시예 10Example 10
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Basic Red 32를 3중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. 3% by weight of Basic Red 32 (based on the weight of the copolymerized aramid polymer) was simultaneously added to prepare a polymerization solution including the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
실시예 11Example 11
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Basic Red 111을 4.9중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. 4.9% by weight of Basic Red 111 (by weight of the copolymerized aramid polymer) was simultaneously added to prepare a polymerization solution including the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
실시예 12Example 12
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Basic Blue 140을 0.3중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. 0.3 wt% of Basic Blue 140 (by weight of the copolymerized aramid polymer) was added at the same time to prepare a polymerization solution including the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
실시예 13Example 13
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Basic Blue 10을 0.3중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. 0.3 parts by weight of Basic Blue 10 (based on the weight of the copolymerized aramid polymer) was added at the same time to prepare a polymerization solution including the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
실시예 14Example 14
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Basic Blue 12를 3중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. 3% by weight of Basic Blue 12 (based on the weight of the copolymerized aramid polymer) was simultaneously added to prepare a polymerization solution including the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
비교실시예 1Comparative Example 1
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%를 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다. Subsequently, 100 mol% of terephthaloyl dichloride was added to the reactor containing the mixed solution, thereby preparing a polymerization solution including a copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 섬유를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare copolymerized aramid fibers.
상기와 같이 제조된 공중합 아라미드 섬유 0.5g을(증류수 100㎖에 상기 염색성 염료(C.I. Basic Red 22) 0.2g과 빙초산 1.2㎖를 첨가하여 제조된 염기성염료 염옥에 넣고 100℃에서 1시간 염색한 후 수세, 건조하였다.0.5 g of the copolymerized aramid fiber prepared as described above (0.2 g of the dyeable dye (CI Basic Red 22) and 1.2 ml of glacial acetic acid were added to 100 ml of distilled water, added to basic dye salt jade and dyed at 100 ° C. for 1 hour, followed by washing with water). And dried.
제조한 공중합 아라미드 염색사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The results of evaluating the color strength and color fastness of the manufactured copolymer aramid dye were as shown in Table 1.
비교실시예 2Comparative Example 2
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 100몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 100 mol% of cyano-p-phenylenediamine was added. Into the reactor was dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 폴리비닐피리딘 57중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and 57 wt% of polyvinylpyridine (relative to the weight of the copolymerized aramid polymer) were simultaneously added to the reactor containing the mixed solution, thereby preparing a polymerization solution including a copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 섬유를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare copolymerized aramid fibers.
상기와 같이 제조된 공중합 아라미드 섬유 0.5g을(증류수 100㎖에 상기 염색성 염료(C.I. Basic Red 22) 0.2g과 빙초산 1.2㎖를 첨가하여 제조된 염기성염료 염옥에 넣고 100℃에서 1시간 염색한 후 수세, 건조하였다.0.5 g of the copolymerized aramid fiber prepared as described above (0.2 g of the dyeable dye (CI Basic Red 22) and 1.2 ml of glacial acetic acid were added to 100 ml of distilled water, added to basic dye salt jade and dyed at 100 ° C. for 1 hour, followed by washing with water). And dried.
제조한 공중합 아라미드 염색사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The results of evaluating the color strength and color fastness of the manufactured copolymer aramid dye were as shown in Table 1.
비교실시예 3Comparative Example 3
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Acid Blue 25를 0.3중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. Acid Blue 25 was added simultaneously with 0.3% by weight (based on the weight of the copolymerized aramid polymer) to prepare a polymerization solution containing the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
비교실시예 4Comparative Example 4
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Acid Red 138을 2중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. 2% by weight of Acid Red 138 (relative to the weight of the copolymerized aramid polymer) was added to prepare a polymerization solution including the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
비교실시예 5Comparative Example 5
3중량%의 CaCl2를 포함하는 N-메틸-2-피롤리돈(NMP) 유기용매를 질소 분위기 하에서 반응기 내에 넣고, 파라-페닐렌디아민(p-phenylenediamine) 50몰%와 시아노-파라-페닐렌디아민(cyano-p-phenylenediamine) 50몰%를 상기 반응기에 넣고 녹여서 혼합용액을 제조하였다.An N-methyl-2-pyrrolidone (NMP) organic solvent containing 3% by weight of CaCl 2 was placed in a reactor under a nitrogen atmosphere, and 50 mol% of p-phenylenediamine and cyano-para- 50 mol% of phenylenediamine (cyano-p-phenylenediamine) was added to the reactor and dissolved to prepare a mixed solution.
이어서 상기 혼합용액이 담긴 반응기에 테레프탈로일 디클로라이드 100몰%와 C.I. Acid Black 60를 4중량%(공중합 아라미드 중합체 중량대비)를 동시에 첨가하여 공중합 아라미드 중합체를 포함하는 중합용액을 제조하였다.Subsequently, 100 mol% of terephthaloyl dichloride and C.I. 4% by weight of Acid Black 60 (by weight of the copolymerized aramid polymer) was added at the same time to prepare a polymerization solution including the copolymerized aramid polymer.
이어서, 상기 중합용액을 방사구금을 통해 압출한 후 에어 갭 및 응고액을 순차적으로 통과하도록 함으로써 3,000denier의 선밀도를 갖는 멀티필라멘트를 형성하였다. 방사팩의 압력은 2,800psi이었고, 방사속도는 600mpm(meter per minuite)이었다.Subsequently, the polymer solution was extruded through a spinneret and then passed through an air gap and a coagulation solution, thereby forming a multifilament having a linear density of 3,000 denier. The spin pack pressure was 2,800 psi and the spinning speed was 600 mpm (meter per minuite).
이어서, 상기 멀티필라멘트를 수세하고 수세된 멀티필라멘트를 150℃의 온도로 설정된 건조 롤러에서 건조 및 연신한 후 연신된 멀티필라멘트를 250℃에서 열처리하고 권취하여 공중합 아라미드 원착사를 제조하였다.Subsequently, the multifilament was washed with water, and the washed multifilament was dried and stretched on a drying roller set at a temperature of 150 ° C., and then the stretched multifilament was heat treated at 250 ° C. and wound to prepare a copolymerized aramid yarn.
제조한 공중합 아라미드 원착사의 색강도, 견뢰도를 평가한 결과는 표 1과 같았다.The color strength and color fastness of the manufactured copolymer aramid primary yarns were evaluated as shown in Table 1.
표 1
구분 색강도(K/S값) 일광견뢰도(급) 세탁견뢰도(급)
실시예 1 50 4급 5급
실시예 2 120 4급 4급
실시예 3 180 4급 4급
실시예 4 200 4급 5급
실시예 5 60 4급 4급
실시예 6 110 4급 4급
실시예 7 170 4급 5급
실시예 8 210 5급 4급
실시예 9 100 4급 4급
실시예 10 150 4급 4급
실시예 11 180 5급 4급
실시예 12 50 4급 4급
실시예 13 60 4급 4급
실시예 14 120 4급 5급
비교실시예 1 5 2급 2급
비교실시예 2 40 2-3급 3급
비교실시예 3 10 2급 2급
비교실시예 4 30 2급 2급
비교실시예 5 25 2급 2급
Table 1
division Color intensity (K / S value) Daylight Fastness (Grade) Wash fastness (class)
Example 1 50 Grade 4 Grade 5
Example 2 120 Grade 4 Grade 4
Example 3 180 Grade 4 Grade 4
Example 4 200 Grade 4 Grade 5
Example 5 60 Grade 4 Grade 4
Example 6 110 Grade 4 Grade 4
Example 7 170 Grade 4 Grade 5
Example 8 210 Grade 5 Grade 4
Example 9 100 Grade 4 Grade 4
Example 10 150 Grade 4 Grade 4
Example 11 180 Grade 5 Grade 4
Example 12 50 Grade 4 Grade 4
Example 13 60 Grade 4 Grade 4
Example 14 120 Grade 4 Grade 5
Comparative Example 1 5 2nd class 2nd class
Comparative Example 2 40 2-3 grade Level 3
Comparative Example 3 10 2nd class 2nd class
Comparative Example 4 30 2nd class 2nd class
Comparative Example 5 25 2nd class 2nd class
상기 표1의 색강도 및 견뢰도는 아래와 같은 방법으로 평가하였다.Color intensity and color fastness of the above Table 1 were evaluated by the following method.
색강도Color intensity
KS K 0205에 의거하여 측색하여 색강도를 확인하였다. 구체적으로 아라미드 섬유를 가로 7.5cm 세로 6.5cm의 소형 카드에 촘촘히 감은 다음 분광측색계 (Konica-Minolta CM-3600d spectrophotometer)를 사용하여 D65광원에서 10도 시야로 측색하였다. 이 때 측색된 값은 위치를 바꾸어 가며 3회 측색한 평균값을 구하였다.Color intensity was confirmed based on KS K 0205. Specifically, the aramid fibers were wound tightly on a small card 7.5 cm long and 6.5 cm wide, and then measured with a 10 degree field of view at a D65 light source using a spectrophotometer (Konica-Minolta CM-3600d spectrophotometer). At this time, the average value measured three times by changing the position was measured.
Figure PCTKR2014012809-appb-I000018
Figure PCTKR2014012809-appb-I000018
Figure PCTKR2014012809-appb-I000019
Figure PCTKR2014012809-appb-I000019
Figure PCTKR2014012809-appb-I000020
Figure PCTKR2014012809-appb-I000020
Figure PCTKR2014012809-appb-I000021
Figure PCTKR2014012809-appb-I000021
Figure PCTKR2014012809-appb-I000022
Figure PCTKR2014012809-appb-I000022
Figure PCTKR2014012809-appb-I000023
Figure PCTKR2014012809-appb-I000023
K : 흡수계수(Absorption coefficient)K: Absorption coefficient
S : 분산계수(Scattering coefficient)S: Scattering coefficient
K : 반사율(Reflectance)K: Reflectance
일광 견뢰도Daylight fastness
KS K 0700에 의거하여 진행하였고, 변퇴색은 KS K ISO 105-A05 측색계를 사용한 변퇴색 등급 측정을 따랐다. Progress was made according to KS K 0700, and fading was followed by fading grading measurements using the KS K ISO 105-A05 colorimeter.
세탁견뢰도Color fastness
KS K ISO 105-C06에 의거하여 진행하였고, 시험 후 원단의 변퇴색은 KS K ISO 105-A05 측색계를 사용한 변퇴색 등급 측정을 따랐다.It proceeded according to KS K ISO 105-C06, and the discoloration of the fabric after the test followed the fading grade measurement using the KS K ISO 105-A05 colorimeter.
본 발명에 따른 공중합 아라미드 원착사는 방호용 장갑이나 방호복 소재로 유용하다.Copolymer aramid primary yarn according to the invention is useful as a protective glove or protective clothing material.

Claims (13)

  1. 시아노기를 포함하는 방향족 디아민이 용해되어 있는 유기용매에 테레프탈로일 디클로라이드를 첨가, 반응시켜 공중합 아라미드 중합체를 포함하는 중합용액을 중합한 다음 상기 중합용액을 방사, 응고하여 제조되는 공중합 아라미드 원착사에 있어서,Copolymer aramid primary yarn prepared by adding and reacting terephthaloyl dichloride in an organic solvent in which an aromatic diamine containing cyano group is dissolved to polymerize a polymerization solution containing a copolymerized aramid polymer, and then spinning and solidifying the polymerization solution. To
    양이온(cation)을 가지는 색소를 함유하여 색강도가 50 이상인 것을 특징으로 하는 공중합 아라미드 원착사.Copolymerized aramid primary yarns containing a dye having a cation, the color intensity is 50 or more.
  2. 제1항에 있어서, 양이온(cation)을 가지는 색소의 함량이 공중합 아라미드 중합체 중량 대비 0.1~5중량%인 것을 특징으로 하는 공중합 아라미드 원착사.The copolymerized aramid primary yarn according to claim 1, wherein the content of the pigment having a cation is 0.1 to 5% by weight based on the weight of the copolymerized aramid polymer.
  3. 제1항에 있어서, 일광견뢰도가 4급 내지 5급인 것을 특징으로 하는 공중합 아라미드 원착사.The copolymerized aramid primary yarn according to claim 1, wherein the daylight fastnesses are grades 4-5.
  4. 제1항에서, 세탁견뢰도가 4급 내지 5급인 것을 특징으로 하는 공중합 아라미드 원착사.The copolymer aramid primary yarns, characterized in that the wash fastness of the fourth to fifth grade.
  5. 제1항에 있어서, 양이온(cation)을 가지는 색소는 씨.아이.베이직 블랙 2(C.I.Basic Black 2), 씨.아이.베이직 블루 22(C.I.Basic Blue 22), 씨.아이.베이직 블루 64(C.I.Basic Blue 64), 씨.아이.베이직 레드 22(C.I.Basic Red 22), 씨.아이.베이직 블랙 7(C.I.Basic Black 7), 씨.아이.베이직 블루 10(C.I.Basic Blue 10), 씨.아이.베이직 블루 12(C.I.Basic Blue 12), 씨.아이.베이직 블루 74(C.I.Basic Blue 74), 씨.아이.베이직 블루 24(C.I.Basic Blue 24), 씨.아이.베이직 블루 25(C.I.Basic Blue 25), 씨.아이.베이직 블루 47(C.I.Basic Blue 47), 씨.아이.베이직 레드 32(C.I.Basic Red 32), 씨.아이.베이직 레드 111(C.I.Basic Red 111) 및 씨.아이.베이직 블루 140(C.I.Basic Blue 140) 중에서 선택된 1종 이상인 것을 특징으로 하는 공중합 아라미드 원착사.The dye according to claim 1, wherein the pigment having a cation is C. Basic Black 2, C. Basic Blue 22, C. Basic Blue 64 (C. CIBasic Blue 64), C.Basic Red 22, C.Basic Black 7, C.Basic Blue 10, and C.Basic Blue 10 I.Basic Blue 12 (CIBasic Blue 12), C.Basic Blue 74 (CIBasic Blue 74), C.Basic Blue 24 (CIBasic Blue 24), C.Basic Blue 25 (CIBasic) Blue 25), C. Basic Blue 47, C. Basic Red 32, C. Basic Red 111 and C. Basic. Copolymer aramid yarns, characterized in that at least one selected from among Basic Blue 140 (CIBasic Blue 140).
  6. 제1항에 있어서, 양이온을 가지는 색소는 양이온을 가지는 안료, 양이온을 가지는 염료 및 양이온을 가지는 안료와 양이온을 가지는 염료의 혼합물인 것을 특징으로 하는 공중합 아라미드 원착사.The copolymer aramid primary yarn according to claim 1, wherein the dye having a cation is a mixture of a pigment having a cation, a dye having a cation, and a pigment having a cation and a dye having a cation.
  7. 시아노기를 포함하는 방향족 디아민이 용해되어 있는 유기용매에 테레프탈로일 디클로라이드를 첨가, 반응시켜 공중합 아라미드 중합체를 포함하는 중합용액을 중합한 다음 상기 중합용액을 방사, 응고하여 공중합 아라미드 원사를 제조함에 있어서,Terephthaloyl dichloride is added and reacted with an organic solvent in which an aromatic diamine containing cyano group is dissolved to polymerize a polymerization solution containing a copolymerized aramid polymer, followed by spinning and solidifying the polymerization solution to prepare a copolymerized aramid yarn. In
    상기의 공중합 아라미드 중합체를 포함하는 중합용액을 중합하는 공정중에 양이온(cation)을 가지는 색소를 첨가하는 것을 특징으로 하는 공중합 아라미드 원착사의 제조방법.The pigment | dye which has a cation is added in the process of superposing | polymerizing the superposition | polymerization solution containing said copolymerization aramid polymer, The manufacturing method of the copolymerized aramid original yarn characterized by the above-mentioned.
  8. 제7항에 있어서, 양이온(cation)을 가지는 색소의 첨가량은 공중합 아라미드 중합체 중량대비 0.1~5중량%인 것을 특징으로 하는 공중합 아라미드 원착사의 제조방법.The method according to claim 7, wherein the amount of the pigment having a cation is 0.1 to 5% by weight based on the weight of the copolymerized aramid polymer.
  9. 제7항에 있어서, 양이온(cation)을 가지는 색소는 씨.아이.베이직 블랙 2(C.I.Basic Black 2), 씨.아이.베이직 블루 22(C.I.Basic Blue 22), 씨.아이.베이직 블루 64(C.I.Basic Blue 64), 씨.아이.베이직 레드 22(C.I.Basic Red 22), 씨.아이.베이직 블랙 7(C.I.Basic Black 7), 씨.아이.베이직 블루 10(C.I.Basic Blue 10), 씨.아이.베이직 블루 12(C.I.Basic Blue 12), 씨.아이.베이직 블루 74(C.I.Basic Blue 74), 씨.아이.베이직 블루 24(C.I.Basic Blue 24), 씨.아이.베이직 블루 25(C.I.Basic Blue 25), 씨.아이.베이직 블루 47(C.I.Basic Blue 47), 씨.아이.베이직 레드 32(C.I.Basic Red 32), 씨.아이.베이직 레드 111(C.I.Basic Red 111) 및 씨.아이.베이직 블루 140(C.I.Basic Blue 140) 중에서 선택된 1종 이상인 것을 특징으로 하는 공중합 아라미드 원착사의 제조방법.8. The pigment of claim 7, wherein the pigment having a cation is C. Basic Black 2, C. Basic Blue 22, C. Basic Blue 64 (C. CIBasic Blue 64), C.Basic Red 22, C.Basic Black 7, C.Basic Blue 10, and C.Basic Blue 10 I.Basic Blue 12 (CIBasic Blue 12), C.Basic Blue 74 (CIBasic Blue 74), C.Basic Blue 24 (CIBasic Blue 24), C.Basic Blue 25 (CIBasic) Blue 25), C. Basic Blue 47, C. Basic Red 32, C. Basic Red 111 and C. Basic. Method of producing a copolymer aramid primary yarn, characterized in that at least one selected from among Basic Blue 140 (CIBasic Blue 140).
  10. 제7항에 있어서, 양이온을 가지는 색소는 양이온을 가지는 안료, 양이온을 가지는 염료 및 양이온을 가지는 안료와 양이온을 가지는 염료의 혼합물인 것을 특징으로 하는 공중합 아라미드 원착사의 제조방법.8. The method according to claim 7, wherein the dye having a cation is a pigment having a cation, a dye having a cation, and a mixture of a pigment having a cation and a dye having a cation.
  11. 제7항에 있어서, 상기 유기용매에 시아노기를 포함하는 방향족 시아노기를 포함하는 디아민으로 파라페닐렌디아민과 시아노-파라-페닐렌디아민을 1:9 ~ 9:1의 몰비로 용해하는 특징으로 하는 공중합 아라미드 원착사의 제조방법.8. The method of claim 7, wherein the organic solvent is a diamine containing an aromatic cyano group containing a cyano group to dissolve paraphenylenediamine and cyano-para-phenylenediamine in a molar ratio of 1: 9 to 9: 1. The manufacturing method of copolymerized aramid primary yarn to be used.
  12. 제7항에 있어서, 상기 유기용매에 시아노기를 포함하는 방향족 디아민으로 시아노-파라-페닐렌디아민을 단독으로 용해하는 것을 특징으로 하는 공중합 아라미드 원착사의 제조방법.The method for producing a copolymerized aramid primary yarn according to claim 7, wherein the cyano-para-phenylenediamine is dissolved alone with an aromatic diamine containing a cyano group in the organic solvent.
  13. 제7항에 있어서, 시아노기를 포함하는 방향족 디아민이 용해된 유기용매에 테레프탈로일 디클로라이드를 유기용매에 용해된 시아노기를 포함하는 방향족 디아민과 동일한 몰량(Molar amount)으로 첨가하는 것을 특징으로 하는 공중합 아라미드 원착사의 제조방법.8. The terephthaloyl dichloride is added to the organic solvent in which the aromatic diamine containing cyano group is dissolved in the same molar amount as the aromatic diamine incorporating the cyano group dissolved in the organic solvent. Method for producing a copolymerized aramid primary yarn to be.
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JP2017504731A (en) 2017-02-09
EP3091107A1 (en) 2016-11-09
JP6185184B2 (en) 2017-08-23
EP3091107A4 (en) 2017-08-09
BR112016015170A2 (en) 2017-08-08
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US20180195207A1 (en) 2018-07-12
KR20150079425A (en) 2015-07-08

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