CN109825894B - Preparation method of chlorine-resistant black polyurethane urea elastic fiber - Google Patents
Preparation method of chlorine-resistant black polyurethane urea elastic fiber Download PDFInfo
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- CN109825894B CN109825894B CN201810071664.5A CN201810071664A CN109825894B CN 109825894 B CN109825894 B CN 109825894B CN 201810071664 A CN201810071664 A CN 201810071664A CN 109825894 B CN109825894 B CN 109825894B
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- 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
- D01F1/10—Other agents for modifying properties
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- 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
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- 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
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
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- 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
- D01F6/72—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyureas
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/32—Elastic yarns or threads ; Production of plied or cored yarns, one of which is elastic
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- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention provides a chlorine-resistant black polyurethaneurea elastic yarn having chlorine resistance and black color, while having excellent spinning characteristics without cutting, and a method for preparing the same.
Description
Technical Field
The present invention relates to a method for preparing black Polyurethaneurea (Polyurethaneurea) elastic fiber having excellent mode characteristics while remarkably improving dyeability, and a chlorine resistant black Polyurethaneurea elastic fiber prepared thereby.
Background
Polyurethane urea elastic fibers are polymers obtained by extending the chain of an isocyanate-terminated Prepolymer (Prepolymer) synthesized from a high molecular weight Polyol (Polyol) and an excess of an organic Diisocyanate (Diisocyanate) with a Diamine (Diamine), and are used as elastic functional materials in clothing in various fields such as tights, socks, pantyhose, and swimwear by being prepared mainly by dry-type and melt-spinning and knitted with Polyamide (Polyamide) fibers, polyester (polyester) fibers, and natural fibers.
However, polyurethane urea elastic yarns have a problem that when dyed black with a disperse dye or an acid dye, they are not dyed uniformly, and particularly when washed, they have low wash fastness due to fading. That is, when a woven or knitted fabric is produced using a common polyurethaneurea elastic yarn and polyester or polyamide yarn and then dyed with these disperse dyes or acid dyes (black), there is a problem that the deep color and/or color fastness are poor.
In order to solve these problems, korean patent laid-open No. 10-646648 discloses a method of preparing black elastic fiber by adding Carbon black (Carbon black) during polymerization and polymerizing, but the black elastic fiber still has a dyeing problem when black is used and dyed thereon, and has a problem that spinning property is poor due to addition of Carbon black, productivity of the fiber is deteriorated, and a cut occurs during spinning.
In addition, in the case of conventional black elastic fibers, chlorine resistance is poor, and thus it is difficult to use the fibers in places exposed to chlorine, such as swimwear.
Prior patent literature
Patent document
Korean patent publication No. 10-646648 (09/11/2006)
Disclosure of Invention
The present invention provides a method for preparing a black polyurethaneurea elastic fiber having excellent spinning characteristics and remarkably improved dyeability.
Also, the present invention provides a method for preparing a polyurethaneurea elastic fiber having excellent black fastness, when preparing a black polyurethaneurea by using carbon black, since the dispersibility of the carbon black is remarkably improved.
Also provided is a method for producing a black polyurethaneurea elastic fiber having a chlorine resistance function for use in swimwear and the like.
The present invention for achieving the above objects provides a chlorine resistant black polyurethaneurea elastic fiber which improves physical properties of the elastic fiber according to color fastness, color, spinning property and dispersibility, and provides an elastic fiber having excellent physical properties by preparing and charging a slurry composition containing a Polyurethane prepolymer (Polyurethane prepolymer) when a chlorine resistant agent and carbon black are added, preparing a spinning dope in which the slurry composition and the polyurethaneurea polymer are mixed, and spinning the dope.
The present invention relates to a method for preparing a chlorine-resistant black polyurethaneurea elastic fiber, the chlorine-resistant black polyurethaneurea elastic fiber including carbon black, the method comprising: a step of preparing a polyurethaneurea polymer; a step of mixing a slurry composition containing a chlorine inhibitor, carbon black, and a polyurethane prepolymer having an unreacted terminal Isocyanate group (Isocyanate group) with the polyurethane urea polymer to prepare a spinning dope; and spinning by using the spinning solution.
Also, the present invention relates to a chlorine resistant black polyurethaneurea elastic fiber prepared by the above preparation method.
ADVANTAGEOUS EFFECTS OF INVENTION
The chlorine-resistant black polyurethaneurea elastic fiber of the present invention can provide an elastic fiber excellent in uniformity and spinnability of black color, and excellent in black fastness and dyeability.
The elastic fiber of the present invention can provide excellent fabric color, and is excellent in strength retention and elastic recovery, and excellent in elastic recovery and strength retention after dyeing.
Detailed Description
The present invention will be described in more detail below with reference to specific examples and examples. However, the following specific examples or embodiments are merely illustrative of one type of the invention in detail, and the invention is not limited thereto, but may be implemented in various forms.
Also, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the present invention is for the purpose of effectively describing particular embodiments only and is not intended to be limiting of the invention.
Also, as used in the specification and the appended claims, the singular forms "a", "an", and "the" may include plural referents unless the context clearly dictates otherwise.
One embodiment of the present invention is a method for producing a chlorine-resistant black polyurethaneurea elastic fiber, the chlorine-resistant black polyurethaneurea elastic fiber including carbon black, the method comprising: a step of preparing a polyurethaneurea polymer; a step of mixing a slurry composition containing a chlorine inhibitor, carbon black and a polyurethane prepolymer having an unreacted terminal isocyanate group with the polyurethane urea polymer to prepare a spinning dope; and spinning by using the spinning solution.
In one embodiment of the present invention, the polyurethane prepolymer may contain 2.4 mol% to 3.5 mol% of unreacted terminal isocyanate groups. In one embodiment of the present invention, the polyurethane urea polymer may be prepared by: a polyurethane urea polymer is prepared by charging Polytetramethylene ether glycol (Polytetramethylene ether glycol) and Diphenylmethane-4, 4'-diisocyanate (Diphenylmethane-4, 4' -diisocyanate) and mixing them so that the NCO/OH molar ratio is 1.50 to 2.50 to prepare a polyurethane prepolymer having an unreacted Isocyanate at the terminal end (Isocyanate) content of 2.4 to 3.5 mol%, and then reacting the polyurethane prepolymer with a chain extender, a chain terminator and a crosslinking agent.
In an embodiment of the present invention, the chlorine resistant black polyurethane urea elastic fiber may include 0.1 to 3 weight percent of carbon black and 0.5 to 4.0 weight percent of chlorine resistant agent, based on the total weight of the chlorine resistant black polyurethane urea elastic fiber.
In an embodiment of the present invention, the slurry composition may include 1 to 20 weight percent of the polyurethane prepolymer.
In one embodiment of the present invention, the slurry composition may further comprise one or more components selected from a whiteness improving agent, an antioxidant, a gas stabilizer, a dyeability improving agent, a spinnability improving agent, and a strength improving agent.
In one embodiment of the present invention, the chlorine inhibitor and the carbon black may have an average particle diameter of 3 μm or less.
In an embodiment of the present invention, the slurry composition may further include 0.01 to 1 weight percent of Polyacrylonitrile (Polyacrylonitrile).
In another embodiment of the present invention, the chlorine resistant black polyurethaneurea elastic fiber is prepared by the above preparation method.
In one embodiment of the present invention, the elastic fiber may be spun by mixing a polyurethane urea polymer, an unreacted terminal polyurethane prepolymer, a chlorine inhibitor, and carbon black.
In an embodiment of the present invention, the elastic fiber may include 0.1 to 3 weight percent of carbon black, and 0.5 to 4.0 weight percent of chlorine inhibitor.
In an embodiment of the present invention, the elastic fiber may include 1 to 20 weight percent of polyurethane prepolymer.
The process for producing the chlorine resistant black polyurethaneurea elastic fiber of the present invention is described in more detail below.
In one embodiment of the production method of the present invention, the first polymerization step for producing a polyurethane prepolymer may be performed at a time; a step of preparing a polyurethane prepolymer mixed solution (alternatively referred to as "polyurethane polymer solution"); a second polymerization step of preparing a polyurethaneurea polymer (alternatively referred to as "polyurethaneurea polymer") by mixing the above polyurethane prepolymer mixed solution with an Amine (Amine) solution; preparing a spinning dope by adding and uniformly mixing a slurry composition to the polyurethane urea polymer, the slurry composition containing a chlorine inhibitor, carbon black, and a polyurethane prepolymer having an unreacted terminal isocyanate group; and spinning the spinning dope. The step of preparing the above amine solution may be prepared in advance to be charged regardless of the order listed above.
More specifically, in one embodiment of the preparation method of the present invention, the method comprises: a first polymerization step of polymerizing polytetramethylene ether glycol and diphenylmethane-4, 4' -diisocyanate in an NCO/OH molar ratio of 1.5 to 2.5 to prepare a polyurethane prepolymer having an isocyanate content of 2.4 to 3.5 mol%; a step of adding N, N-dimethylacetamide (N, N-dimethylacetamide) to the polyurethane prepolymer to prepare a polyurethane polymer solution having a solid content of 35 to 45 weight percent; a step of adding a solution in which a chain extender, a chain terminator, a viscosity stabilizer, and a crosslinking agent are dissolved in N, N-dimethylacetamide to the polyurethane polymer solution, and performing a second polymerization to prepare a polyurethane urea polymer having a solid content of 35%; the method for producing a spinning dope includes the step of mixing an additive slurry composition, which is prepared by adding and dispersing an additive composition containing carbon black, a chlorine inhibitor and a polyurethane prepolymer to N, N-dimethylacetamide, to the polyurethane urea polymer, wherein the additive composition contains the carbon black, the chlorine inhibitor and the polyurethane prepolymer.
The chlorine-resistant black polyurethaneurea elastic fiber prepared by the above preparation method is characterized by excellent chlorine resistance and improved black fastness and dyeability.
In one embodiment of the present invention, the first polymerization step for preparing the polyurethane prepolymer is specifically described.
In one embodiment of the present invention, a polyurethane prepolymer having a terminal unreacted isocyanate content of 2.4 to 3.5 mol% can be prepared by polymerizing the polytetramethylene ether glycol and Diphenylmethane-4, 4' -diisocyanate so that the NCO/OH molar ratio is 1.5 to 2.5.
In this case, the polytetramethylene ether glycol and the diphenylmethane-4, 4' -diisocyanate are continuously transferred to a static mixer (static mixer) as a homomixer by using a fixed displacement pump so that they can be mixed at 30 to 50 ℃, more preferably 35 to 45 ℃, and then put into a continuous polymerization tube in the form of a cylindrical tube so that polymerization can be carried out at a reaction temperature of 60 to 100 ℃, more preferably 70 to 98 ℃. The temperature is not limited to the above range, but the formation of gel in the polyurethane prepolymer is reduced as much as possible in the above range.
And, polytetramethylene ether glycol and diphenylmethane-4, 4' -diisocyanate at an NCO/OH molar ratio of 1.5 to 2.5 can be used to prepare a polyurethane prepolymer so that the content of unreacted isocyanate at the terminal is 2.4 to 3.5 mol%. The content of the terminal unreacted isocyanate is in the range of 2.4 to 3.5 mol%, and viscosity formation enabling spinning and physical properties required after spinning can be ensured.
Then, the process for preparing the polyurethane polymer solution is specifically described.
After cooling the prepared polyurethane prepolymer to 30 to 50 ℃ and stabilizing the same, the polyurethane prepolymer and N, N-dimethylacetamide as the first polymer are put into a high-end mixer and completely dissolved before being put into the second reactor, thereby preparing a polyurethane prepolymer mixed solution. By this procedure, the content of the unreacted diisocyanate can be sufficiently reduced and then supplied to the second polymerization reactor. In this case, it is preferable to remove unreacted materials by vigorously stirring at 3000 to 4000rpm in a high-end stirrer to completely dissolve the unreacted materials. And then cooling to 30-50 ℃ to prepare a polyurethane prepolymer mixed solution with the solid content of 35-45 weight percent. The above solid content is preferably in the range of 35 to 45% by weight because the amine solution having a solid content of 7% is added at the time of Urea (Urea) reaction, but the solid content is maintained higher than that of the final polymer in order to adjust the solid content of the final polymer to 35 to 40%.
Next, the second polymerization step for preparing a polyurethaneurea polymer by mixing the above polyurethane polymer solution and the amine solution is more specifically explained.
Next, a second polymerization step of preparing a polyurethane urea polymer by mixing the polyurethane polymer solution and the amine solution will be described more specifically, and the polyurethane urea polymer may be added together with the polyurethane prepolymer mixed solution at the time of second polymerization. In terms of facilitating the adjustment of the equivalent ratio, it is preferable to prepare in advance the post-mixing before carrying out the second polymerization step.
The amine solution is prepared by dissolving Diethylenetriamine (Diethylenetriamine) in N, N-dimethylacetamide using a chain extender, a chain terminator and a crosslinking agent.
Specifically, in the present invention, diamines such as Ethylenediamine (ethylene diamine) are used as the chain extender, and dialkylmonoamine (Diethylamine) is used as the chain terminator, but the present invention is not limited thereto. The crosslinking agent is Diethyl triamine (Diethyl triamine) or the like, but a chain terminator, a chain extender and a crosslinking agent used in the technical field can be used without limitation.
In the present invention, the object of the present invention is suitably achieved when the amount of diethylamine as a chain terminator is 1/5.0 to 8.0 (amine equivalent ratio) relative to ethylenediamine as a chain extender, and when the amine equivalent ratio is less than 5.0, physical properties cannot be expressed when the yarn is produced due to a decrease in the molecular weight of the polymer, and when the amine equivalent ratio is more than 8.0, viscosity increases and gelation occurs due to an increase in the molecular weight, and therefore, heat resistance and chlorine resistance required in the above ranges can be expressed.
When 100 to 300ppm of diethyltriamine as a viscosity stabilizing and crosslinking agent is added to the final dope solid, excellent dispersion and spinning characteristics can be achieved in the carbon black of the present invention, but the present invention is not limited thereto.
In one embodiment of the present invention, when the polyurethane urea polymer is prepared by mixing the polyurethane polymer solution and the amine solution, the mixing is performed so that the amine/isocyanate equivalent ratio is 1.01 to 1.06/1. When the amine/isocyanate equivalent ratio is less than 1.01, the method forms a desired spinning viscosity, and when it exceeds 1.06, the viscosity is increased to a large extent and a gelling phenomenon may occur, and therefore, it is preferable to add the surfactant in the above range, but the method is not limited thereto.
In the second polymerization step, a cooling device is provided, and the reaction can be carried out in a second polymerization machine equipped with a blade, and preferably, the stirring speed of the second polymerization machine is adjusted so that the reaction efficiency of the polyurethane polymer solution and the amine solution becomes 80% or more. The proper stirring speed can be determined by measuring the stirring efficiency at the outlet of the second polymerizer. The solid content of the polyurethaneurea polymer synthesized by the chain extension reaction and the chain termination reaction may be 35 to 40 wt% and in the case where the solid content is less than 35 wt%, spinning is impossible due to low viscosity, physical properties are difficult to express when preparing a raw yarn, and in the case where the solid content is more than 40 wt%, spinning is impossible due to high viscosity, and thus, it is preferable to be within the above range, but not limited thereto.
In one embodiment of the present invention, the above-mentioned polyurethaneurea polymer is suitably used for achieving the object of the present invention, and the polyurethaneurea polymer has an apparent viscosity of 1000 poise to 2500 poise measured at 40 ℃ and an intrinsic limit of 1.0. + -. 0.2, but is not limited thereto. An after-viscosity having an apparent viscosity of about 1000 to 2500 poise at 40 ℃, that is, a post-polymerization time of the second polymerization after charging the Slurry (Slurry), is required for generating a spinning viscosity, and an increased viscosity is easily controlled during the aging process, so that it is preferable. And, preferably, the inherent viscosity of the polyurethane polyurea polymer measured at a concentration of 0.5g per 100ml of the solution in N, N-dimethylacetamide is 1.0 ± 0.2.
Next, the process of preparing the spinning dope will be specifically described.
In one embodiment of the present invention, when preparing the spinning solution, the slurry composition may be added to and mixed with the polyurethane urea polymer to prepare the spinning solution having a solid content of 35 to 40 wt%, but is not limited thereto. At this time, preferably, a static mixer is used to mix the mixture, but not limited thereto.
Specifically, the process of preparing the slurry added to the spinning dope is described. In the present invention, when preparing a spinning dope, a chlorine inhibitor and carbon black are mixed with a polyurethane prepolymer or a polyurethane polymer solution prepared in advance, and the mixture is dispersed and pulverized by a sand mill or the like to prepare a slurry form, and the slurry form is mixed with the above-mentioned polyurethaneurea polymerization solution and spun, thereby preparing a chlorine-resistant spun fiber having excellent color fastness, dyeability and black dispersibility.
In the present invention, for the above-mentioned slurry composition, the chlorine-resistant black polyurethaneurea fiber, which is the object of the present invention, is prepared by preparing a slurry composition comprising 0.1 to 3 weight percent of carbon black, 0.5 to 4.0 weight percent of chlorine inhibitor, and 1 to 20 weight percent of polyurethane prepolymer, and preferably, when spinning is performed, spinning can be stably performed, but is not limited to the above-mentioned range.
The chlorine inhibitor is not limited as long as it is used in the art, but for example, Magnesium carbonate (Magnesium carbonate) represented by the following chemical formula may be mentioned, but not limited thereto.
M2+x(An-)yM2+(OH)z·mH2O
(in the above formula, M2+Is Mg2+Or Ca2+，An-Is CO3 2-X is 1 to 5, y is 1 to 5, z is 0 to 2, and m is 0 to 5. )
In one embodiment of the present invention, the chlorine inhibitor and the carbon black preferably have an average particle size of 5 μm or less, more preferably 2 μm or less. More specifically, it may be 0.1 μm to 5 μm. In the above particle range, the possibility that the color of the final product becomes gray (a value is lowered) and the color of the product is deteriorated can be prevented, and the spinning continuity and the production stability are also excellent.
In addition, in one embodiment of the present invention, when polyacrylonitrile is further contained in the size composition, elastic fibers having more excellent washing fastness, more excellent spinning property, and more excellent mechanical properties and color of the raw yarn can be provided. The weight average molecular weight of the polyacrylonitrile is 50000 to 300000, more specifically, preferably, 100000 to 200000, and the physical properties can be expected to be more improved, but not limited thereto. And, when the content thereof is in the range of 0.01 to 1.0 weight percent, more specifically, 0.2 to 0.7 weight percent, of the content of the size composition, it is preferable to provide elastic fiber having improved washing fastness, excellent spinnability, more excellent mechanical properties and strand color, but not limited thereto.
In one embodiment of the present invention, the slurry composition is prepared by adding, as necessary, various components that can be used in the fields of Titanium dioxide (Titanium dioxide), an antioxidant, a gas stabilizer, a dyeing property improver, a spinning property improver, and a strength improver, in addition to the carbon black and the chlorine inhibitor, to the slurry composition, and these components are not limited as long as they are known in the art.
The whiteness-improving agent may be titanium dioxide, and the desired effect of the whiteness-improving agent can be effectively obtained by using 0.01 to 0.5 weight% of titanium dioxide based on the solid content of the final product, but the whiteness-improving agent is not limited thereto.
As a specific example of the antioxidant for capturing a group which is decomposed by heat or sunlight, 1, 3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzene) -1, 3, 5-triazine-2, 4, 6- (1H, 3H, 5H) -triene 1, 3, 5-tris (4-t-butyl-3-hydroxy-2, 6-dimethylbenezene) -1, 3, 5-triazine-2, 4, 6- (1H, 3H, 5H) -triene, triethylene glycol-bis-3(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1, 3, 5-tris (2, 6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate (1, 3, 5-tris (2, 6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate), 4 '-butylidenebis (6-tert-butyl-3-methylphenol) (4, 4' -butylidenebis (6-tert-butyl-3-methylphenol)), and the like. Preferably, the content is in the range of 0.5 to 1.5 weight percent relative to the solid content of the final product, which can sufficiently exert the antioxidant effect, but is not limited thereto.
The gas stabilizer plays a role of preventing nitrogen oxide from yellowing, and for example, 1, 1, 1', 1' -tetramethyl-4, 4'(methylene-di-p-phenylene) dicarbazine (1, 1, 1', 1'-tetramethyl-4, 4' (methyl-di-p-phenylene) disilocarbazide) or the like can be used, but not limited thereto. Preferably, the content is 0.1 to 1.0 weight percent with respect to the solid content of the final product, but is not limited thereto.
The dyeing promoter may be Poly (N, N-diethyl-2-aminoethyl methacrylate), or the like, but is not limited thereto. Preferably, the content is 0.1 to 0.5 weight percent with respect to the solid content of the final product, but is not limited thereto.
The spinnability improver may be Magnesium stearate (Magnesium stearate), and preferably, the content is 0.01 to 0.5 wt% with respect to the solid content of the final product, but is not limited thereto.
In one embodiment of the present invention, the content of the polyurethane prepolymer in the slurry composition is adjusted to a viscosity of 60 to 70 poise and a content of 1400 to 2000 poise at 40 ℃, and the content of the polyurethane prepolymer in the slurry composition is 1 to 20 weight percent of the total slurry composition. In the above range, when preparing the spinning dope, it is preferable that the mixing and dispersibility with the polyurethaneurea polymer can be further improved, but not limited thereto.
Next, the spinning step will be specifically described.
In one embodiment of the present invention, dry spinning can be performed by using the spinning dope prepared as described above, the direct spinning nozzle temperature is 250 to 270 ℃, and the spinning speed is 700 to 1200 m/min, and it is preferable that the physical properties required for the spandex fiber (spandex) precursor and the number of times of using a solvent are easily expressed, but not limited thereto.
Hereinafter, the method for producing the composition of the present invention will be specifically described by way of examples.
While specific examples of the invention are provided for the understanding of the invention, it will be apparent to those of ordinary skill in the art that various modifications may be made in the specific examples described below and still fall within the scope of the invention.
In the method for preparing the chlorine resistant black polyurethaneurea elastic fiber of the present invention, in the case of additionally adding the existing carbon black and chlorine resistant agent, by improving the effect that a sufficiently uniform black color cannot be expressed due to the occurrence of a phenomenon of agglomeration or poor dispersion, there is an effect that the black fastness and uniformity of the whole fiber are very excellent, and particularly, when spinning is performed, the spinnability is very excellent without cutting or the like.
With respect to such effects, in the present invention, in the case of preparing a slurry composition comprising carbon black and an anti-chlorine agent and mixing it with a polyurethaneurea solution, when the above slurry composition is prepared, the problem of the resulting decrease in the dispersing effect is solved by using a dispersant or the like, which dissolves a polyurethane prepolymer having unreacted isocyanate in the slurry composition, whereby the present invention can be accomplished.
In particular, in the present invention, in order to further improve the above physical properties, when the above polyurethane prepolymer is prepared, in the case of using a polyurethane prepolymer in which polytetramethylene ether glycol and diphenylmethane-4, 4' -diisocyanate (MDI) are charged/polymerized at a molar ratio of 1.50 to 2.50(NCO/OH ═ 1.50 to 2.50) so that the terminal unreacted diisocyanate is 2.4 to 3.5 mol%, it is preferable because of having a more remarkable effect. In particular, the strength retention rate or the elasticity retention rate is further improved.
Further, in the case of using a polyurethane prepolymer having unreacted terminal isocyanate, and further, in the case of using a polyurethane prepolymer that retains 2.4 to 3.5 mol% of the above-mentioned unreacted terminal diisocyanate, not only the dispersibility is satisfied, but also the various physical properties of the present invention are satisfied, the present invention has an effect that not only the dispersion of carbon black and chlorine inhibitor is more excellent, but also the remarkable effect to be achieved in the present invention can be obtained, and further, as other additive whiteness-degree enhancers to be added to the slurry composition, the dispersibility is maintained even if titanium dioxide, an antioxidant, a gas stabilizer, a dyeability enhancer, a spinnability improver, a strength improver and the like, which can be used in this field, are added, and the effect of enabling the performance of maintaining the dispersion for a long time can be further improved.
The present invention will be described in further detail based on the following examples and comparative examples. However, the following examples and comparative examples are merely illustrative for further describing the present invention, and the present invention is not limited to the following examples and comparative examples.
Physical properties were measured by the following methods.
1) Measurement of the viscosity of polymers
The polymer was determined from type B and expressed in poise units at 40 ℃ using a Brookfield Viscometer (Brookfield Viscometer) 6 times using a spindle (spindle).
2) Intrinsic viscosity measurement
The viscosity of a solution prepared at a polymer concentration of 0.5g per 100ml of an N, N-dimethylacetamide solution was measured by a Ubbelohde viscometer in a constant temperature bath at 30. + -. 0.5 ℃.
3) Strength and elongation
The cutting strength (g/d) and the cut elongation (%) were measured by a tensile tester (UTM manufactured by Instron corporation) at 25 ℃ and 65% RH, with a sample length of 5cm, and with a speed of 50cm/min, by full tensile.
Cut elongation { (actual length stretched to the position of cut point x number of filaments)/(strand length + value obtained by converting the length of sample elongated from auxiliary jaw into strand length) } × 100
4) Elastic recovery rate
After the sample was stretched 5 times at 300% with a tensile tester (UTM, ltd.) heavy load, the length of the sample and the initial length of the sample in a state without tension were expressed in percentage.
5) Fastness to washing
The measurement was carried out by the KS K0430 AI method (AATCC 61).
Grade 1 to grade 5, the higher the number, the more excellent the fastness.
6) L value (deep chroma), chromaticity coordinates a value and b value
After measuring the reflectance of the strands by using a spectrophotometer (Color-Eye 30000, Mecbeth corporation), the calculation was performed using the calculation formula of CIE 76CIE Lab Color difference equation. In the L-value coordinates, the range of all names is 0 to 100, and a value of 0 indicates complete black, and a value of 100 indicates white. Therefore, a lower L value indicates a better degree of darkness. At the coordinates a + indicates Red (Red), -Green (Green), b + indicates Yellow (Yellow), -Blue (Blue).
7) Chlorine resistance determination method of protofilament
The sample was immersed in a 50% stretched state in an effective chlorine concentration of 20ppm at a pH of 7, and the chlorine resistance was increased as the strength retention ratio was higher in terms of 24 hours, 48 hours, and 72 hours. The elastic recovery was measured by measuring the length of the sample before and after the chlorine treatment, and the higher the recovery, the higher the chlorine resistance.
8) Spinnability
Spinning was carried out for 24 hours, and the number of times that truncation would occur was expressed as a percentage of the total number of windings.
9) Method for measuring color of protofilament
The surface of the spandex fiber winding body was measured 3 times with a spectrocolorimeter (Meneta CM-508D) to determine the L/a/b value of the precursor.
10) Filtration Test (Filter Test)
After a predetermined amount of slurry was put into the vessel, a Filter (Filter) was placed at 0.03mm in the outlet portion of the vessel, and the amount and time of extraction by the Filter were determined by pressurizing.
The extraction amount is the amount passing through the filter/the amount of slurry put in the filter multiplied by 100
Example 1
1) A polyurethane prepolymer as a first polymer was synthesized by continuously transferring 155.43g/min of polytetramethylene ether glycol (molecular weight: 1800) and 36.71g/min of diphenylmethane-4, 4' -diisocyanate to a homomixer (Static Mixer) at 40 ℃ by means of a metering pump, mixing them, charging them into a continuous polymerization tube in the form of a cylindrical tube at 80 ℃ for 135 minutes, and adjusting the reaction so that the unreacted diisocyanate at the terminal end was 2.64. + -. 0.02 mol%.
The first polymer was cooled to 40 ℃ and stabilized for 24 hours, and then continuously charged with 309.93g/min of N, N-dimethylacetamide in a high-end stirrer before being charged into the second reactor, and stirred vigorously at 3500rpm for 20 seconds. The first polymer was completely dissolved and cooled to produce a 40 c polyurethane polymer solution having 38.27 weight percent solids.
2) An amine solution was prepared which was mixed with 4.955kg of ethylenediamine as a chain extender and 0.914kg of diethylamine as a chain terminator, 120ppm with respect to the final spinning solution solids, 0.036kg of diethyltriamine as a crosslinking agent, and 84.36kg of an amine solution having a solids content of 7% by weight which was mixed with 78.45kg of N, N-dimethylacetamide.
3) 502.08g/min of the above polyurethane polymer solution and 58.58g/min of the amine solution having a solid content of 7% by weight prepared in the above 2) were put into a static mixer as a second polymerizer and mixed so that the amine/isocyanate equivalent ratio was 1.02/1, thereby obtaining a polyurethaneurea polymer having a solid content of 35% by weight.
4) 3.0kg of carbon black (Shanghai Trade, average particle size of 2 μm) as a black additive, 5.1kg of a chlorine resistant agent as hydromagnesite (product of nanotechnology Co., Ltd., average particle size of 3 μm), and 4.4kg of the polyurethane polymer solution prepared in 1) above, 0.3kg of titanium dioxide as a whiteness promoting agent, 2.85kg of an antioxidant (SongNox-2450, SongWeun chemistry), 1.2kg of a gas stabilizer (HN-150, JFC), 1.5kg of a dyeability promoting agent (LMA-100, Daeseong chemistry), 0.66kg of magnesium stearate as a spinning improving agent, 1.29kg of a strength improving agent (SCM-660H, Daeseong chemistry), 29.529kg of N, N-dimethylacetamide as a solid correction were mixed, dispersed and pulverized by a sand mill, thereby preparing a slurry composition.
5) 560.63g/min of the polyurethaneurea polymer prepared in 3) above and 34.6g/min of the additive slurry composition prepared in 4) above were mixed to prepare a dope having 35% solids. Relative to the solid of the final product, the carbon black is contained by 1.0 weight percent and the anti-chlorine agent is contained by 1.7 weight percent.
6) A spinning barrel is formed at the temperature of 250-270 ℃, a certain amount of the spinning solution is discharged by a gear pump, and simultaneously, the polyurethane elastic fiber is prepared at the speed of 1000m/min by dry spinning of a hair-increasing solvent.
After spinning, the residual solvent content of the spandex fiber is adjusted to be less than 1.0 weight percent.
Example 2
In example 1, the same was carried out except that the unreacted diisocyanate whose reaction was adjusted to the end was 2.24 ± 0.02 mol% to prepare a polyurethane prepolymer as the first polymer.
Example 3
In example 1, the same procedure was carried out except that the polyurethane prepolymer as the first polymer was synthesized with unreacted diisocyanate whose reaction was adjusted to the end in a molar percentage of 3.65 ± 0.02.
Example 4
In example 1, the same procedure was performed except that 0.2 weight percent of polyacrylonitrile (olycrylonitrile, having a weight average molecular weight of 150000) was further added to the slurry composition content.
Example 5
In example 1, the same procedure was performed except that 0.7 weight percent of polyacrylonitrile (olycylonitrile, having a weight average molecular weight of 150000) was further added to the slurry composition.
Comparative example 1
In example 1, the same procedure was carried out except that the polyurethane polymer solution containing the polyurethane prepolymer was not used to prepare the slurry composition, and each additive was directly charged into the polyurethaneurea polymer.
Comparative example 2
In example 1, the same procedure was carried out except that the chlorine inhibitor was not used.
The physical properties of the results of the filtration test are shown in Table 1 below.
TABLE 1
De' in table 1 above is enlightening, SS100 is the strength of the strand at 100% elongation, and SS200 and SS300 are the strengths of the strand at 200% and 300%, respectively.
TABLE 2
TABLE 3
The chlorine-resistant black polyurethaneurea elastic fiber of the present invention is excellent in black uniformity and spinnability, and is known to be an elastic fiber excellent in black fastness and dyeability, as compared with comparative examples.
As shown in table 3, it is found that the examples of the present invention have significantly improved physical properties in the strength retention rate and the elastic recovery rate, as compared with the comparative document, with respect to the chlorine resistance elastic recovery rate. Can provide a fabric having excellent elastic recovery and strength recovery after dyeing.
Claims (6)
1. A method for producing a chlorine-resistant black polyurethaneurea elastic fiber, the chlorine-resistant black polyurethaneurea elastic fiber containing carbon black, the method comprising:
a step of preparing a polyurethaneurea polymer;
a step of mixing a slurry composition containing a chlorine inhibitor, carbon black and a polyurethane prepolymer having an unreacted terminal isocyanate group with the polyurethane urea polymer to prepare a spinning dope; and
spinning by using the spinning solution;
0.1 to 3 weight percent of carbon black, 0.5 to 4.0 weight percent of chlorine resisting agent are contained in the total weight of the chlorine resisting black polyurethane urea elastic fiber;
the slurry composition comprises 1 to 20 weight percent of a polyurethane prepolymer;
the polyurethane prepolymer contains 2.4 to 3.5 mole percent unreacted terminal isocyanate groups.
2. The method of preparing chlorine-resistant black polyurethaneurea elastic fiber according to claim 1, wherein the polyurethaneurea polymer is prepared by the steps of: adding polytetramethylene ether glycol and diphenylmethane-4, 4' -diisocyanate and polymerizing so that the NCO/OH molar ratio is 1.50 to 2.50 to prepare a polyurethane prepolymer having a terminal unreacted isocyanate content of 2.4 mol% to 3.5 mol%, and then reacting the polyurethane prepolymer with an amine solution to prepare a polyurethane urea polymer; wherein the mixing is carried out in a manner that the equivalent ratio of amine/isocyanate is 1.01-1.06/1.
3. The method of claim 1, wherein the slurry composition further comprises one or more components selected from the group consisting of a whiteness enhancer, an antioxidant, a gas stabilizer, a dyeability enhancer, a spinnability improver, and a strength improver.
4. The method for preparing chlorine-resistant black polyurethaneurea elastic fiber according to claim 1,
characterized in that the chlorine inhibitor and the carbon black have an average particle diameter of 5 μm or less.
5. The method of claim 1, wherein the slurry composition further comprises 0.01 to 1 wt% of polyacrylonitrile.
6. A chlorine-resistant black polyurethaneurea elastic fiber produced by the method of any one of claims 1 to 5.
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