KR101766269B1 - Polyurethaneurea elastic fiber - Google Patents

Abstract

The present invention relates to a polyurethane-urea elastic fiber having excellent heat resistance and anti-chlorine resistance and, more specifically, to a polyurethane-urea elastic fiber having excellent heat resistance and anti-chlorine resistance, by containing whole hydroxylated hydrotalcite.

Description

[0001] POLYURETHANEUREA ELASTIC FIBER [0002] BACKGROUND OF THE INVENTION [0003]

The present invention relates to a polyurethane urea elastic fiber having excellent heat resistance and anti-chlorine resistance. More specifically, the present invention relates to a polyurethane-urea elastic fiber containing a total hydrous hydrotalcite.

The polyurethane-urea elastic fiber is produced by extending the chain of the isocyanate-terminated prepolymer synthesized with a high-molecular-weight polyol and an excess of an organic diisocyanate to a diamine, mainly by dry spinning and kneading nylon, polyester, It has been used as a stretch material for various kinds of clothing such as foundation, socks, pantyhose, and swimwear.

Also, the polyurethane-urea elastic fiber is produced by stretching a chain of a prepolymer of an isocyanate end synthesized with a high molecular weight polyol and an excess of an organic diisocyanate with a diamine, mainly through dry and melt spinning to obtain a polyamide fiber or a polyester fiber And is knitted with natural fibers to be used as a stretchable material for various kinds of clothing such as foundation, sock, pantyhose, and swimwear.

However, polyurethane urea elastic fibers are degraded in polyether glycol structure, which is a soft segment of the polymer due to chlorine bleaching or active chlorine for disinfection of swimming pool, resulting in deterioration of physical properties. Therefore, in order to improve anti-chlorine resistance of polyurethane-urea elastic yarn, polyurethane elastic yarn using polyester glycol has been produced. However, due to its high biological activity, aliphatic esters are easily attacked by fungi, and anti-chlorine is not satisfactory.

Accordingly, the applicant of the present invention has filed a Korean Patent Application No. 10-1166807 to provide a composition for producing a polyether-based polyurethane-urea elastic fiber excellent in anti-chlorine resistance.

In this patent, additives are added to improve anti-chlorine. At this time, the surface modified basic magnesium carbonate and hydro-magneite are mixed with the polymer to prepare a radiation dope. However, in order to uniformly disperse the additive in the radiation dope A large amount of solvent was required.

In addition, the surface modified basic magnesium carbonate, hydro-magneite, and the like were immersed in the composition, and the compositions were uneven during the preparation of the radiation dope, and environmental problems were caused by the generation of dust when added to the solvent.

Korean Patent No. 10-1166807

It is an object of the present invention to prepare and add additive slurries in order to improve the dispersibility in the production of radiant doughs and to use hydrotalcites which are totally hydrotreated with an anti-chlorine agent so that there is less dispersion and deposition in the slurry additive .

In addition, the present invention aims to further improve the heat resistance and anti-chlorine fusing property when mixed with the whole hydroxide hydrotalcite by using a dihydroxy phenoxy antioxidant as an antioxidant.

In order to solve the above problems, the inventors of the present invention have conducted research and found that when the hydrotalcite is completely hydrolyzed with an anti-chlorine agent, the dispersibility in the preparation of the radiation dope is further improved, It is possible to provide a polyurethane-urea elastic fiber excellent in energy saving effect and excellent in heat resistance and anti-chlorine resistance, thereby completing the present invention.

Further, it has been found that, when a polyurethane-urea polymer is prepared, a polyurethane-urea elastic fiber excellent in mechanical properties and excellent in heat resistance and anti-chlorine resistance can be provided by combining specific ranges of components and content and adjusting the order of addition Thereby completing the present invention.

Specifically, the present invention relates to a polyurethane-urea elastic fiber containing a total hydroxylated hydrotalcite of the following formula (1).

[Chemical Formula 1]

Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .2.3H ₂ O

In one embodiment of the present invention, the total hydroxylated hydrotalcite may be from 1 to 5% by weight based on the total weight of the polyurethaneurea elastic fibers.

In one embodiment of the present invention, the polyurethane-urea elastic fiber may be one comprising an asymmetric dihydroxyphenol-based antioxidant.

The present invention also relates to a process for producing a polyurethane-urea elastic fiber having excellent heat resistance and anti-chlorine-

Polytetramethylene ether glycol and diphenylmethane-4,4'-diisocyanate were polymerized to have an NCO / OH molar ratio of 1.5 to 2.5 to prepare a polyurethane prepolymer such that the end unreacted isocyanate content was 2.4 to 3.5 mol% A primary polymerization step;

Adding the polyurethane prepolymer to N, N-dimethylacetamide to prepare a polyurethane prepolymer mixed solution having a solid content of 35 to 45% by weight;

Diethylenetriamine as a chain extender, diethylamine as a chain terminator, and diethylenetriamine as a crosslinking agent were dissolved in N, N-dimethylacetamide while the amine equivalent ratio of diethylamine / ethylenediamine was 1 / 5.0 to 8.0 , And diethylene triamine in an amount of 100 to 300 ppm based on the solids content of the final spinning solution to prepare an amine solution;

A second polymerization step of mixing the polyurethane prepolymer mixed solution and the amine solution with an amine / isocyanate equivalent ratio of 1.01 to 1.06 / 1 to prepare a polyurethane urea polymer solution having a solid content of 35 to 40 wt%;

Adding an additive slurry containing the entire hydroxylated hydrotalcite of the following formula (1) to the polyurethane-urea polymer solution and uniformly mixing them to prepare a radiation dope having a solid content of 35 to 40% by weight; And

Radiating the radiation dope;

.

[Chemical Formula 1]

Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .2.3H ₂ O

In one embodiment of the production process of the present invention, the additive slurry is an anticorrosive agent comprising the entire hydroxideated hydrotalcite of Formula 1; A whiteness improving agent, an antioxidant, a gas stabilizer, and a dyeability improver; N, N-dimethylacetamide, and the polyurethane prepolymer mixture; and pulverizing and dispersing the mixture.

In one embodiment of the production method of the present invention, the antioxidant may include an asymmetric dihydroxyphenol antioxidant.

In one embodiment of the production process of the present invention, the total hydroxylated hydrotalcite may be contained in an amount of 1 to 5% by weight based on the total weight of the polyurethane-urea elastic fiber.

The method for producing polyurethane-urea elastic fibers according to the present invention has the effect of improving the dispersibility of additives and reducing the energy required for the spinneret preparation and shortening the manufacturing time.

In addition, it is possible to provide a polyurethane-urea elastic fiber having a low occurrence of gel formation and deposition and capable of producing a stable radiation dope, improved productivity, excellent mechanical properties, and excellent heat resistance and anti-chlorine resistance.

Hereinafter, the present invention will be described in more detail with reference to specific embodiments thereof. It should be understood, however, that the invention is not limited thereto and that various changes and modifications may be made without departing from the spirit and scope of the invention.

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 description of the invention is merely intended to effectively describe a specific embodiment and is not intended to limit the invention.

Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

One embodiment of the present invention is a polyurethane-urea elastic fiber having excellent heat resistance and anti-chlorine-containing property, containing the entire hydroxylated hydrotalcite represented by the following formula (1).

[Chemical Formula 1]

Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .2.3H ₂ O

The total hydroxylated hydrotalcite is an additive for improving the heat resistance and anti-chlorine resistance of the polyurethane-urea elastic fiber, and is fully hydrolyzed to improve the dispersibility in the slurry when the additive slurry is prepared. Thus, the conventional surface modified basic magnesium carbonate, hydrogagnesium It is possible to shorten the manufacturing time of the polyurethane-urea elastic fiber. In addition, there is an effect that the heat resistance and the anti-chlorine burning ability equal to or higher than those of the conventional anti-chlorine scouring agent can be exhibited.

In one embodiment of the present invention, the total hydroxylated hydrotalcite is a metal hydroxide, wherein a divalent or trivalent metal cation is located at the center of the metal hydroxide, and six hydroxide ions (OH < ^- > As a unit, it has a double layer structure in which two octahedral units are repeated to form two layers, and anion and water molecules are positioned between the two layers, and the equilibrium of the charge amount is maintained.

In one embodiment of the present invention, the total hydroxylated hydrotalcite may be of the order HKL 003: d = 7.444, HKL 006: d = 3.803 as analyzed by X-ray diffractometer (XRD), but is not limited thereto.

In one embodiment of the present invention, the total hydroxylated hydrotalcite may contain, but is not limited to, 1 to 5% by weight based on the total weight of the polyurethane-urea elastic fibers. More preferably 1 to 3% by weight, and it is possible to provide a polyurethane-urea elastic fiber having excellent heat resistance and anti-chlorine resistance, and excellent mechanical properties in the range of 1 to 5% by weight. If the content exceeds 5% by weight, mechanical properties such as strength and elongation may be lowered due to excessive use of the inorganic material.

In addition, the polyurethane-urea elastic fiber of the present invention can further improve heat resistance and anti-chlorine resistance by including an asymmetric dihydroxyphenol-based antioxidant.

When the asymmetric dihydroxyphenol-based antioxidant is mixed with the above-mentioned whole hydroxide hydrotalcite, the specific reason is unknown, but it has been confirmed that the heat resistance and anti-chlorine resistance are further improved. Specific examples of the asymmetric dihydroxyphenol antioxidant include 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzene) -1,3,5-tri Triene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, bis-3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,3,5-tris (2,6- (3, 5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate), 4,4'-butylidenebis Commercialized examples thereof include CYANOX1790 manufactured by Cynamid of USA, SongNox-2450, SongNox-1790, SongNox-1790 of Korea Songwon Industrial Co., 4425, and the like.

In one embodiment of the present invention, the polyurethane-urea elastic fiber has a yarn color value L of 89 to 93, a of -1.00 to -1.4 and b of 2.0 to 5.0, Is 90 to 98%, the strength change rate after 90 hours treatment with 20 ppm chlorine water is 90 to 98%, the cutting strength is 1.0 to 2.0 g / denier, and the cut elongation is 450 to 700%. A satisfactory result can be obtained in radioactive and other post-processing processes within a range satisfying all of the above physical properties.

Hereinafter, a method for producing the polyurethane-urea elastic fiber having excellent heat resistance and anti-chlorine resistance of the present invention will be described in more detail.

One aspect of the production process of the present invention relates to a process for producing a polyurethane prepolymer, comprising the steps of: a first polymerization step of producing a polyurethane prepolymer; a step of producing a polyurethane prepolymer mixture liquid; a step of mixing the polyurethane prepolymer mixture solution with an amine solution to prepare a polyurethane- Adding an additive slurry containing the total hydroxylated hydrotalcite of formula 1 to the polyurethane-urea polymer solution to prepare a radiation dope; , And the step of preparing the amine solution may be prepared and prepared in advance, regardless of the order described above, and then the amine solution may be added.

[Chemical Formula 1]

Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .2.3H ₂ O

More specifically, one aspect of the manufacturing method of the present invention is

Polytetramethylene ether glycol and diphenylmethane-4,4'-diisocyanate were polymerized to have an NCO / OH molar ratio of 1.5 to 2.5 to prepare a polyurethane prepolymer such that the end unreacted isocyanate content was 2.4 to 3.5 mol% A primary polymerization step;

Adding the polyurethane prepolymer to N, N-dimethylacetamide to prepare a polyurethane prepolymer mixed solution having a solid content of 35 to 45% by weight;

Diethylenetriamine as a chain extender, diethylamine as a chain terminator, and diethylenetriamine as a crosslinking agent were dissolved in N, N-dimethylacetamide while the amine equivalent ratio of diethylamine / ethylenediamine was 1 / 5.0 to 8.0 , And diethylene triamine in an amount of 100 to 300 ppm based on the solids content of the final spinning solution to prepare an amine solution;

A second polymerization step of mixing the polyurethane prepolymer mixed solution and the amine solution with an amine / isocyanate equivalent ratio of 1.01 to 1.06 / 1 to prepare a polyurethane urea polymer solution having a solid content of 35 to 40 wt%;

Adding an additive slurry containing the entire hydroxylated hydrotalcite of the following formula (1) to the polyurethane-urea polymer solution and uniformly mixing them to prepare a radiation dope having a solid content of 35 to 40% by weight; And

Radiating the radiation dope;

.

[Chemical Formula 1]

Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .2.3H ₂ O

Each step of the method for producing the polyurethane-urea elastic fiber of the present invention will be described in more detail.

The method for producing the polyurethane-urea elastic fiber of the present invention is characterized by the order of each step and the content of the raw materials, and it is possible to provide an excellent polyurethane-urea elastic fiber having excellent heat resistance and anti-chlorine resistance have.

In one embodiment of the present invention, the first polymerization step for producing the polyurethane prepolymer will be described in more detail.

In one embodiment of the present invention, the polytetramethylene ether glycol and diphenylmethane-4,4'-diisocyanate are polymerized so as to have an NCO / OH molar ratio of 1.5 to 2.5 to obtain a non-reactive isocyanate content of 2.4 to 3.5 mol% By weight of the polyurethane prepolymer.

At this time, the polytetramethylene ether glycol and diphenylmethane-4,4'-diisocyanate are continuously fed to a static mixer, which is a homogeneous mixer, by using a metering pump, and the mixture is stirred at 30 to 50 ° C, It is preferable to mix them at 45 ° C. Then, it is preferable that the polymerization is carried out at a reaction temperature of 60 to 100 ° C, more preferably 70 to 98 ° C, in a continuous polymerization tube of a cylindrical pipe type. The production of the gel in the polyurethane prepolymer in the above range can be minimized, though not limited to the above temperature range.

The polyurethane prepolymer was prepared so that the content of terminal unreacted isocyanate was 2.4 to 3.5 mol% in the range of NCO / OH molar ratio of 1.5 to 2.5 in the case of polytetramethylene ether glycol and diphenylmethane-4,4'-diisocyanate. can do. It is possible to ensure the required physical properties after spinning and spinning in the range of 2.4 to 3.5 mol% of the terminal unreacted isocyanate content.

Next, the process for producing the polyurethane prepolymer mixture liquid will be described in detail.

The prepared polyurethane prepolymer was cooled to 30 to 50 ° C. and stabilized. Then, a polyurethane prepolymer and N, N-dimethylacetamide, which were the first polymerizers, were added in a high shear mixer just before the second reactor was charged, To prepare a urethane prepolymer mixture. Through this process, the content of unreacted diisocyanate can be sufficiently reduced and then supplied to the secondary polymerization reactor. At this time, it is preferable to stir vigorously at 3000 to 4000 rpm in a high-shear mixer to completely dissolve the unreacted material. Thereafter, the mixture is cooled to 30 to 50 캜 to prepare a polyurethane prepolymer mixed solution having a solid content of 35 to 45% by weight. The reason why the solid content is in the range of 35 to 45% by weight is that a solid solution of 7% amine solution is added during the urea reaction so as to maintain a solid content higher than that of the final polymer in order to control the solid content of the final polymerizer to 35 to 40% .

Next, the secondary polymerization step for preparing the polyurethane-urea polymer solution by mixing the polyurethane prepolymer mixed solution with the amine solution will be described in more detail.

In one embodiment of the present invention, the amine solution may be prepared in advance before the secondary polymerization step, or may be mixed with the polyurethane prepolymer mixture in the secondary polymerization. It is preferable to prepare beforehand the mixture before the secondary polymerization step in view of favorable control of the equivalence ratio. The amine solution is prepared by dissolving ethylenediamine as a chain extender, diethylamine as a chain terminator, and diethylenetriamine as a crosslinking agent in N, N-dimethylacetamide. At this time, the solid content in the desired radiant dope can be increased by mixing such that the amine equivalent ratio of diethylamine / ethylenediamine is 1 / 5.0 to 8.0. When the amine equivalent ratio is less than 5.0, the molecular weight of the polymer decreases, and thus, the physical properties can not be exhibited during the production of the yarn. When the amine equivalent ratio is more than 8.0, viscosity increase and gel phenomenon may occur due to an increase in molecular weight. Heat resistance and anti-chlorine resistance. Further, it is preferable to add diethylene triamine at 100 to 300 ppm based on the solids content of the final spinning solution. When it is used in an amount of less than 100 ppm, the viscosity stability of the radiation dope is lowered, and the crosslinking reaction is little in the spinning process, and the heat resistance of the yarn is deteriorated. If it exceeds 300ppm, viscosity increase is delayed, and it takes a lot of time to obtain a desired viscosity, and excessive crosslinking reaction causes gel formation and non-uniformity of polymer, resulting in poor radioactivity.

In one embodiment of the present invention, when preparing the polyurethane-urea polymer solution by mixing the polyurethane prepolymer mixed solution and the amine solution, it is preferable that the amine / isocyanate equivalent ratio is 1.01 to 1.06 / 1. When the amine / isocyanate equivalent ratio is less than 1.01, it is impossible to form a desired radial viscosity. When the amine / isocyanate equivalent ratio is more than 1.06, the viscosity increase is large and gel phenomenon may occur.

The secondary polymerization may be performed in a secondary polymerization reactor equipped with a cooling apparatus and the secondary polymerization reactor may be operated such that the reaction efficiency of the polyurethane prepolymer mixture and amine is 80% It is preferable to adjust it. The stirring efficiency at the outlet of the secondary polymerization reactor can be measured to determine an appropriate stirring speed of the reaction. The polyurethane-urea polymer synthesized by the chain extension reaction and the chain termination reaction preferably has a solid content of 35 to 40% by weight, has an intrinsic viscosity of 1.0 ± 0.2 and an apparent viscosity of about 1000 to 2500 poise It is preferable to have viscosity. If the solid content is less than 35% by weight, spinning may be impossible due to low viscosity, and it may be difficult to exhibit physical properties in the production of yarn. If it exceeds 40% by weight, spinning may not be possible due to high viscosity. In addition, it is necessary to have a post-curing time in the range of apparent viscosity ranging from about 1000 to 2500 poise at 40 DEG C, that is, a second polymerizing, a polymer aging time for producing a radial viscosity after slurry input, So that it is preferable. In addition, the intrinsic viscosity of the polyurethane polyurea polymer measured at a concentration of 0.5 g per 100 ml of the solution in N, N-dimethylacetamide is preferably 1.0 ± 0.2.

Next, the process of manufacturing the radiation dope will be described in detail.

In one embodiment of the present invention, the additive slurry may be added to the polyurethane-urea polymer solution prepared in the preparation of the emulsion dope and uniformly mixed to prepare a radiant dope having a solid content of 35 to 40% by weight. It is not. At this time, it is preferable to use a static mixer for uniform mixing, but the present invention is not limited thereto.

The process of preparing the additive slurry added to the radiation dope will be described in detail. The present invention solves the problem that when the additives are added and mixed in the preparation of the radiation dope, the dispersibility is lowered and the yarn breaks during spinning, and in order to prevent the gel from being generated, Urethane-urea polymer solution, and uniformly dispersed and pulverized to prepare a slurry, thereby further improving the productivity.

More specifically, the additive slurry is a mixture of the total hydroxide hydrotalcite of the above formula (1) as an anti-chlorine agent; A whiteness improving agent, an antioxidant, a gas stabilizer, and a dyeability improver; N, N-dimethylacetamide, and may also contain the polyurethane prepolymer mixture to appropriately control the viscosity. The mixture is preferably dispersed and pulverized by using a sand grinder to prepare a uniformly mixed additive slurry. The additive slurry may have an average particle diameter of 0.1 to 1.0 占 퐉 and a viscosity of 60 to 70 poise in the additive slurry, but the present invention is not limited thereto.

In one embodiment of the present invention, the additive slurry comprises 1 to 5% by weight of the total hydroxylated hydrotalcite anti-scavenger of Formula 1, 0.01 to 0.5% by weight of whiteness enhancer, 0.5 to 1.5% of antioxidant, By weight, a gas stabilizer in an amount of 0.1 to 1.0% by weight, a dyeability improver in an amount of 0.1 to 0.5% by weight, and a total content of additive slurries of 5 to 10% by weight of the polyurethane prepolymer mixture, % ≪ / RTI > to N, N-dimethylacetamide.

Specifically, the total hydroxylated hydrotalcite is an additive for improving the heat resistance and anti-chlorine resistance of the polyurethane-urea elastic fiber, and is fully hydrolyzed to improve the dispersibility in the slurry when the additive slurry is prepared. As a result, the conventional surface modified basic magnesium carbonate, It is possible to shorten the manufacturing time of the polyurethane-urea elastic fiber as compared with the antiseptic agent such as hydro-magneite. In addition, there is an effect that the heat resistance and the anti-chlorine burning ability equal to or higher than those of the conventional anti-chlorine scouring agent can be exhibited.

In one embodiment of the present invention, the total hydroxylated hydrotalcite is a metal hydroxide, wherein a divalent or trivalent metal cation is located at the center of the metal hydroxide, and six hydroxide ions (OH < ^- > As a unit, it has a double layer structure in which two octahedral units are repeated to form two layers, and anion and water molecules are positioned between the two layers, and the equilibrium of the charge amount is maintained.

In one embodiment of the present invention, the total hydrolytic hydrotalcite may be such that HKL 003: d = 7.444, HKL 006: d = 3.803 when analyzed by X-ray diffractometer (XRD).

In one embodiment of the present invention, the total hydroxylated hydrotalcite may contain, but is not limited to, 1 to 5% by weight based on the total weight of the polyurethane-urea elastic fibers. More preferably 1 to 3% by weight, and it is possible to provide a polyurethane-urea elastic fiber having excellent heat resistance and anti-chlorine resistance, and excellent mechanical properties in the range of 1 to 5% by weight. If the content exceeds 5% by weight, mechanical properties such as strength and elongation may be lowered due to excessive use of the inorganic material.

Titanium dioxide can be used as the whiteness improving agent, and the whiteness improving agent can be effectively used as a whiteness improving agent by using 0.01 to 0.5% by weight based on the solid content of the final product.

The antioxidant serves to capture radicals that cause degradation of the polymer generated by heat or sunlight. In one embodiment of the present invention, the antioxidant preferably includes an asymmetric dihydroxyphenol-based antioxidant, The synergistic effect when used together with the hydrotalcite hydroxide can further improve the heat resistance and anti-chlorine resistance. Specific examples of the asymmetric dihydroxyphenol antioxidant include 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzene) -1,3,5-tri Triene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, bis-3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,3,5-tris (2,6- (3, 5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate), 4,4'-butylidenebis Commercialized examples thereof include CYANOX1790 manufactured by Cynamid of USA, SongNox-2450, SongNox-1790, SongNox-1790 of Korea Songwon Industrial Co., 4425, etc. However, it is not limited thereto, and its content is preferably 0.5 to 1.5% by weight based on the solid content of the final product. Hi can be expressed is preferred.

The gas stabilizer serves to prevent yellowing caused by nitrogen oxides. For example, 1,1,1 ', 1'-tetramethyl-4,4' (methylene-di-p-phenylene) And the like can be used. But is not limited thereto. The content thereof is preferably 0.1 to 1.0% by weight based on the solid content of the final product.

The dyeability improver may be poly (N, N-diethyl-2-aminoethyl methacrylate) or the like, but is not limited thereto. The content thereof is preferably 0.1 to 0.5% by weight based on the solid content of the final product.

The radioactive modifier may be magnesium stearate or the like, and the content thereof is preferably 0.01 to 0.5% by weight based on the solid content of the final product.

The polyurethane-urea polymer may be used in an amount such that the viscosity of the additive slurry is adjusted to be 60 to 70 poise and 1400 to 2000 poise at 40 ° C, and 5 to 10% by weight of the total additive slurry may be used have. The polyurethane-urea polymer can further improve the mixing and dispersibility with the polyurethane-urea polymer solution during the production of the radiation dope.

The N, N-dimethylacetamide is used to control the solid content, and it is preferable that the solid content is 35 to 40% by weight in order to form the spinning viscosity.

In one embodiment of the present invention, a static mixer may be used to uniformly mix the polyurethaneurea polymer solution and the additive slurry during the manufacture of the emulsion dope, but is not limited thereto. As described above, the uniform mixing of the additive slurry and the final polymer is a very important parameter that determines the physical properties of the spinning yarn. Therefore, by adding a part of the polyurethaneurea polymer component when preparing the additive slurry as described above, Can be further improved. Gelation can be prevented.

Although the mixing ratio of the polyurethane-urea polymer solution and the additive slurry is not limited, it is possible to mix 90 to 99% by weight of the polyurethane-urea polymer solution and 1 to 10% by weight of the additive slurry, 1 to 5% by weight of the total hydrolyzed hydrotalcite anti-scavenger of the formula 1, 0.01 to 0.5% by weight of the whiteness enhancer, 0.5 to 1.5% by weight of the antioxidant, 0.1 to 1.0% by weight of the gas stabilizer, 0.5% by weight of the additive slurry.

Next, the spinning process will be described in detail.

In one embodiment of the present invention, dry spinning may be performed using the prepared spinning dope, and dry spinning at a spinning nozzle temperature of 250 to 270 DEG C and a spinning speed of 700 to 1200 m / It is preferable because it is easy to express the required physical properties and recover the solvent used.

Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

The physical properties were measured by the following method.

1) Viscosity

The viscosity was measured at 40 ° C using a Brookfield Viscometer using a spindle No. 6.

2) Measurement of stirring efficiency of polymer

The polymer was collected at the outlet of the secondary polymerization reactor and dissolved in the N, N-dimethylacetamide solution to measure the content of amine present in the dope and the polymer terminal. The reaction product was then titrated with 0.1N hydrochloric acid, The efficiency was measured.

3) Intrinsic viscosity measurement

The viscosity of the solution prepared at a concentration of 0.5 g of polymer per 100 ml of N, N-dimethylacetamide solution was measured with a Uvold viscometer in a thermostatic chamber at 30 ± 0.5 ° C to measure the intrinsic viscosity of the polymer.

4) Cutting strength, cutting elongation

The cut strength (g / d) and the cut elongation (%) were measured by a tensile tester (UTM, manufactured by INSTRONG CO., LTD.) At 25 ° C and 65% RH at a sample length of 5 cm and at a rate of 50 cm / min.

Cutting elongation = {(actual length extended to cutting point x number of filaments) / (length of yarn + length of sample extended from auxiliary clamp to yarn length)} x 100

5) Stripe evaluation

Stripe evaluation method: Visual evaluation using a tester

The number of embroidery stitches at the time of knitting, the number of fine streaks in the fabric during the visual evaluation using the measuring machine, and the Wale spacing were evaluated comprehensively.

A: no more than 3 fine lines

B: fine line 4 ~ 10 or less + Wale line 2 lines or less

C +: fine line 11 ~ 20 points + Wale spacing narrow line 3 ~ 5 points

C: More than 21 fine lines + Wale spacing More than 6 narrow lines or Wale spacing Wide lines

D: Continuous Wale interval When wide line occurs

6) Knitted de Levante, Max de Left

Knitted Dreft measures the rate of injection of spandex and main filament in a circular knitting machine.

The input speed was measured and calculated by the RPM measuring machine in the rollers of the circular knitting machine.

Knitted de Left = injection rate of injection / spandex injection rate

The maximum Dreft was calculated by calculating the ratio of the injection rate of the coverer to the injection rate of the covering machine in the covering machine.

7) Anti-chlorine (strong retention rate g)

The samples were immersed in a bath having a pH of 7 and an effective chlorine concentration of 20 ppm in a state of 25% elongation, treated with hot air at 180 ° C for 24 hours and 48 hours, respectively, and then measured for strength using a tensile tester (INSTRON, The higher the strength, the higher the anti-chlorine resistance.

8) Anti-chlorine (elastic recovery (%))

The samples were immersed in a bath having an effective chlorine concentration of 20 ppm at a pH of 7 with a 25% elongation, treated with hot air at 180 ° C for 24 hours and 48 hours, respectively, and elongation was measured.

The length of the initial sample was 16 cm and the length of the 25% elongated sample was 20 cm.

Elastic recovery rate (%) = (25% length of elongated sample - length after treatment) / (length of 25% elongated sample - length of initial sample) x 100

9) Color value of yarn

Color Meter (Nikon).

10) Running value

The running values were measured using a tension meter.

R is the deviation between running tensions.

The screening rate was the running tension value, and the screening rate (%) according to the management reference range of R value was calculated.

 [Example 1]

Polytetramethylene ether glycol molecular weight 1800 158.00 g / min and diphenylmethane-4,4'-diisocyanate 37.33 g / min were continuously transferred to a 40 ° C static mixer using a metering pump and mixed, And the reaction was carried out for 135 minutes to adjust the reaction so that the unreacted diisocyanate was 2.64 ± 0.02 mol% at the terminal. Thus, a polyurethane prepolymer was prepared as the first polymer. The molar ratio of NCO / OH of the polytetramethylene ether glycol and diphenylmethane-4,4'-diisocyanate used in the reaction was 1.7.

The polyurethane prepolymer was cooled to 40 ° C. and stabilized for 24 hours. The mixture was continuously fed into a high shear mixer with 3143.46 g / min of N, N-dimethylacetamide at 3500 rpm for 20 seconds Lt; / RTI > The polyurethane prepolymer was completely dissolved in N, N-dimethylacetamide and cooled to 40 캜 to prepare a polyurethane prepolymer mixture solution having a solid content of 38.39% by weight.

5.038 kg of ethylenediamine as a chain extender, 0.929 kg of diethylamine as a chain stopper, 0.039 kg of diethylene triamine as a crosslinking agent so as to be 130 ppm relative to the solids content of the final spinning solution, and 79.79 kg of N, N-dimethylacetamide 85.79 kg of an amine solution in weight% was prepared. At this time, an amine equivalent ratio of diethylamine / ethylenediamine was 1 / 6.6.

The mixture of 508.80 g / min of the polyurethane prepolymer mixture and 59.58 g / min of the amine solution having a solid content of 7 wt% was added to a static mixer as a secondary polymerizer and mixed so that the amine / isocyanate equivalent ratio was 1.02 / 1, To prepare a polyurethane-urea polymer solution having 35.10% by weight.

0.3 g of titanium dioxide (0.1% by weight based on the solid content of the final product) as a whiteness improving agent, triethyleneglycol-bis-3- (3-tert-butyl- (Methylphenyl) propionate (0.9 wt% based on the final product solids content), 1,1,1, 1'-tetramethyl-4,4 '- (methylene-di- para-phenylene) 1.2 kg of carbazide (0.4% by weight based on the final solid content), 0.75 kg of poly (N, N-dimethyl-2-aminoethyl methacrylate (weight average molecular weight 20,000 g / mol) 0.3 kg of magnesium stearate as radioactive improver (0.1% by weight based on the solid content of the final product), total hydrous hydrotalc which satisfies the formula Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .2.3H ₂ O as an anti-chlorine agent (1.0% by weight based on the solid content of the final product), N, N- 23.678 kg of dimethylacetamide and 3.528 kg of the polyurethane prepolymer mixture (8.83% by weight of the total content of the slurry) were mixed and pulverized and dispersed with a sand grinder to prepare an additive slurry. The total additive slurry had a total solid content of 35 wt% %, And the viscosity was 65 poise.

568.35 g / min of the polyurethane-urea polymer solution and 27.75 g / min of the additive slurry were uniformly mixed in a static mixer to prepare a radiation dope having a solid content of 35% by weight. The viscosity of the prepared radiation dope was 12000 poise. Polyurethane urea elastic fibers were prepared by using dry spinning in which the spinning dope was discharged by discharging the spinning nozzle at a temperature of 260 ° C directly under the spinning nozzle at a spinning speed of 1100 m / min using a gear pump.

The physical properties are shown in Tables 1 and 2 below.

[Example 2]

The same procedure as in Example 1 was repeated except for using 6.0 kg of TD-800, which is hydrotalcite hydroxide, so that the content of the anti-scavenging agent in Example 1 was 2% by weight based on the total weight of the final product. Fiber.

The physical properties are shown in Tables 1 and 2 below.

[Example 3]

The same procedure as in Example 1 was repeated except for using 9.0 kg of TD-800, which is a hydrotalcite-containing hydroxide, so that the content of the antiseptic agent in Example 1 was 3 wt% based on the total weight of the final product. Fiber.

The physical properties are shown in Tables 1 and 2 below.

[Example 4]

In the same manner as in Example 1, except that 12.0 kg of TD-800, which is a hydrotalcite of total hydroxide, was used so that the content of the antiseptic agent in Example 1 was 4% by weight based on the total weight of the final product, the polyurethaneurea elasticity Fiber.

The physical properties are shown in Tables 1 and 2 below.

[Example 5]

In the same manner as in Example 1, except that 15.0 kg of TD-800, which is the hydrolytic hydroxide, was used so that the content of the antiseptic agent in Example 1 was 5% by weight based on the total weight of the final product, the polyurethaneurea elasticity Fiber.

The physical properties are shown in Tables 1 and 2 below.

[Example 6]

The same procedure as in Example 1 was repeated except for using 1.5 kg of TD-800, which is hydrotalcite hydroxide, so that the content of the antiseptic agent in Example 1 was 0.5% by weight based on the total weight of the final product, Fiber.

The physical properties are shown in Tables 1 and 2 below.

[Example 7]

In the same manner as in Example 1, except that 18 kg of TD-800, which is a total hydrolytic site, was used so that the content of the antiseptic agent in Example 1 was 6% by weight based on the total weight of the final product, polyurethane- .

The physical properties are shown in Tables 1 and 2 below.

[Example 8]

In Example 1, 1,3,5-tris (2,6-dimethvl-3-hydroxy-4-tert-butylbenzyl) isocyanurate was used as an asymmetric dihydroxyphenol- kg, the polyurethane-urea elastic fiber was prepared.

The physical properties are shown in Tables 1 and 2 below.

[Example 9]

Example 1 was repeated except that 4.924 kg of ethylenediamine as a chain extender and 1.198 kg of diethylamine as a chain terminator were used in Example 1 so that the amine equivalent ratio of diethylamine / ethylenediamine was 1 / 5.0. Polyurethane-urea elastic fibers were produced in the same manner.

The physical properties are shown in Tables 1 and 2 below.

[Example 10]

Example 1 was repeated except that 5.002 kg of ethylenediamine as a chain extender and 1.014 kg of diethylamine as a chain terminating agent were used in Example 1 so that the amine equivalent ratio of diethylamine / ethylenediamine was 1 / 6.0. Polyurethane-urea elastic fibers were produced in the same manner.

The physical properties are shown in Tables 1 and 2 below.

[Example 11]

Example 1 was repeated except that 5.059 kg of ethylenediamine as chain extender and 0.879 kg of diethylamine as chain terminator were added so that the amine equivalent ratio of diethylamine / ethylenediamine was 1 / 7.0. Polyurethane-urea elastic fibers were produced in the same manner.

The physical properties are shown in Tables 1 and 2 below.

[Example 12]

A polyurethane-urea elastic fiber was prepared in the same manner as in Example 1, except that diethylene triamine was used as a crosslinking agent in Example 1 so as to be 100 ppm based on the solid content of the final spinning solution.

The physical properties are shown in Tables 1 and 2 below.

[Example 13]

Polyurethane-urea elastic fibers were prepared in the same manner as in Example 1, except that diethylene triamine was used as a crosslinking agent in Example 1 so as to be 300 ppm based on the solids content of the final spinning solution.

The physical properties are shown in Tables 1 and 2 below.

[Example 14]

(Tetrakis [methylene-2- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate] methane), which is symmetrical dihydroxyphenol-based, was used as the antioxidant in Example 1 kg, the polyurethane-urea elastic fiber was produced in the same manner as in Example 1. The polyurethane-

The physical properties are shown in Tables 1 and 2 below.

[Comparative Example 1]

A polyurethane-urea elastic fiber was prepared in the same manner as in Example 1, except that 6 kg of Hydro Magnesite (manufactured by NanoTech Co., Ltd.) was used instead of the hydrotalcite hydroxide which was completely hydrolyzed as the anti-salt material in Example 1.

Powder spalling occurred in the slurry preparation process when hydro-magne- sate was used, and the dispersion time in the slurry was poor and the preparation time was longer than that in Example 1.

The physical properties are shown in Tables 1 and 2 below.

[Comparative Example 2]

A polyurethane-urea elastic fiber was prepared in the same manner as in Example 1, except that the hydrotalcite partially dehydrated and oxidized in the Example 1 was used.

The partially dehydrogenated hydrotalcite is added to water so as to be 2% by weight of stearic acid and 1% by weight of melamine polyphosphate in comparison with the weight of hydrotalcite, and the structural Mg ₈ Al ₄ (OH) ₂₄ (CO ₃ ) ₂ Hydrotalcite of 6H ₂ O was added, followed by stirring at 160 ° C for 30 minutes, followed by filtering and drying to obtain hydrotalcite coated with stearic acid and melamine phosphate. Then, the partially dehydrogenated hydrotalcite of the structural Mg ₈ Al ₄ (OH) ₁₆ O ₄ (CO ₃ ) ₂ coated with stearic acid and melamine polyphosphate was prepared and used by heat treatment at 250 ° C. for 4 hours.

The physical properties are shown in Tables 1 and 2 below.

[Comparative Example 3]

In the same manner as in Example 1 except that the hydrotalcite of the structural formula Mg ₄ Al ₂ (OH) ₁₃ CO _{3 3} H ₂ O having 4 wt% of dimethicone pyrophosphate coated as a anti-salt material was used in Example 1 To prepare a polyurethane-urea elastic fiber.

The physical properties are shown in Tables 1 and 2 below.

[Comparative Example 4]

Example 1 was repeated except that 4.812 kg of ethylenediamine as a chain extender and 1.464 kg of diethylamine as a chain terminator were added so that the amine equivalent ratio of diethylamine / ethylenediamine was 1 / 4.0. Polyurethane-urea elastic fibers were produced in the same manner.

The physical properties are shown in Tables 1 and 2 below.

[Comparative Example 5]

Example 1 was repeated except that 5.102 kg of ethylenediamine as a chain extender and 0.776 kg of diethylamine as a chain terminator were added so that the amine equivalent ratio of diethylamine / ethylenediamine was 1 / 8.0. Polyurethane-urea elastic fibers were produced in the same manner.

The physical properties are shown in Tables 1 and 2 below.

[Comparative Example 6]

Example 1 was repeated except that 5.164 kg of ethylenediamine as a chain extender and 0.628 kg of diethylamine as a chain terminator were used in Example 1 so that the amine equivalent ratio of diethylamine / ethylenediamine was 1/10.0. Polyurethane-urea elastic fibers were produced in the same manner.

The physical properties are shown in Tables 1 and 2 below.

[Comparative Example 7]

The polyurethane-urea elastic fiber was prepared in the same manner as in Example 1, except that diethylene triamine was added as a crosslinking agent in Example 1 so as to be 50 ppm based on the solids content of the final spinning solution.

The physical properties are shown in Tables 1 and 2 below.

[Comparative Example 8]

The polyurethane-urea elastic fiber was prepared in the same manner as in Example 1, except that diethylene triamine was used as a crosslinking agent in Example 1 so as to be 350 ppm based on the solids content of the final spinning solution.

The physical properties are shown in Tables 1 and 2 below.

[Comparative Example 9]

A polyurethane-urea elastic fiber was prepared in the same manner as in Example 1, except that the additive slurry was not added to the polyurethane-urea polymer solution at the time of preparing the radiation dope in Example 1, and then mixed.

The physical properties are shown in Tables 1 and 2 below.

Physical property Driving De burglar
(g / de) Shindo
(%) Driving value
(g) R Screening rate (%) Example 1 20.1 1.59 554 4.95 0.7 58.8 Example 2 20.1 1.57 542 4.91 0.8 59.4 Example 3 20.1 1.42 567 4.77 0.8 56.5 Example 4 20.0 1.25 598 4.63 0.9 51.5 Example 5 19.9 1.13 634 4.55 0.9 57.5 Example 6 20.1 1.57 556 5.01 0.8 60.1 Example 7 20.0 0.99 687 4.20 0.7 57.7 Example 8 20.1 1.55 551 4.92 0.8 58.5 Example 9 20.2 1.59 514 5.05 0.8 57.5 Example 10 20.1 1.57 535 4.98 0.7 60.2 Example 11 20.0 1.45 550 4.93 0.8 59.9 Example 12 20.1 1.51 535 4.85 0.8 58.4 Example 13 20.1 1.62 562 4.70 0.8 60.4 Example 14 20.1 1.48 542 4.85 0.8 55.5 Comparative Example 1 19.4 1.59 530 4.69 0.7 58.3 Comparative Example 2 19.6 1.53 545 4.71 0.8 57.5 Comparative Example 3 19.6 1.54 535 4.61 0.8 54.5 Comparative Example 4 19.7 1.62 495 4.45 0.7 57.5 Comparative Example 5 Radiation failure Comparative Example 6 Comparative Example 7 19.6 1.55 550 4.82 0.7 58.5 Comparative Example 8 19.5 1.55 540 4.71 0.7 58.4 Comparative Example 9 Radiation failure

Anti-chlorine Yarn color 0 hours 24 hours 48 hours L a b strong
(g) strong
(g) Rate of change (%) strong
(g) Rate of change
(%) Example 1 31.9 29.7 97.2 30.1 96.4 92.58 -1.39 2.67 Example 2 32.0 31.1 93.2 30.3 94.4 92.48 -1.29 3.68 Example 3 29.1 28.3 97.2 28.2 96.9 91.15 -1.33 3.78 Example 4 26.2 25.6 97.7 25.5 97.5 90.03 -1.02 3.97 Example 5 24.1 23.7 98.2 23.6 97.9 90.00 -1.00 4.02 Example 6 31.6 24.0 76.0 25.1 79.3 92.67 -1.25 2.25 Example 7 21.6 21.4 99.0 21.3 98.5 89.5 -1.15 4.51 Example 8 31.6 30.6 96.7 30.5 96.5 92.33 -1.22 3.65 Example 9 32.5 31.4 96.5 31.2 96.0 92.43 -1.33 3.67 Example 10 32.2 31.0 96.4 31.0 96.2 92.41 -1.25 3.61 Example 11 31.0 29.9 96.4 29.7 95.9 92.50 -1.21 3.70 Example 12 30.4 29.3 96.3 29.2 96.1 92.45 -1.29 3.68 Example 13 32.6 31.3 96.0 31.1 95.5 92.47 -1.29 3.66 Example 14 29.7 28.5 96.1 28.5 95.8 92.35 -1.18 4.12 Comparative Example 1 29.7 29.5 91.3 28.9 92.3 91.25 -1.17 3.88 Comparative Example 2 30.0 28.4 92.6 28.0 91.4 92.37 -1.21 3.69 Comparative Example 3 30.2 28.5 86.5 28.0 87.8 92.38 -1.27 3.61 Comparative Example 4 31.9 29.7 80.3 29.4 85.2 92.45 -1.23 3.59 Comparative Example 5 Radiation failure Comparative Example 6 Comparative Example 7 30.4 29.3 96.4 29.2 95.9 92.50 -1.21 3.69 Comparative Example 8 30.2 29.1 96.4 28.9 95.8 92.45 -1.23 3.48 Comparative Example 9 Radiation failure

As shown in Tables 1 and 2, the examples of the present invention show excellent heat resistance and anti-chlorine resistance.

In Comparative Example 1, hydro-magneite was used instead of hydrotalcite. When compared with Example 1, it was found that the anti-chlorine firing was low.

Comparative Example 2 uses partially dehydrogenated hydrotalcite. When compared with Example 1, it was confirmed that the strength, run value, and selectivity were lowered, and the anti-chlorine resistance was low.

Comparative Example 3 was obtained by using hydrotalcite having a structure other than hydrotalcite of the present invention. Compared with Example 1, it was confirmed that the strength, running value, and post-processability were lowered, I could.

In Comparative Example 4, the amine equivalence ratio of diethyleneamine / ethylenediamine was less than the range of the present invention. Compared with Example 1, it was confirmed that the elongation and running value were lowered, and the anti-chlorine resistance was low.

Comparative Example 5 is a case where the amine equivalent ratio of diethyleneamine / ethylenediamine exceeds the range of the present invention, and Comparative Example 6 is a case where the amine equivalent ratio of diethyleneamine / ethylenediamine exceeds the range of the present invention, The physical properties could not be measured.

Comparative Example 7 was a case where the crosslinking agent was used in an amount less than the range of the present invention. Compared with Example 1, it was confirmed that the strength and running value were lowered and the anti-chlorine resistance was low.

In Comparative Example 8, when the cross-linking agent was used in excess of the range of the present invention, it was confirmed that the strength, elongation, run value and post-processability were lowered as compared with Example 1, and the anti-chlorine resistance was low.

In Comparative Example 9, when the additive slurry was not prepared and the additive was directly added to the polymer solution, the spinning failed and the physical properties could not be measured.

Claims (7)

delete delete delete Polytetramethylene ether glycol and diphenylmethane-4,4'-diisocyanate were polymerized to have an NCO / OH molar ratio of 1.5 to 2.5 to prepare a polyurethane prepolymer such that the end unreacted isocyanate content was 2.4 to 3.5 mol% A primary polymerization step;
Adding the polyurethane prepolymer to N, N-dimethylacetamide to prepare a polyurethane prepolymer mixed solution having a solid content of 35 to 45% by weight;
Diethylenetriamine as a chain extender, diethylamine as a chain terminator, and diethylenetriamine as a crosslinking agent were dissolved in N, N-dimethylacetamide while the amine equivalent ratio of diethylamine / ethylenediamine was 1 / 5.0 to 7.0 , And diethylene triamine in an amount of 100 to 300 ppm based on the solids content of the final spinning solution to prepare an amine solution;
A second polymerization step of mixing the polyurethane prepolymer mixed solution and the amine solution with an amine / isocyanate equivalent ratio of 1.01 to 1.06 / 1 to prepare a polyurethane urea polymer solution having a solid content of 35 to 40 wt%;
Adding an additive slurry containing the entire hydroxylated hydrotalcite of the following formula (1) to the polyurethane-urea polymer solution and uniformly mixing them to prepare a radiation dope having a solid content of 35 to 40% by weight; And
Radiating the radiation dope;
≪ / RTI >
[Chemical Formula 1]
Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .2.3H ₂ O 5. The method of claim 4,
Wherein the additive slurry is an anticorrosive agent comprising the total hydroxide hydrotalcite of Formula 1; One or more additives selected from whiteness improvers, antioxidants, gas stabilizers, and dyeability improvers; N, N-dimethylacetamide; And a polyurethane prepolymer mixture liquid, and pulverizing and dispersing the polyurethane prepolymer mixture. 6. The method of claim 5,
Wherein the antioxidant comprises an asymmetric dihydroxyphenol-based antioxidant. The method of claim 4, wherein
Wherein the entire hydrolytic hydrotalcite contains from 1 to 5% by weight based on the total weight of the polyurethane-urea elastic fibers.