KR950002604B1 - Method of producing polymeric solution for elastic fiber - Google Patents

Abstract

Polymeric solution for elastic fiber having good releasibility is prepared by Pre-polymerising high melecular diol cpd. and diisocyanate cpd., and mixing with solvent; chain-extending terminal isocyanate with diamine cpd.; and adding silica cpd., Pref. the silica based cpd. is added in the amount of 0.05-3wt.% w.r.t. the whole solid part. The process reduces the adhesiveness and keeps the good properties of the polyurethane polymer and then provides good releasibility. The obtd. polyurethane elastic fiber is useful for clothes.

Description

Method for producing polymer solution for elastic fibers having excellent sea-resistance

The present invention relates to a method for preparing a polymerized crab solution for elastic fibers while maintaining excellent elasticity, which is an inherent physical property of elastic fibers. More specifically, the high molecular weight diol compound and the diisocyanate compound are prepolymerized, mixed with a solvent at a predetermined ratio, and then a suitable amount of the diamine compound is used to chain grow the isocyanate at the terminal to obtain a suitable viscosity for spinning. It relates to a method for producing a polymer solution for elastic fibers excellent in the sea-resistance, characterized in that the end is sealed using, and the silica crab compound is added immediately before spinning.

Polyurethane elastic fibers are used in various apparel products such as socks, swimwear, gym clothes, medical (bandages, protective socks) and women's underwear, and is one of the closest synthetic fibers in our daily life. However, polyurethane elastic fibers have a very high adhesiveness to adhere to other objects compared to other fibers, and are attached to the needles of a roller or a knitting machine during the production process, causing excessive fiber tension and cutting the fibers. Being

Various methods for improving the problem have been proposed. That is, U.S. Patent No. 3,039,895 describes a method of reducing the tension by mixing metal soap particles with a spinning oil, and U.S. Patent No. 4,296,174 describes polytetramethylene ether glycol and excess 4 After reacting 4,4'-diphenylmethane diisocyanate (4,4'-Diphenylmetha1le diisocyanate) and dissolving it in an inert organic solvent, chain growth with aromatic diamine and lower fatty acid diamine, followed by monoamine A method of lowering the adhesiveness and improving the properties by adding a metal soap-based compound to a polymer prepared by terminating in ()) is described.

However, the above-described methods can be used in the case of producing a dul1 fiber having a tint by adding titanium dioxide (TiO ₂ ), which is a pigment, but in the case of producing a bright fiber in which the pigment is not added. It could not be applied due to the change in color tone of fiber yarn by the addition of metal soap-based compound.

Accordingly, it is an object of the present invention to provide a method for producing a polymer solution for elastic fibers, which significantly reduces the adhesiveness while maintaining the inherent physical properties of the polyurethane polymer. In order to achieve the above object as well as another object that can be easily expressed in the present invention, the prepolymerization of a high-molecular weight diol compound and diisocyanate compound is mixed with a solvent at a constant ratio, and then a suitable amount of diyne compound is used. Isocyanate chains were grown to obtain a viscosity suitable for spinning, and then, a monoamine compound was used to block the ends and a silica-based compound was added to the radial line to prepare a polymer solution for elastic fibers having excellent sea-degradability.

The present invention will be described in more detail as follows.

After prepolymerizing 1 mole of a high molecular weight diol compound having a number average molecular weight of 1,000 to 3,000 and 1.5 to 2.7 moles of niisocyanate compound, a solution of a prepolymer of the dissolution time in an inert organic solvent was prepared. A monoamine compound in an amount corresponding to 1 to 10 mole% of the niamine compound used for chain growth is produced by chain growth of the terminal diisocyanate using 0.7 to 0.95 moles of diamine compound per 1 mole of the prepolymer. After the chain growth was terminated, 0.05 to 3% by weight of the silica-based compound was added to the polymer solids in the polymer solution to prepare the polymer solution for elastic fiber oil of the present invention.

Examples of the high molecular weight diol compound that acts as a soft-scgment in the elastomer include polyether compounds such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, and polyoxypentamethylene glycol, and polyethylene. Polyester-based compounds such as adipate, polybutylene adipate, polyneopentyl adipate, polyhexameltylene adipate, polycaflolactone, or polycarbonate compounds such as polybutylene carbonate and polyhexamethylene carbonate may be used. have. However, considering the physical properties and reactivity of the elastomer, the polyether-based compound having a number average molecular weight of 1,000 to 3,000, preferably 1,500 to 2,500, particularly polytetramethylene ether glycol, is most effective.

Moreover, as a diisocyanate compound which combines with the amine compound which is a chain growth agent, and acts as a hard segment, 2, 4- toluene diisocyanate. 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-phenylene diisocyanate, polymethylene polyphenyl diisocyanate, paraphenyl diisocyanate, metaphenylene diisocyanate, 4,4 ' -Diphenylisopropylidine diisocyanate, 3,3'-dimethyl 4,4'-diphenyl isocyanate, etc., and 4,4'diphenylmethine diisocyanatle is used in consideration of the reactivity and the physical properties of the polymer. Most preferably.

For the use of diisocyanate compounds, 1.5 to 2.7 moles are suitable for 1 mole of high molecular weight diol compound, and when used below 1.5 moles, the elongation at polymerization is excellent but the strength is lowered and the elastic recovery rate is insufficient. It is restricted to use, and when it is used more than 2.7 mole, its strength and elastic recovery rate is good but its elongation is poor, so it is restricted to use as an elastic fiber.When it is used more than 2.7 mole, its strength and elastic recovery rate is good, but its elongation is poor, it is elastic There was a disadvantage in that the intrinsic properties as a polymer are lowered.

Examples of the diamine compound for chain-growing the prepolymer include methylenediamine, ethanoldiamine, 1.2-propylenediamine, 2,3-butylenediamine, pentamethylenediamine, and hexamethylenediamine. Amine compounds, such as paraphenylenediamine, and low molecular weight glycol compounds, such as ethylene glycol, 1, 3- propylene glycol, pentamethylene glycol, 1, 4- butanediol, are used. It is effective to use 0.7 to 0.9 moles with respect to 1 mole of the prepolymer in consideration of the physical properties of the polymer and the economical aspect of the diamine compound during chain growth of this prepolymer.

However, in order to minimize the generation of gel, improve the mechanical properties and improve the chlorine resistance of the chain growth compound by maintaining the reaction rate at an appropriate level, linear diamines and aromatic diamines in an appropriate ratio. It must be mixed. The molar ratio of linear diamine and aromatic diamine is preferably in the range of 1.7 to 25 moles: 1 mole. When the molar ratio of linear diamine is more than 25 moles, the reaction rate is too fast, so that the side reactions including the gel are excessive. When the molar ratio of linear diamine is used at 1.7 mole or less, the reactivity is poor, resulting in a polymer having an appropriate molecular weight or less, which causes mechanical properties such as strength and elongation of the polymer. .

On the other hand, in order to maintain the reaction rate at an appropriate speed and lower the adhesiveness without lowering the mechanical properties of the polymer, it is most effective to use ethyllandiamine as linear diamine and 1,3-cyclohexylenediamine as aromatic diamine. to be.

Examples of the monoamine-based compound which is a chain stopper for blocking the terminal of the chain-grown prepolymer include monoethanolamine, diethanolamine, diethyleneamine, diisopropylamine, diisobutylamine, di (2-ethylhexyl) amine, and the like. There is a compound, diethanolamine is excellent in the chain stop effect is advantageous to the stability of the polymer, and by maintaining the molecular weight in an appropriate size, it is possible to obtain a balance of the physical properties, strength, elongation and elastic recovery rate of the polymer.

The amount of monoamine used is 1-10 mol% of the mole used in the diamine, which is a chain growth system, and below 1 mol%, the chain stopping effect is poor and the viscosity of the polymer is severely changed over time. Since it impedes growth, it is impossible to obtain a polymer having an appropriate molecular weight, which is not suitable for spinning, and the physical properties, strength, and elongation of the polymer are poor.

As a solvent for improving the radioactivity by adjusting the solid content of the polymer, diethylformamide, dimethylacetamide, hexaethylphosphoramide, dimethylnitrosoamine dimethylpropionamide, ethoxydiethylacetamide, N-ethylpyridine , Diethyl sulfoxide, tatrimethylene silpon and the like, and diethylmoramide or dimethylacetide is effective considering the compatibility with the polymer, radioactivity and solvent recovery. It is preferable to use the solvent in such a manner that the solid content of the polymer is 15 to 40%, and adversely affects the radioactivity at 15% or less or 40% or more.

Compounds for reducing the adhesiveness include compounds such as silica, titanium dioxide, barium titanate, zinc thiosinide, magnesium desartite, and the use of silica compounds not only increases the effect of reducing the adhesiveness but also brightly colored fibers. Does not affect the color tone at all. The proper amount of the adhesive lowering agent is 0.05 to 3% by weight with respect to the polymer solids, the adhesive lowering effect is poor at 0.05% by weight or less, and the adhesive lowering effect is not large at 3% or more by weight, which is uneconomical and inherent in the elastic polymer. This inhibited problem occurs.

In the above-described method, an additive commonly used in the art to which the present invention pertains may be added to the prepared polymerized crab solution for elastic fibers, such as compounds for improving the fastness to harmful gases in sunlight and air, and other fillers. have. That is, as a compound for improving the electrical conductivity to harmful gases in daylight and air, triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4'-vidylidene bis ( 3-methyl-6-t-

Phosphorus compounds and 2-hydroxy-4-methoxybenzo- such as butyl phenyl dietreneyl) phosphite, pentaerythriol phosphite, cyclonepentane tetrabis (octanesyl) phosphite, tris (nonylphenyl) phosphite Phenone, 2-hydroxy-4-octoxy benzophenone. Benzogenol compounds, such as 2,2'-dihydroxy-4- methoxy benzophenone, 2- (2'- hydroxy-5-edylphenyl ) Benzotriazole compounds, such as benzotriazole and a bis 'hydride-3', 5'-di-t-butylphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3 Compounds of daamine acrylates such as' -diphenyl acrylate, aryl-2-cyano-3,3'-diphenylacrylate and edyl-2-cyano-3,3'-diphenylate And particularly preferred compounds are pentaerythrido phosphite compounds.

Appropriate amount of compound that improves the fastness to harmful gases in sunlight and air is appropriate in the range of 0.05 to 3% by weight with respect to the polymer cross-linking, and in the case of 0.05% or less by weight, the effect of improving light resistance is insufficient. The improvement is not uneconomical because it does not rise above a certain effect, but also impairs the inherent physical properties of the elastomer and adversely affects radioactivity.

The elastic solution was prepared by wet spinning a polymer solution prepared by the above method, which is commonly used in the art.

The following examples and comparative examples further illustrate the present invention, but do not limit the scope of the present invention.

Example 1

250 g of 4,4'-diphenyl ethane isocyanate was added to l000 g of polytetraethylene ether glycol having a molecular weight of 2000 and mixed, followed by heating and polymerization under a nitrogen gas atmosphere for 801 C x 70 minutes to prepare a prepolymer. This was dissolved in 370 g of diethylformamide, and the temperature of the solution was cooled to 3 ° C. A solution of 22 g of ethylenediamine, 1 lg of 1,3--cyclosecylenediamine, and 5 g of amine dibutyl was added to 500 g of diethylformamide. And polymerization. At this time, the temperature of the polymer was maintained at 30 ℃ or less.

After the completion of the polymerization, the solid content of the final polymer was adjusted to 20% by adding a solution obtained by dissolving 25 g of pentaerythrol phosphite, which is a fastening agent against harmful gases in sunlight and air, and 13 g of silica, which is a tackifier, to 600 g of dimethylformamide. The viscosity at this time was 500 poise (poise).

After the polymer was spun to 70De / 7fi1 through a conventional wet spinning process, the yarn's tension, ie, the sea resolution, was measured by Toray Engineering's TTA-80l, and its tensile strength, elongation, and elastic recovery rate were KSK-0219. The results are shown in Table 1 below.

Comparative Example 1-5.

The elastic yarn was produced in the same manner as in Example 1 except that the kind and amount of the tackifier was performed as described in Table 1, and then the physical properties thereof were measured in the same manner as in Example 1, and the results are shown in Table 1. It was.

Table 1

Claims (2)

Prepolymerization of high molecular weight diol compound and diisocyanate compound is mixed with solvent, followed by chain growth of terminal isocyanate using diamine compound, blocking of terminal using monoamine compound, and addition of silica-based compound. Method for producing a polymer solution for elastic fibers excellent in sea-water. The method for producing a polymer solvent for elastic fibers according to claim 1, wherein the list price ratio of the silica compound is 0.05 to 3% by weight based on the polymer solid.