KR970010729B1 - Manufacturing process of polyurethane elastic fiber having excellent light and heat-resistant properties - Google Patents

Abstract

A long chain diol(A) which is produced by mixing polyeter diol(A-1) and polycarbonate diol(A-2) and an organic diisocyanate compound (C) containing polyol(B) of hydroxy group 3-6, carbonate 4-10, that includes at least one of the hydroxy group, are preliminary polymerized, to be compounded in regular rate with a solvent. Further, using a diamine compound(D) as a chain growing agent in 0.60-0.98 mol% of whole preliminary polymer, the chain is grown and added so as to complete the polymerization. The ultra violet stabilizer(F) is added to the hardened material in the ratio of 0.05-3wt% and spun to produce a polyurethane elastic fiber.

Description

Manufacturing method of polyurethane-based elastic fiber excellent in light resistance and heat resistance

The present invention relates to a method for producing a polyurethane elastic fiber that is stable to ultraviolet rays and excellent in heat resistance while maintaining the inherent physical properties of the elastic fiber.

Polyurethane elastic fibers are used for stretch fabrics such as stockings, women's underwear and swimwear due to their excellent elasticity and elasticity. However, due to their poor light resistance, physical degradation occurs due to light (ultraviolet rays) and discoloration. There are disadvantages such as various problems, especially when used in the external exposed areas, such as stockings, polyurethane fibers are also weak to heat when used in combination with other materials, such as polyester fibers 130 ℃ It is difficult to dye at high temperature, so there is a restriction in use.

As a method for improving light resistance among the drawbacks described above, as described in Japanese Patent Laid-Open Nos. 56-11948 and 61-478l9, a method of improving daylight fastness by containing 0.01 to 10% by weight of a phenol compound, A method of improving discoloration prevention using a chlorine bleach as described in point 57-176260, a method of achieving light stability using a bisbenzotriazole urea system as mentioned in U.S. Pat. However, a satisfactory level of effect could not be obtained, and the improvement of heat resistance is difficult to expect, and furthermore, it has disadvantages such as lowering the elastic recovery rate, which is inherent to polyurethane elastic fibers. In addition, as a method for improving heat resistance, as described in Japanese Patent Application Laid-Open No. 5-5217, a polyether-based polyurethane having an allophanite bond and a polyester-based or polycarbonate-free having no malopite bond Although a method of producing a composite by spun polyurethane is known, the light resistance and heat resistance of the produced polyurethane elastic fiber is somewhat improved, but there are various problems in manufacturing, such as a satisfactory level and complex spinning.

Therefore, an object of the present invention is to maintain the inherent properties of the polyurethane elastic fiber while preventing the degradation of physical properties and discoloration by light (ultraviolet rays), and to improve the light resistance and heat resistance to enable high temperature dyeing method of producing a polyurethane elastic fiber To provide.

In order to achieve the above object as well as another object that can be easily expressed in the present invention, a long-chain diol (A) and a tertiary mixture of polyether diol (A-1) and polycarbonate diol (A-2) Having at least one hydroxyl group, the polyol (B) having 3 to 6 hydroxyl groups and 4 to 10 carbon atoms is prepolymerized with an excess of diisocyanate (C), mixed with a solvent in a fixed ratio, and the terminal isocyanate is diamine compound ( Polyurethane Crab elastic fiber which significantly improved light resistance and heat resistance by adding UV stabilizer (F) after blocking the end by using monoamine compound (E) after obtaining appropriate viscosity for spinning by growing chain by using appropriate amount of D). Could get

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

The polyurethane-based elastic fiber of the present invention is a long-chain diol (A) and a third obtained by mixing a polyether diol (A-1) having a number average molecular weight of 1,000 to 3,000 and a polycarbonate diol (A-2) having a number average molecular weight of 800 to 2500. Polyamine (C) having 3 to 6 hydroxyl groups and 4 to 10 carbon atoms (B) is prepolymerized with an excess of an organic diisocyanate compound (C), mixed with a solvent at a fixed ratio, and diamine as a chain growth agent. Ultraviolet stabilizer (F) after completion of polymerization by chain growth using compound (D) of 0.60-0.98 mol% of prepolymer and addition of monoamine (E) as chain stopper to 1-30 mol% of total amine usage. It is prepared by adding and spinning to 0.05 to 3% by weight based on the polymer solids.

The polyurethane-based elastic fiber of the present invention has a molar ratio of a polyether diol (A-1) having excellent elasticity performance and a polycarbonate diol (A-2) having excellent light resistance and heat resistance as a long chain diol (A) component serving as a soft segment. (A-2) / (A-1) = 0.01 to 10, in particular 0.5 to 5 by using a mixture to compensate for each of the shortcomings while maintaining the elastic performance and improved light resistance and heat resistance.

As the polyether diol (A-1), polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or the like can be used, and it is effective that the molecular weight is in the range of 1000 to 3000, more preferably 1500 to 2500.

Examples of the polycarbonate diols (A-2) include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 Glycols alone or mixtures thereof, such as, 4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol, 1,8-octanediol, or a diaryl carbonate, dialkyl Diols having a molecular weight of 800 to 2500 and more preferably 1000 to 2000 synthesized by condensation with carbonate, phosgene and the like are effective.

If the molecular weight and molar ratio of the polyether diol (A-1) and the polycarbonate diol (A-2) are out of the above range, there is a problem in strength, elongation, light resistance, heat resistance, etc., which are inherent physical properties of the elastic yarn. Performance will not be obtained.

In addition, the polyurethane elastic fiber of the present invention has at least one or more tertiary hydroxyl groups and is made of side chains at positions other than the sock end using polyols (B) having 3 to 6 hydroxyl groups and 4 to 10 carbon atoms. The introduction of a tertiary hydroxyl group has a network structure by urethane bonds with isocyanates to form a strong bond, thereby improving heat resistance and elastic recovery ability, and improving viscosity stability of the polymer to maintain a suitable viscosity for spinning.

As a polyol (B) component which has a tertiary hydroxyl group, 1,2, 3- hydroxy special 2-ethyl propane, 1,2, 3-hydroxy-2- methyl propane, 1, 2, 4-hydroxy -2-methylbutane, 1,2,5-hydroxy-2-methylpentane, 1,3,5-hydroxy-3-methylpentane, 1,3,6-hydroxy-3-methylhexane, l, 2,3,6-hydroxy-2,3-dimethylhexane, 1,2,4,6-hydroxy-2,4-dimethylhexane and the like may be used alone or in a mixture thereof.

The molar ratio between the long-chain diol (A) and the polyol (B) having a tertiary hydroxyl group is A / B = 5 to 50, particularly 10 to 40 is suitable, and less than 5 does not dissolve well in the solvent, so there is a problem in spinning. In the case of exceeding 50, the degree of improvement in heat resistance and elastic recovery force is minimal.

Examples of the diisocyanate compound (C) which combines with an amine compound as a chain growth agent and acts as a hard segment include paraphenyl diisocyanate, metaphenylene diisocyanate, 2,4-torylene diisocyanate, and 2,6-tori Ethylene diisocyanate, 1-chloro-2,1-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,4-phenylene diisocyanate, chlorophenylene-2,4'-diisocyanate, methylenebis-4 -Phenyldiisocyanate, hexamethylene diisocyanate, polymethylenepolyphenyl diisocyanate, methylcyclohexylene diisocyanate, paraphenyl diisocyanate, paraphenylene diisocyanate, 4, 4'-diphenylisopropylidine diisocyanate, 3,3'-dimethyl-4, 4'-diphenyl diisocyanate, 3,3'-dimethoxy-4, 4'-diphenylene diisocyanate, 4, 4'-diphenylmethane diisocyane There are compounds of the agent such as 4,4'-diphenylmethane di-isocyanate compound it is best at 4, considering the physical properties of the elastomer and reactive with the diol compound.

The amount of the diisocyanate compound (C) is appropriate for C / (A + B) = 1.25 to 2.5 mol based on the compound (A + B) in which the long-chain diol (A) and the polyol (B) having a tertiary hydroxyl group are mixed. When the polymer content is less than 1.25 moles, the polymer is excellent in elongation but the strength is low and the elastic recovery power is insufficient. When it is used more than 2.5 moles, the strength and elastic recovery are excellent, but the elongation is poor, resulting in the inherent deterioration of physical properties as an elastomer.

The prepolymer obtained by combining the long chain diol (A), the polyol (B), and the diisocyanate compound (C) is chain-grown by the diamine compound and chain-grown at a constant molecular weight, and then chain-stopped with monoamine to obtain a polymer having an appropriate molecular weight. Can be.

As diamine compound (D) which chain-grows a prepolymer, methyliminobispropylamine, 2, 5- dimethyl piperazine, 1, 2- propylene diamine, 2, 3- butylene diamine, meta xyliandiamine, and para-zyrendiamine , 2-methylpiperazine, ethylenediamine, ethanoldiamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1-methyl-2,4-diaminebenzene, 1,2-cyclohexanediamine, 1, 3-cyclohexane Compounds such as diamine, 1,4-cyclohexanediamine, octamethylenediamine, paraphenylenediamine and the like are used, and the range of use thereof is 0.6 to 0.98 mol% based on the prepolymer, and the characteristics required by the present invention are out of this range. This is not obtained.

However, in order to improve the viscosity stability of the polymer in the chain growth compound and the properties of the elastic yarn after spinning, a linear amine and a cyclic amine should be mixed in an appropriate ratio.

The molar ratio (D-1) / (D-2) of linear diamine (D-1) to cyclic diamine (D-2) is in the range of 2 to 20, and the ratio of (D-1) / (D-2) If the molar ratio is less than 2, a low molecular weight polymer is produced, resulting in deterioration of mechanical properties such as strength, elongation, elastic recovery rate, and a molar ratio of (D-1) / (D-2) to exceed 20. In this case, the reaction rate is too fast to generate a large amount of side reactions, thereby degrading the stability of the polymer and reducing the heat resistance.

Examples of the monoamine-based compound (E) which is a chain stopper for blocking the terminal of the chain-grown evipolymer include monoethanolamine, diethanolamine, propylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, and di (2). Compounds such as ethylhexyl) amine, butylamine, and diethylamine may be used, and the amount of the compound may be used in an amount of 1 to 30% (mol%) of the total amine. The viscosity increases rapidly and the viscosity changes so much that the viscosity continues to rise, making it unsuitable for spinning, and when it exceeds 30%, it does not grow into a polymer having an appropriate molecular weight because it hinders the chain growth of the polymer, and thus it is impossible to obtain a suitable viscosity for spinning The physical properties of the polymer are poor in strength, elongation and elastic recovery.

As a solvent for improving the radioactivity by controlling the solid content of the polymer, dimethylacetamide, dimethylformromamide, hexamethylphosphoramide, dimethylnitrosoamine, dimethylpropionamide, methoxydimethylacetamide, N-methylpyrrolidine, dimenyl There are compounds such as sulfoxide, tetramethylenesulfone and the like. Dimethylacetamide or dimethylformamide is advantageous in terms of compatibility with the polymer, radioactivity and solvent recovery. It is good to use so that the solid content of the polymer of the usage-amount of a solvent may be 15 to 45%, and when it is less than 15% or more than 45%, it will have a bad influence on radioactivity.

As a compound (F) for preventing the physical property fall and discoloration by light (ultraviolet rays), 2-hydroxy-4- methoxy benzophenone, 2-hydroxy-4- dodecyloxy benzophenone, 2-hydroxy-4 -Methoxy-5-sulfobenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 2, -dihydroxy-4,4'-dimethoxybenzophenone, phenylsalicylate, P-t-butylphenylsalicylate, 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl There are compounds such as 2-cyano-3,3'-diphenyl acrylate, and benzophenone compounds are the best.

Suitable amount of UV stabilizer is 0.05 to 5% by weight with respect to the polymer solids, less than 0.05% by weight lacks stability to light (ultraviolet), and more than 3% by weight of stability to light (ultraviolet) is more than a certain effect Not rising is not only economical, but also impairs the inherent properties of the elastomer and adversely affects radioactivity.

Tensile strength, elongation and elastic recovery rate shown in the examples were based on KSK 0219, and the stability against ultraviolet rays was evaluated by physical properties after exposure to sunlight for a certain time according to the method according to KSK 0700. After 60 minutes treatment in the dryer was evaluated by strength retention and color change (Gray scale; water supply determination using the ISO international standard). On the other hand, the viscosity of the polymer was measured by Brook Field product model No. DV-III.

The following Examples and Comparative Examples illustrate the present invention more specifically, but do not limit the scope of the present invention.

(Example 1)

1 mol of polyhexamethylene carbonate diol having a molecular weight of 2,000 synthesized by condensation reaction of 1,6-hexanediol with diphenyl carbonate, 1 mol of polytetramethylene glycol having a molecular weight of 2,000, 1,3,5-hydroxy-3 0.2 mol of methylpentane was stirred at 80 ° C. under reduced pressure to remove water, and then 4,4′-diphenylmethane diisocyanate, 4.4 mol, pre-heated at 50 ° C. was added, and polymerization was performed at 90 ° C. for 60 minutes in a nitrogen gas atmosphere. To prepare a prepolymer. The prepolymer was dissolved in dimethylacetamide and the solution was cooled to 5 ° C., and then, as a chain growth agent, 1 mol of ethylenediamine, linear amine, 0.9 mol of 1,2-propylenediamine, and 0.1 mol of metaxylenediamine as cyclic amine. A chain growth agent solution obtained by dissolving 0.1 mol of 1,4-cyclohexanediamine in 15% concentration in dimethylacetamide was slowly added to the prepolymer to obtain a polymer having a viscosity of 3,500 poise.

To the polymer was slowly added a solution obtained by dissolving isopropylamine 0.2 mol in 15% concentration in dimethylacetamide to obtain a polymer having a viscosity of 3,000 poise. 2-hydroxy-4-methoxybenzophenone, a stabilizer against ultraviolet rays, was added to this polymer in a concentration of 10% in dimethylacetamide so as to be 0.2% by weight of the final polymer solids to adjust the solid content of the final polymer to 32%. At this time, the viscosity is 2,900 poise. This polymer was prepared by spinning a conventional 70-denier polyurethane elastic yarn using a dry spinning method, the results of the evaluation of physical properties are shown in Table 1.

Comparative Example 1

Polymerization was carried out in the same manner as in Example 1 except that 0.1 mol of polyhexamethylene carbonate diol having a molecular weight of 2,000 and 1.9 mol of polytetramenylene glycol having a molecular weight of 2,000 were used. The results of the evaluation of the physical properties are shown in Table 1.

Comparative Example 2

Polymerization was carried out in the same manner as in Example 1 except that 1,3,5-hydroxy-3-methylpentane having a tertiary hydroxyl group was not used. The results of the evaluation of the physical properties are shown in Table 1.

Comparative Example 3

Polymerization was carried out in the same manner as in Example 1 except that the metacyclic diamine, which is a cyclic amine, and 1,4-cyclohexanediamine were not used in the chain-grown amine.

Comparative Example 4

Polymerization was carried out in the same manner as in Example 1 except that 0.02 mol of isopropylamine, which was a chain growth agent, was used.

Comparative Example 5

Polymerization was carried out in the same manner as in Example 1 except that 2-hydroxy-4-methoxybenzophenone for improving light resistance was not used, and the results of evaluation of physical properties are shown in Table 1.

[Table 1] Property evaluation results

Claims (6)

Having at least one long-chain diol (A) and a tertiary hydroxyl group in which a polyether diol (A-1) having a number average molecular weight of 1,000 to 3,000 and a polycarbonate diol (A-2) having a number average molecular weight of 800 to 2500 are mixed. The polyol (B) having 3 to 6 hydroxyl groups and 4 to 10 carbon atoms is prepolymerized with an excess of an organic diisocyanate compound (C), mixed with a solvent and in a fixed ratio, and then a prepolymer of a diamine compound (D) as a chain growth agent. Of 0.60-0.98 mol% of amine and monoamine (E) as a chain stopper was added to 1-30 mol% of the total amine usage to complete the polymerization, so that the UV stabilizer (F) was 0.05-3 weight% based on the polymer solids. Method for producing a polyurethane elastic fiber excellent in light resistance and heat resistance, characterized in that the addition and spinning. The light resistance and heat resistance according to claim 1, wherein the molar ratio (A-2) / (A-1) of the polyether diol (A-1) and the polycarbonate diol (A-2) is from 0.1 to 10. Excellent polyurethane elastic fiber manufacturing method. The method for producing a polyurethane elastic fiber having excellent light resistance and heat resistance according to claim 1, wherein the molar ratio A / B of the long-chain diol (A) and the polyol (B) is 5 to 60. The diisocyanate compound is used in an amount of a ratio C / (A + B) = 1.25 to a mixture (A + B) in which a long-chain diol (A) and a polyol (B) having a tertiary hydroxyl group are mixed. Method for producing a polyurethane elastic fiber excellent in light resistance and heat resistance, characterized in that 2.5 moles. The method for producing a polyurethane elastic fiber having excellent light resistance and heat resistance according to claim 1, wherein the diamine compound (D) is a combination of a linear diaman (D-1) and a cyclic diamine (D-2). The method for producing a polyurethane elastic fiber according to claim 5, wherein the molar ratio (D-1) / (D-2) of linear diamine (D-1) to cyclic diamine (D-2) is 2 to 20.