KR0145400B1 - Manufacturing method of polyurethan fiber with easily dyealele - Google Patents

Abstract

The object of the present invention is to obtain a polyurethane elastic fiber excellent in dyeing and heat resistance while maintaining the intrinsic properties of the elastic fiber. The polyurethane elastic fiber used in the present invention is a long-chain diol component that acts as a soft segment and has high elastic performance. Complementing the shortcomings by mixing the excellent polyether diol and the polycarbonate diol with excellent heat resistance with each other, the technical composition of the polyether diol (A-1) having a number average molecular weight of 1,000 ~ 3,000 and the number average molecular weight of 800 ~ 25, Excess organic diol (A) mixed with 00 polycarbonate diol (A-2) and 3-6 hydroxyl groups and 4-10 carbon atoms (B) having at least one tertiary hydroxyl group After prepolymerization with an isocyanate compound (C) and mixing with a solvent at a constant ratio, a diamine mixture (D), a chain growth agent, is used for 0.60 to 0.98 moles of the prepolymer, After adding the noamine (E) to 1 to 30 mol% of the total amine usage, the polymerization is completed, and then the dyeability improving additive (F) and the property deterioration inhibitor (G) represented by the following formula (1) are added to the final polymer solids. By adding 0.05 to 4% by weight, the method of producing polyurethane elastic fibers having excellent heat resistance and dyeing properties while maintaining the inherent properties of elastic yarns. In this case, not only does not adversely affect radioactivity, but also the process is simple and economically beneficial. It is a novel manufacturing method.

Description

Manufacturing method of polyurethane elastic fiber with excellent dyeing and heat resistance

The present invention relates to a method for producing a polyurethane elastic fiber having excellent heat resistance and dyeing properties while maintaining the inherent physical properties of the elastic fiber.

Polyurethane-based elastic fibers are widely used in stretch fabrics such as stockings, women's underwear and swimwear because of their excellent elasticity and elastic recovery.

However, polyurethane-based fibers are weak to heat, so when mixed with other materials such as polyester fibers, it is difficult to dye at a high temperature of about 130 ° C., so there is a limitation in use.

In addition, polyurethane-based fibers are dyed in acid dyes because there are no dye seats in the molecular structure, but dyes using disperse dyes, but have a significantly lower fastness than acid dyes.

Conventional techniques that have been studied to improve heat resistance among these drawbacks include Japanese Patent Publication No. 5-5217, Polyether-based polyurethane having an allophanate bond and a polyether-based or polycarbonate-based polyether having no allophanate bond. Although there is a method of complex spinning of urethane, in the case of polyurethane elastic fibers manufactured by this method, the light resistance and heat resistance are somewhat improved, but are not satisfactory, and there is a manufacturing problem because composite spinning should be performed.

In addition, Japanese Patent Laid-Open Publication No. 49-99193 discloses a tertiary nitrogen-containing low-molecular weight diol and an excess of isocyanate and then chain-extends it with an amine to provide a certain amount of polymer. After the preparation, a method of improving the dyeability by adding a predetermined amount of the polymer to the elastic polyurethane polymer has been disclosed, and Japanese Patent Laid-Open No. 58-45221 has prepared a tertiary nitrogen-containing polyester glycol and then adding an excess of isocyanate. And a method of preparing polyurethane polymers having a constant viscosity by chain extension using amines after the prepolymerization, has been known. US Pat. There is a known method for improving the dyeability by adding a certain amount to the , In the case of the method a polyurethane elastic material produced by the dyeability is improved but there is a disadvantage not only degrade the unique property of elastic recovery ratio of the polyurethane elastic body exerting a bad influence on the radiation.

The present invention relates to a method for producing an excellent polyurethane elastic fiber improved heat resistance and dyeing function while maintaining the inherent physical properties of the polyurethane elastic fiber in order to solve the above-mentioned drawbacks, polyether diol (A-1) And excess diisocyanate (C) containing 3 to 6 hydroxyl groups and 4 to 10 carbon atoms (B) having at least one long-chain diol (A) mixed with a polycarbonate diol (A-2) and a tertiary hydroxyl group. ) And pre-polymerized with a solvent and mixed in a certain ratio, and the terminal isocyanate is chain-grown using an appropriate amount of diamine compound (D) to obtain a suitable viscosity for spinning, and then the terminal is blocked using monoamine compound (E). Next, the present invention relates to a method for producing a polyurethane elastic fiber that significantly improves dyeing function by adding a dyeability improving additive (F) and a property deterioration preventing agent (G) immediately before spinning. .

Hereinafter, the present invention will be described in detail.

Polyurethane elastic fiber used in the present invention is a long-chain diol (A) component that acts as a soft segment, the molar ratio of polyether diol (A-1) excellent in elastic performance and polycarbonate diol (A-2) excellent in heat resistance ( A-2) / (A-1) = 0.1 ~ 10 In particular, the mixture is used to be 0.5 ~ 5 to compensate for each disadvantage and improve the heat resistance while maintaining elastic performance.

As the polyether diol (A-1), polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or the like may be used, and the molecular weight is in the range of 1,000 to 3,000, particularly 1,500 to 2,500. Examples of the polycarbonate diols (A-2) include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butane diol, 1,3-butane diol, 1,5-petane diol, 1,6 hexane diol, Glycols alone or mixtures thereof, such as 1,4-cyclohexane diol, 1,4-cyclohexane dimethanol, 2,2-dimethyl-1,3 propane diol, and 1,8-octane diol, and diaryl carbonates and dialkyls By condensation reaction with carbonate, phosgene, etc., a diol having a molecular weight of 800 to 2,500 in particular 1,000 to 2,000 may be used.

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

In addition, the polyurethane elastic fiber is a class 3 hydroxyl group by the side chain at positions other than both ends by using 3 to 6 hydroxyl groups having 4 or more hydroxyl groups and 4 to 10 carbon atoms (B) having at least one tertiary hydroxyl group. By introducing a has a network structure by the urethane bond with the isocyanate to form a strong bond, thereby improving the heat resistance and elastic recovery ability, improve the viscosity safety of the polymer to maintain a suitable viscosity for spinning.

As the polyol (B) component having the tertiary hydroxyl group, 1,2,3-hydroxy-2-ethylpropane, 1,2,3-hydroxy-2-methylpropane, 1,2,4-hydroxy 2-methylbutane, 1,2,5-hydroxy-2-methylpentane, 1,3,5-hydroxy-2-methylpentane, 1,3,6-hydroxy-3-methylhexane, 1,2 Single or a mixture thereof, such as, 3,6-hydroxy-2,3-dimethylhexane, 1,2,4,6-hydroxy-2,4-dimethylhexane, is used.

The molar ratio of the long-chain diol (A) and the polyol (B) having a tertiary hydroxyl group is A / B = 5 ~ 50 in particular 10 ~ 40 is suitable, less than 5 is not dissolved well in the solvent there is a problem in spinning 50 In the above, the improvement degree, such as heat resistance and elastic recovery force, is insignificant.

Examples of the diisocyanate compound (C) which combines with an amine compound as a chain growth agent to serve as a hard segment include paraphenyl diisocyanate, metaphenylene diisocyanate, 2,4-torylene diisocyanate, and 2,6-torylene. Diisocyanate, 1-chlor-2,1-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,4-phenylene diisocyanate, chlorphenylene-2,4'-diisocyanate, methylenebis-4- Phenyl diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl diisocyanate, methylcyclo hexylene diisocyanate, paraphenyl diisocyanate, paraphenylene diisocyanate, 4,4'-diphenyl isopropylidine diisocyanate, 3,3 '-Dimethyl-4,4'-dipetyl diisocyanate, 3.3'-dimethoxy-4.4'-diphenylene diisocyanate, 4,4'-diphenylmethane diisocyane There are compounds in the tree, such as when considering the physical properties of the elastomer and reactive with the diol compound of 4,4'-diphenylmethane diisocyanate compound is best.

C / (A + B) = 1.25 to 2.5 mol is appropriate for the compound (A + B) in which the amount of the diisocyanate compound (C) is mixed with the long-chain diol (A) and the polyol (B) having a tertiary hydroxyl group. At 1.25 moles or less, the polymer is excellent in elongation but its strength is low and its elastic recovery ability is insufficient. When 2.5 moles or more is used, the strength and elastic recovery rate 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), polyol (B), and diisocyanate compound (C) is chain-grown by the diamine compound and chain-grown to 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, methyliminobispropyl amine, 2, 5- dimethyl piperazine, 1, 2- propylene diamine, 2, 3- butylene diamine, meta styrene diamine, and para styrene diamine , 2-methyl piperazine, ethylene diamine, ethanol diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 1-methyl-2,4-diamine benzene, 1,2-cyclohexane diamine, 1,3-cyclohexane Compounds such as diamine, 1,4-cyclohexane diamine, octamethylene diamine, paraphenylene diamine and the like are used, and the range of use thereof is 0.6 to 0.98 moles with respect to the prepolymer, and the characteristics required by the present invention are obtained when out of this range. I do not lose.

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

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

Examples of the monoamine-based compound (E) which is a chain stopper for blocking the ends of the chain-grown prepolymer are monoethanol amine, diethanol amine, propyl amine, isopropyl amine, diisopropyl amine, 2-ethylhexyl amine, and di (2). Compounds such as ethylhexyl) amine, butyl amine, and diethyl amine may be used, and the amount of the compound may be used in an amount of 1 to 30% (mol%) of the total amine, and at 1% or less, the chain stopping effect is poor. The viscosity increases sharply and the viscosity changes so much that the viscosity continues to rise, making it unsuitable for spinning, and at 30% or more, it prevents the chain growth of the polymer and does not grow into a polymer having an appropriate molecular weight. Physical strength, elongation and elastic recovery rate are poor.

Examples of solvents for improving radioactivity by controlling the solid content of the polymer include dimethylacetamide, dimethylformamide, hexamethylphosphoramide, dimethylnitrosoamine, dimethyl propionamide, methoxydimethylacetamide, N-methylpyrrolidine, and dimethyl sulfoxide. There are compounds such as seeds, tetramethylene sulfone, etc. Dimethylacetamide or dimethylformamide is advantageous in terms of compatibility with the polymer, radioactivity and solvent recovery. The amount of solvent used should be adjusted so that the solid content of polymer is 15-45%. If it is less than 15% or more than 45%, it will adversely affect radioactivity.

The polyurethane elastic yarn used in the present invention adds a dyeability improving additive (F) and a property deterioration preventing agent (G) represented by the following formula (1) to improve the dyeing function for acid dyes.

Wherein R is H or CH ₃ ,

R ¹ is-(CH ₂ ) _n-

n is an integer of 1 or more,

R ² and R ³ are the same or different groups and are an alkyl group having 1 to 10 carbon atoms.)

Examples of the dyeability improving additive (F) represented by the formula (1) include poly (dimethylaminoethyl methacrylate), poly (dimethylaminoethyl methacrylate), poly (diisopropylaminoethyl methacrylate), and poly (ter Tertiary nitrogen-containing polymethacrylate compounds such as sherry-butylmethylaminomethylmethacrylate) and poly {2- (di-normal-propylamino) -1-methylethylmethacrylate} are used.

However, when only the tertiary nitrogen-containing polymethacrylate compound is added, the physical properties are lowered, so in the present invention, poly (2) hydroxyethyl methacrylate) and poly (glycidyl methacrylate) are used as the physical property inhibitor (G). ), Poly (aryl methacrylate), poly (ethylene glycol dimethyl methacrylate), poly (triethylene glycol dimethacrylate), poly (tetraethylene glycol dimethacrylate), poly (methyl methacrylate), Compounds, such as poly (lauryl methacrylate), poly (oxyl methacrylate), and poly (decyl methacrylate), are added and used.

The proper amount of the dyeing-improving additive (F) is suitably 0.05 to 4% by weight relative to the polymer solids, but less than 0.05% by weight is insufficient dyeing effect, when exceeding 4% by weight inhibits the inherent physical properties of the elastomer It also adversely affects radioactivity. The property deterioration inhibitor (G) is preferably added in an amount of 1 to 3% by weight based on the polymer solid content, and when less than 1% by weight is used, the physical property is largely deteriorated, and when it is used in excess of 3% by weight, it is not economical.

In addition, a copolymer obtained by copolymerizing the tertiary nitrogen-containing methacrylate compound with a property deterioration inhibitor can be used in place of a dyeability improving additive and a property deterioration inhibitor, and in particular, dyeability and sunlight without deteriorating inherent physical properties and without inhibiting radioactivity. As a compound which improves fastness, the copolymer compound which consists of poly (dimethylamino ethyl methacrylate) and poly (lauryl methacrylate) is suitable.

40 denier polyurethane elastic yarns were prepared after spinning the polymer solution prepared by the above method using a conventional dry spinning method to measure various physical properties.

The present invention will be described in detail with reference to the following Examples.

Tensile strength, elongation and elastic recovery rate shown in the examples are in accordance with KSK 0219 and heat resistance after maintaining the elastic yarn in a hot air dryer at 130 ° C. for 60 minutes, strength retention rate and color change (Gray scale; water supply determination using ISO international standard) Evaluated as. The radioactivity is expressed as the number of trimmings. The number of yarns broken during spinning for a certain period of time was measured and this value was evaluated by averaging the number of trimmings in producing 1 billion meters of yarn. Dyeing property After refine | purifying 40 denier polyurethane fiber, it dyed for 60 minutes at 100 degreeC on condition of the following bath property, and evaluated the dyeing property and washing fastness (JIS L-0844, A-2 method).

C.I. Acid Red 6; 1% owf

New Born TS; 5% owf

pH; 3.5

Bath ratio; 1:50

Dyeing was evaluated based on the following criteria compared to the degree of dyeing of nylon fibers.

○: dyed to the same degree as nylon

△: dyed weaker than nylon

×: slightly dyed

Example 1

1 mol of polyhexamethylene carbonate diol having a molecular weight of 1,500 synthesized by condensation reaction of 1,6-hexanediol with diphenyl carbonate, 1 mol of polytetramethylene glycol having a molecular weight of 1,500, 1,3,5-hydroxy-3 0.2 mol of methylpentane was stirred at 80 ° C. under reduced pressure to remove moisture, and then 4.4 mol of 4,4′-diphenylmethane diisocyanate preheated at 50 ° C. was added, followed by polymerization at 90 ° C. for 60 minutes under nitrogen gas atmosphere. The polymer was prepared. The prepolymer was dissolved in dimethyl acetamide, the solution was cooled to 5 ° C., and then 1.1 mol of ethylene diamine, linear amine, 0.8 mol of 1,2-propylene diamine, and 0.1 mol of metaxylene diamine were used as cyclic amine. A chain growth agent solution in which 0.1 mol of 1,4-cyclohexane diamine was dissolved in dimethyl acetamide at a concentration of 15% was slowly added to the prepolymer to obtain a polymer having a viscosity of 3,500 poise.

A solution obtained by dissolving 0.2 mol of butyl amine in 15% concentration in dimethyl acetamide was slowly added to the polymer to obtain a polymer having a viscosity of 3,000 poises. A tertiary nitrogen-containing polydimethylaminoethyl methacrylate as a dyeability improving additive and a polylauryl methacrylate compound as a property deterioration inhibitor were added to the polymer so that 0.3% by weight and 2% by weight of the final polymer solids were respectively added to the dimethyl acetamide. After dissolution at 10% concentration, the solid content of the final polymer was adjusted to 32%, and the viscosity was 2,900 poise. This polymer was prepared by spinning a normal spinning method to prepare a polyurethane elastic yarn of 40 denier after spinning and 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 1,500 and 1.9 mol of polytetramethylene glycol having a molecular weight of 1,500 were used.

Comparative Example 2

The polymerization was performed in the same manner as in Example 1 except that 1,3,5-hydroxy-3-methylpentane having a tertiary hydroxyl group was not used.

Comparative Example 3

Among the chain-grown amines, the polymerization was carried out in the same manner as in Example 1 except for not using metacyclic diamine, which is a cyclic amine, and 1,4-cyclohexane diamine, and the results of the evaluation of the physical properties are shown in Table 1.

Comparative Example 4

Polymerization was carried out in the same manner as in Example 1 except that 0.02 mole of butyl amine as a chain stopper was used, and the results of the evaluation of the physical properties are shown in Table 1.

Comparative Example 5

Polymerization was carried out in the same manner as in Example 1 except that tertiary nitrogen-containing polydimethylaminoethyl methacrylate as a dye-improving additive and a polylauryl methacrylate compound as a property deterioration inhibitor were not used. same.

Comparative Example 6

Polymerization was carried out in the same manner as in Example 1 except that the polylauryl methacrylate compound, which is a property deterioration inhibitor, was evaluated.

Claims (4)

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 2,500 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 proportion, and then a diamine mixture (D) as a chain growth agent is added to the prepolymer. Dyeing enhancer (F) and property deterioration inhibitor represented by the following formula (1) after completion of the polymerization by adding 0.60 to 0.98 moles and adding the monoamine (E) as a chain stopper to 1 to 30 mole% of the total amine usage. (G) is a method for producing a polyurethane elastic fiber excellent in heat resistance and dyeing, characterized in that the addition of 0.05 to 4% by weight, 1 to 3% by weight relative to the final polymer solids. (Wherein R is H or CH ₃ , R ¹ is — (CH ₂ ) _n − n is an integer of 1 or more, and R ² , R ³ are the same or different groups and are alkyl groups having 1 to 10 carbon atoms.) The molar ratio of the polyether diol (A-1) and the polycarbonate diol (A-2) in the long chain diol (A); is (A-2) / (A-1) = 0.1 to 10. Polyurethane elastic, characterized in that the molar ratio of the long-chain diol (A) and the polyol (B) is A / B = 5 ~ 50, the molar ratio of NCO / OH is used in the range of C / (A + B) = 1.25 ~ 2.5 Method of making fibers. The molar ratio of linear diamine (D-1) to cyclic diamine (D-2) in the diamine compound (D) as a chain growth agent is (D-1) /) (D-2) = 2 to 2. Method for producing a polyurethane elastic fiber, characterized in that used in the range of 20. The physical property-lowering agent (G) according to claim 1, wherein the poly (2-hydroxyethyl methacrylate), poly (glycidyl methacrylate), poly (aryl methacrylate), poly (tetraethylene glycol dimethyl) Polyurethane elasticity characterized by adding compounds such as methacrylate), poly (methyl methacrylate), poly (lauryl methacrylate), poly (oxyl methacrylate), poly (decyl methacrylate), and the like. Method of making fibers.