KR100307214B1 - Melt-spinnable thermoplastic linear polyurethan-urea resin - Google Patents

Abstract

The present invention relates to a new polyurethane urea resin of the following general formula,

[AO- (O) C-NH-D-NH-C (O) -NH-D-NH-C (O) -O] _n

Wherein A represents a residue of an organic polyol having a number average molecular weight of 500 to 5000, a functional group number of 1.8 to 2.2, and a weight average molecular weight / number average molecular weight ratio (M _W / W _n ) of 1.5 to 2.5, and D is a functional group Number represents a residue of an aromatic organic diisocyanate of 1.8 to 2.2, and n represents a repeating unit.)

Polyurethane urea resin of the above structure has high heat resistance and high elasticity recovery can be produced by melt spinning and useful elastic fiber.

Description

Melt-spinnable thermoplastic linear polyurethan-urea resin

The present invention relates to a polyurethane-based elastic resin, and more particularly to a new melt-spun thermoplastic polyurethane urea resin having a high heat resistance and high elasticity recovery properties and a method for producing the same.

As a method for producing elastic fibers, dry spinning, wet spinning, chemical spinning, melt spinning and the like are widely known. Among them, the most widely used and the method that provides the best physical properties so far is dry spinning. Such dry spinning techniques are described, for example, in US Pat. No. 4,973,647 and US Pat. No. 5,362,432.

However, the conventional dry spinning is basically a device to remove the solvent by spinning the polyurethane-urea resin solution obtained by the solution polymerization method, the complex of the device, the solvent removed is high risk of environmental pollution such as water pollution or air pollution The large-scale equipment investment is essential because it is necessary to thoroughly prepare the auxiliary equipment to recover it, and thus the cost is very high compared to other fibers, so that the application of elastic fibers is very limited.

In addition, if the elastic fiber made by the dry spinning method is used in the areas of direct contact with the human body such as swimwear, sports clothing, lingerie, foundation, underwear, panties, stockings, socks, etc. May adversely affect the back.

In addition, the elastic fiber made by dry spinning is basically based on the urethane-urea bond, which is excellent in heat resistance and elastic recovery, but it is difficult to calculate the processing width because the shrinkage occurs during processing of the fabric, and the products made of such fabric are also washed. There is a disadvantage that the shrinkage occurs continuously afterwards, such as elasticity and wear is getting worse.

Wet spinning or chemical spinning has all of the problems inherent in dry, and in addition, it is difficult to control the process conditions, and the properties of the elastic yarn have a lot of deviations, so it is used only in part.

Therefore, the disadvantages of dry spinning, wet spinning, chemical spinning, etc., namely, large-scale equipment investment, solvent recovery, environmental pollution, high manufacturing cost, the effect of solvent residues on the human body, continuous shrinkage during processing and washing, and control of process conditions Many researches have been conducted on the method of manufacturing an elastic fiber that can solve the difficulties.

The basic research direction is the method of producing elastic fibers without using a solvent. The method is to use a melt spinning method of manufacturing elastic fibers by polymerizing a raw material by melt mass polymerization and spinning through an extruder.

However, since the resin that can be used for melt spinning must be melted by applying heat and spun through the spinning nozzle to produce elastic fibers, it should basically have thermoplastic properties. There is a basic prerequisite to be able to form a melt. Therefore, since the substrate of the resin that can be used in the melt spinning method can not contain a large amount of crosslinks as in dry spinning, wet spinning, chemical spinning, etc., there is a limit in increasing heat resistance.

In general, urethane hard segments have melting points at 190 ° C to 230 ° C, while urea hard segments have melting points in the range of 250 ° C to 290 ° C, which results in high heat resistance when urea bonds are present in polymer bonds. do.

However, aliphatic primary amines used to form urea bonds in dry spinning, etc., are too fast to react uniformly with organic isocyanates, so that they are difficult to react after being uniformly mixed. The method is not developed.

In this reaction, if the aliphatic primary amines are not uniformly mixed, the crosslinking reaction proceeds during the melt mass polymerization to form a crosslink, so that the polyurethane resin made of urethane-urea cannot obtain a constant melt in the extruder and thus cannot be used for melt spinning. do.

Recent studies related to this are described in Korean Patent Publication No. 97-705577. In order to control the reactivity, this study adopts a method of preparing prepolymer using organic isocyanate which is very responsive, lowering the temperature of prepolymer to low temperature, and reacting with aliphatic primary amine added with a melt aid.

However, since the polymer obtained by this method does not contain aromatic benzene rings in the hard segment, it is not as heat resistant as conventional dry products, and since the organic isocyanate used is much more expensive than the aromatic organic diisocyanate used in conventional dry spinning, it is practically practical. It may be difficult to commercialize.

Until now, since the substrate of a resin mainly used for melt spinning has a urethane bond as a substrate, since the hydrogen bonding force is lower than that of a resin based on a urethane-urea bond as in dry spinning, wet spinning, and chemical spinning, heat resistance is inferior. It is embraced.

If the hydrogen bonding force is weak, especially physical properties are poor in heat resistance and elastic recovery, etc., thus losing the value as an elastic fiber. For this reason, melt spinning is not widely used as a method for producing elastic fibers.

Recently, however, these problems have been solved by the development of polymerization technology and melt spinning technology of thermoplastic polyurethane resin. The research directions are divided into two categories. The first is a method of preparing a melt spinning resin using a material having high heat resistance and high elasticity in the polymerization step, and the second is allopa by adding a crosslinking agent in the form of a prepolymer in the spinning step. It is divided into the method of inducing crosslinking through a nate bond.

First of all, the technology that has been excellent in the properties of elastic fibers among the known polymerization-related technologies is to specifically select the composition and molecular weight of the polyol, which is a soft segment, among the raw materials constituting the polyurethane resin. The composition and the molecular weight are defined as follows, and it is a technique which has high elastic recovery and high heat resistance.

Examples of prior patent documents in which such technology is published include US Patent No. 5,290,905, US Patent No. 5,310,852, Korean Patent Publication No. 90-18430, Korean Patent Publication No. 91-16808, and Korean Patent Publication No. 93-901645. .

In these studies, polyols have a method of increasing the molecular weight of the polyols to induce crystallization of the polyols, thereby improving elasticity recovery and improving heat resistance.

Alternatively, a method of spinning-crosslinking by adding a crosslinking agent when melt spinning a thermoplastic polyurethane elastomer produced in a specially designed reactor is described in US Pat. No. 5,391,682 and Korean Publication No. 94-701414. In the above study, a prepolymer method is used to prepare a thermoplastic polyurethane resin. That is, the prepolymer is first prepared in a reaction vessel using a porous plate, the prepolymer and the chain coupling agent thus prepared are mixed in a high speed mixer, and then introduced into a twin screw extruder to have an average residence time of about 6 minutes. And the highest polymerization temperature is set at 250 ° C to 260 ° C to produce a resin. According to this method, it is introduced that a polyurethane elastomer having a high molecular weight and a small molecular weight distribution is small can be produced. In addition, it introduces a method for producing elastic fibers by cross-linking spinning the thermoplastic polyurethane resin thus made in a spinning machine connected to a static mixer (static kneading device) to the prepolymer at the end of the extruder.

However, the thermoplastic polyurethane resin prepared in this way takes a long time of 2 hours to prepare the prepolymer, and when the reaction temperature is maintained at a high temperature of 250 ° C. to 260 ° C. for about 6 minutes in the twin screw extruder, the thermoplastic polyurethane resin is yellowed. In some cases, side reactions proceed to inevitably generate gel-like particles (small granules, fisheye). As pointed out in this study, the gel-like particles increase the gear pack pressure on the spinning filter during spinning, and the gel-like particles exiting the nozzle do not stretch when the elastic fibers are wound around the bobbin, causing single yarns, making continuous production impossible. In this study, various reaction conditions are proposed to reduce gel particles, but the gel particles cannot be completely removed. In the radial crosslinking method using a static mixer, the thermoplastic polyurethane resin is first melted in an extruder, and a prepolymer is added in a static mixer to perform the crosslinking reaction, and the effect is best when the prepolymer is added by 15% by weight.

However, the techniques studied so far related to melt spinning, that is, the first method of optimizing the crystallinity of the polyol to maximize the phase separation of the hard and soft segments to improve the heat resistance of the polymer, and the second prepolymer as a crosslinking agent. A method of increasing the heat resistance by inducing allophanate crosslinking during spinning was developed. However, the elastic fiber obtained by melt spinning the polyurethane elastomer prepared by the conventional method is an elastic fiber obtained by dry spinning, wet spinning, and the like. Such high heat resistance or high elasticity recovery is not achieved.

The inventors have considered the advantages and disadvantages of various aspects of elastic fibers with polyurethane substrates. Ultimately, the study was conducted to remove the fundamentally limited elements and to remove all the problems that may arise from the search for the direction in which the elastic fiber should go.

The first limiting factor considered is the absence of solvents. The use of solvents is accompanied by the problems of environmental pollution such as water pollution and air pollution, and in order to resolve this, a lot of equipment investment and solvent recovery costs are added to increase the cost of the elastic fibers and remain in the elastic fibers. Since there is always a possibility that a solvent can have a bad effect on the human body, solution polymerization using a solvent should not be used in the future, so dry radiation, wet spinning, and chemical spinning were excluded.

The second constrained factor is to innovate the cost of elastic fibers to make them more common. In the future, the shape of our garments will be more comfortable for us. In order for the most suitable elastic fiber fabric to be used more easily, the cost of elastic fiber must be greatly reduced at the current level.

A third constrained factor is the need to be able to produce elastic fibers with a small investment. Conventional dry spinning, wet spinning, and chemical spinning are difficult to achieve by spinning completely in time and space, so large investments are premised.

Although the melt spinning method was considered for the three major reasons mentioned above, the elastic fibers produced by the melt spinning methods studied so far could solve the above problems, but could not satisfy all the physical properties that the elastic fibers should have. The growth rate is also not high.

Accordingly, the present invention is to provide a novel melt-spun thermoplastic polyurethane urea resin capable of producing elastic fibers having high heat resistance and high elastic recovery by melt spinning.

In the present inventor's research for solving the above problems, it was found that the polyurethaneurea resin having a hard segment having a specific structure in the molecular chain has surprising properties as desired, thereby completing the present invention.

The present invention therefore provides a new polyurethaneurea resin of formula 1:

[Formula 1]

[AO- (O) C-NH-D-NH-C (O) -NH-D-NH-C (O) -O] _n

In Formula 1, A represents a residue of an organic polyol having a number average molecular weight of 500 to 5000, a functional group number of 1.8 to 2.2 and a weight average molecular weight / number average molecular weight ratio (M _W / W _n ) of 1.5 to 2.5, and D is Representative moieties of aromatic organic diisocyanate having a functional group number of 1.8 to 2.2 are represented, and n represents a repeating unit.

In addition, the method for preparing a polyurethaneurea resin having the structure of Formula 1 according to the present invention includes the following steps:

(a) an organic polyol having a number average molecular weight of 500 to 5000, a functional group number of 1.8 to 2.2, a weight average molecular weight / number average molecular weight ratio (M _W / W _n ) of 1.5 to 2.5, and an excess aromatic organic group having a functional group number of 1.8 to 2.2 Reacting diisocyanate to prepare a prepolymer having an isocyanate group at the sock end,

(b) Amination of a part of the isocyanate groups of the prepolymer.

(c) reacting the aminated prepolymer two molecules to produce urea functionality, and

(d) polymerizing the product in which the urea functional group is formed.

Hereinafter, the present invention will be described in more detail.

The polyurethaneurea resin according to the present invention has a repeating unit of formula (1). The main characteristic of the repeating unit of Formula 1 is that two molecules of aromatic organic diisocyanate are connected by urea bond, and aromatic organic diisocyanate and organic polyol are connected by urethane bond.

The residue D of the aromatic organic diisocyanate in the formula (1) is a residue derived from at least one member selected from the group consisting of aromatic, aromatic aliphatic, cycloaliphatic and aliphatic diisocyanates having a functional group of 1.8 to 2.2. The preferable molecular weight of such aromatic organic diisocyanate is 500 or less. Although not particularly limited, representative examples of the aromatic organic diisocyanate include 4,4'-diphenylethane diisocyanate, P-phenylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanane, 4,4'-dicyclo Hexyl methane diisocyanate, isophorone diisocyanate, and the like.

Residue A of the organic polyol in formula (I) has a number average molecular weight of 500 to 5000, more preferably 1,000 to 2,000, the number of functional groups of 1.8 to 2.2, the weight average molecular weight / number average molecular weight ratio (M _W / M _n ) is 1.5 to 2.5, More preferably, it is a residue derived from at least one member selected from the group consisting of aliphatic polyester polyols, aliphatic polyester polyols, aliphatic polycaprolactone polyols, aliphatic carbonate polyols and aliphatic siloxane polyols which are 1.8 to 2.2. Although not particularly limited, representative examples of the organic polyol include polyether polyols such as polytetramethylene ether glycol, polypropylene glycol, and polyethylene propylene glycol, polybutylene adipate, polyethylene adipate, polyethylene butylene adipate, and polyhex. Polyester polyols such as silane adipate, polybutylene hexylene adipate and poly-3-methyl-pentylene adipate; Polycaprolactone polyols, hexamethylenecarbonate polyols, dimethylsiloxane polyols, and the like.

In the polyurethaneurea resin of Formula 1, the soft segment is A, and the hard segment is -O- (O) C-NH-D-NH-C (O) -NH-D-NH-C (O) -O.

On the other hand, it has a structure of formula (2) showing the structure of the hard segment of the conventional dry, wet spinning elastic resin, and the structure of formula (3) showing the structure of the hard segment of the conventional melt spinning elastic resin.

[Formula 2]

-O- (O) C-NH-D-NH-C (O) -NH-R ₁ -NH-C (O) -NH-D-NH-C (O) -O

In the formula, R ₁ represents an aliphatic chain structure.

[Formula 3]

-O- (O) C-NH-D-NH-C (O) -OR ₂ -OC (O) -NH-D-NH-C (O) -O

In the formula, R ₂ represents an aliphatic chain structure.

Conventional dry spinning and wet spinning elastomeric resins having hard segments of formula (2) are synthesized using aliphatic diamines as chain extenders, resulting in the formation of two urea bonds between two organic isocyanate molecules. Existing melt-spun elastomeric resins have aliphatic diols or aromatic diols as chain extenders, so that two urethane bonds are formed between two organic isocyanate molecules.

In contrast to the structures of Formulas 1, 2 and 3, the structure of the hard segment of the present invention is significantly different from the structure of the hard segment of the conventional compound in that only one urea bond is generated between two aromatic organic isocyanate residues. It can be seen.

Since the hard segment structure of the elastic resin of the present invention is aromatic benzene ring is connected by a direct urea bond, it has a structural feature that is much better packing than the conventional hard segments of Formulas 2 and 3 can exhibit high heat resistance and high elastic recovery .

Hereinafter, a method for producing the polyurethaneurea resin of the present invention will be described.

As described above, the present production method is largely composed of a prepolymer production reaction step (a), an amination reaction step (b), a urea functional group production reaction step (c), and a polymer production reaction step (d).

Prepolymer production reaction step (a) can be carried out in a discontinuous or continuous reaction process.

As an example of the discontinuous method, an organic polyol and an aromatic organic diisocyanate are added in an equivalent ratio to a reactor equipped with a stirrer and a thermostat, and the reactor temperature is 80 to 120 캜, preferably 90 to 100 캜. The prepolymer may be prepared by reacting for 3 hours to 3 hours.

As an example of a continuous method, a reactor equipped with a device capable of continuously metering and supplying a multi-tube type reactant homogeneously mixed with an organic polyol and an aromatic organic diisocyanate using a fin-type mixing head. The prepolymer can be continuously obtained by passing through a static mixer (stop kneading element). The residence time of the static mixer is suitably set to 2 to 30 minutes, preferably 5 to 10 minutes.

In the prepolymer production reaction step (a), the organic polyol and the aromatic organic diisocyanate are preferably added at an equivalent ratio as shown in Equation 1 below and reacted.

[Equation 1]

1.5 ≤ organic diisocyanate equivalent / organic polyol equivalent ≤ 2.5

The range of the organic diisocyanate / organic polyol equivalent ratio is a range that can exhibit physical properties as an elastic fiber, the hardness is in the range of 65A to 85A in Shore hardness and the elongation can be from 550% to 900%. If the equivalent ratio is less than 1.5, the elongation is good, but the heat resistance is insufficient. If the equivalent ratio is more than 2.5, the polymer is heat resistant but the elongation is insufficient. The optimum equivalence ratio may vary slightly depending on the molecular weight of the aromatic organic diisocyanate and organic polyol used.

The prepolymer thus formed forms a polymer through a series of amine formation reactions and urea binding reactions by adding H ₂ O. H ₂ O in the amine forming reaction step (b), it is preferable to use pure water or distilled water free of impurities. However, if you want to specifically control the physical properties may be used by mixing a separate chain extender. The chain extender which can be used in this case is a diol having a molecular weight of 400 or less containing 1.8 to 2.2 hydroxy functional groups, and such chain extenders have a tendency to decrease heat resistance and elasticity recovery as compared with H ₂ O alone. Seems. Representative examples of such diol-based chain extenders include ethylene glycol, 1,4-butanediol, propylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and the like.

In the step (b), the prepolymer and H ₂ O are preferably reacted by adding in an equivalent ratio as shown in Equation 2 below.

[Equation 2]

1.8 ≤ NCO equivalent / H ₂ O equivalent of the prepolymer ≤ 2.2

When the ratio of NCO equivalent to H ₂ O equivalent of the prepolymer is less than 1.8, the equivalent amount of amine produced is greater than the remaining NCO equivalent, so that the high molecular weight cannot obtain a polymer. More than the equivalent of the cross-linking caused by the biuret bond is generated a lot, the thermoplastic properties are lost. When the ratio of NCO equivalent to H ₂ O equivalent of the prepolymer is 2.0, the most linear and high molecular weight polymer can be obtained.

As a method of making a polymer, a predetermined amount of H ₂ O is added to the prepolymer and stirred, and the stirring is continued until the CO ₂ generated when stirring is turned off and settles. When bubbles are removed and the viscosity of the reactant rises, the reactant is transferred to a tray and put into a hot air oven to mature and complete the reaction. At this time, the temperature of the hot air oven is preferably from 120 ° C to 150 ° C. Hot air is preferable to using heated nitrogen than to use oxygen-containing air. If air is used, yellowing is likely to occur during aging. The matured plate-like polymer is put into a pulverizer and flakes are extruded and extruded using an extruder.

For the purpose of understanding the method, the synthetic reaction mechanism of the polyurethaneurea of the present invention will be described using an aromatic organic diisocyanate having 2 functional groups and a polyol having 2 functional groups as an example.

(a) prepolymer production reaction

2 ONC-D-NCO + HO-A-OH → ONC-D-NHC (O) O-A-O (O) CNH-D-CNO

Diisocyanate Polyol Prepolymer

(b) amination reaction

ONC-D-NHC (O) 0-AO (O) CNH-D-CNO + H ₂ O → ONC-D-NHC (O) OAO (O) CNH-D-NHC0OH

¡Æ onc-d-nhc (O) OAO (O) CNH-D-NH ₂ + CO ₂ (↑) (c) urea functional group reaction

2 ONC-D-NH-C (O) -OAO- (O) -C-NH-D-NH ₂ →

ONC-D-NH-C (O) -OAO- (O) -C-NH-D-NH-C (O) -NH-D-NH-C (O) -OAO- (O) C-NH- D-NH ₂

(d) polymer formation reaction

n / 2 ONC-D-NH-C (O) -OAO- (O) C-NH-D-NH-C (O) -NH-D-NH-C (O) -OAO (O) CNH-D -NH ₂ → [AO- (O) C-NH-D-NH-C (O) -NH-D-NH-C (O) -O] _n

Referring to the reaction mechanism, a bifunctional organic isocyanate and a bifunctional polyol are reacted in a molar ratio of 2: 1 to prepare a prepolymer, and 1.0 equivalent of water is reacted with 2.0 equivalents of NCO of the prepolymer. After converting one end of the prepolymer into an amine functional group, and then reacting the two molecules of the aminated prepolymer, one molecule of the amine functional group reacts with the isocyanate functional group of another molecule to form a urea bond between two organic isocyanate residues. And a high molecular weight linear urethane urea resin is synthesized which is linearly polymerized to exhibit high heat resistance and high elastic recovery.

Polyurethane urea resin produced by the production method of the present invention is melt index (MI) 5-30g / 10min, softening point 140-160 ℃, tensile strength 280-400㎏ / cm 3, elongation 600-800%, 300% instantaneous recovery rate 92-94%, 500% Instantaneous recovery 91-93%.

The above properties are measured by the following method.

※ Melt index (MI): The sample is dried for 5 hours at 120 ℃ in a vacuum oven, and then put into a MI measuring instrument under a load of 5000g at 260 ℃.

※ Softening point: Cut the specimens as below in width x length = 10mm x 10mm and put them in the softening point measuring device. The softening point is set at the temperature when the needle is 1 mm deep by applying a load of 1000 g to the needle and raising the temperature.

※ Tensile strength, elongation, 300% instantaneous recovery rate and 500% instantaneous recovery rate: The specimen prepared by the same method as used in the softening point measurement is cut with an ASTM D412 die and measured using a universal testing machine (UTM). At this time, the specimen was manufactured by hot press. Previously, the manufacturing method of the specimen by hot press was inferior and it was not suitable for the measurement of the physical property, but now it is possible to make a very good specimen using Teflon coated woven fabric. The fabrication of specimens using hot presses is currently convenient because they can produce specimens with short production times and small amounts of samples. In the description of the fabrication, the temperature of the heating plate is set to 220 ° C to 240 ° C in a hot press facility designed for both heating and cooling, and 180 g of the sample is weighed on a balance. The specimen fabrication plate consists of three layers, with the iron plate at the bottom and the Teflon sheet hanging over it. Next, after placing the specimen frame of width x length x height = 250 mm x 250 mm x 2 mm, 180 g of the sample weighed in advance is poured into the mold and flattened. Finally, cover the iron plate wrapped with Teflon sheet like a lid and slide it between the hot plates of the hot press. Next, press for 1 minute at 10 Ton pressure and 2 minutes at 30 Ton pressure. Next, the plate is transferred to a cooling plate and cooled again by applying a pressure of 30 Ton for 2 minutes. Open the specimen lid and remove it in order to obtain a specimen of approximately 2.1 mm and weighs around 160 g. The specimen thus prepared is aged at 120 ° C. for 12 hours to measure physical properties.

Since the polymer made in the present invention has a thermoplastic characteristic, it can be molded by an extruder. The components constituting the extrudability are firstly whether the resin is constantly fed. The reason why the feeding is good evenly is that the resin has excellent thermoplasticization characteristics and can guarantee a uniform melt state and a uniform discharge amount. This evaluation can be evaluated by graphically showing the degree of change in the Tq of the extruder over time. Actually, the thermoplastic polyurethane urea resin prepared in the present invention was evaluated by extrusion molding using a Brabender Plasticoder (Plasticoder), RPM 50, barrel temperature (℃) 230-250- At 260-240 conditions, Tq was extruded uniformly, taking 35 to 40 degrees. In addition, the appearance of the extrudate on the rod extruded through the die, the surface was clear without the gel in the extrudate.

The features and other advantages of the present invention as described above will become more apparent from the following examples. It should be understood, however, that the present invention is not limited to the following examples.

Example 1

As the organic polyol, polybutylene hexylene adipate (PBHA, molecular weight 1,000) was dried in a vacuum oven at 120 ° C. for 5 hours to prepare a water content of 150 ppm or less, and prepare as a starting material for a prepolymer reaction. As aromatic organic diisocyanate, 4,4'- diphenylmethane diisocyanate (MDI) is prepared by oven-melting at 45 degreeC.

A round-bottomed cylindrical reactor equipped with a stirrer capable of adjusting the rotation speed is installed in an oil bath maintaining the temperature at 90 ° C., and the prepared diisocyanate and polyol are equivalent ratio (diisocyanate equivalent: polyol). Equivalent) 1.80: 1.00 was metered in and stirred at 1,000 rpm for 5 minutes or more to prepare a prepolymer. At this time, 10-100 ppm of T-10, which is an organotin catalyst, was used. The reaction progress of the prepolymer can be seen by the change in the current applied to the stirrer motor, most of which reaches a maximum in about 2 minutes.

After preparing the prepolymer, H ₂ O was added at an equivalence ratio of 0.80 to prepare an amine function in the prepolymer, followed by stirring. As the CO ₂ gas was generated along with the heat of reaction, the stirrer was continuously turned to remove bubbles, and the viscosity of the polymer rapidly increased. When the polymer began to be wound on the stirrer, the polymer was taken out on a tray on which release paper was laid, and then flattened. The polymer was put into a hot air oven and aged at 120 ° C. for at least 5 hours. As described above, the matured polymer was prepared by using a hot press to measure the physical properties. The measurement results are shown in Table 1 below.

Example 2

The same procedure as in Example 1 was repeated except that the equivalent ratio of MDI / PBHA-1500 / H ₂ O was 2.00 / 1.00 / 1.00. Physical properties of the obtained polymer are shown in Table 1 below.

Example 3

The same procedure as in Example 1 was repeated except that polytetramethylene ether glycol (PTMG, molecular weight 1000) was used as the polyol, and the equivalent ratio of MDI / PTMG-1000 / H ₂ O was set to 1.80 / 1.0 / 0.80. Physical properties of the obtained polymer are shown in Table 1 below.

Example 4

The same procedure as in Example 3 was repeated except that polytetramethylene ether glycol (PTMG, molecular weight 1500) was used as the polyol, and the equivalent ratio of MDI / PTMG-1500 / H ₂ O was set to 2.00 / 1.00 / 1.00. Physical properties of the obtained polymer are shown in Table 1 below.

Comparative Example 1

Butanediol (BD) was added in an equivalent ratio of 0.80 as a chain extender, and then stirred in a prepolymer prepared in the same manner as in Example 1. When the polymer began to be wound on the stirrer, the polymer was taken out on a tray on which release paper was laid, and then flattened. The polymer was put into a hot air oven and aged at 120 ° C. for at least 5 hours. As described above, the matured polymer was prepared by using a hot press to measure the physical properties. The measurement results are shown in Table 1 below.

Comparative Example 2

The same procedure as in Comparative Example 1 was repeated except that the equivalent ratio of MDI / PBHA-1500 / BD was 2.00 / 1.00 / 1.00. Physical properties of the obtained polymer are shown in Table 1 below.

Comparative Example 3

The same procedure as in Comparative Example 1 was repeated except that polytetramethylene ether glycol (PTMG, molecular weight 1000) was used as the polyol, and the equivalent ratio of MDI / PTMG-1000 / BD was 1.80 / 1.0 / 0.80. Physical properties of the obtained polymer are shown in Table 1 below.

[Comparative Example 4]

The same procedure as in Comparative Example 1 was repeated except that polytetramethylene ether glycol (PTMG, molecular weight 1500) was used as the polyol, and the equivalent ratio of MDI / PTMG-1500 / BD was 2.00 / 1.00 / 1.00. Physical properties of the obtained polymer are shown in Table 1 below.

As can be seen from Table 1, according to Examples 1 to 4 according to the present invention is a polyurethane urea resin showing a much higher heat resistance and elastic recovery than the elastic resin of Comparative Examples 1 to 4 prepared by a conventional method It is possible to manufacture, the polyurethaneurea resin of this property can be melt-spun to produce useful fibers.

Claims (9)

Melt spinning thermoplastic linear polyurethane urea resin having the formula [AO- (O) C-NH-D-NH-C (O) -NH-D-NH-C (O) -O] _n (1) Wherein A represents a residue of an organic polyol having a number average molecular weight of 500 to 5000, a functional group of 1.8 to 2.2, and a weight average molecular weight / number average molecular weight (M _W / W _n ) of 1.5 to 2.5, and D represents a functional group of 1.8 to The residue of aromatic organic diisocyanate which is 2.2 is represented, n represents a repeating unit. The molten spinning thermoplastic linear polyurethaneurea resin according to claim 1, wherein the aromatic organic diisocyanate has a molecular weight of 500 or less. According to claim 1, The residue (A) of the organic polyol is an aliphatic poly having a number average molecular weight of 500 to 5000, a functional group number of 1.8 to 2.2 and a weight average molecular weight / number average molecular weight (M _W / W _n ) of 1.5 to 2.5 A melt-spun thermoplastic linear polyurethaneurea resin, characterized in that the residue is derived from at least one member selected from the group consisting of ester polyols, aliphatic polyether polyols, aliphatic polycaprolactone polyols, aliphatic carbonate polyols, and aliphatic siloxane polyols. The residue (A) of claim 3, wherein the residue (A) of the organic polyol is a residue derived from an organic polyol having a number average molecular weight of 1,000 to 2,000 and a weight average molecular weight / number average molecular weight (M _W / W _n ) of 1.8 to 2.2. Melt-spinning thermoplastic linear polyurethaneurea resin. Method for producing a melt-spun thermoplastic linear polyurethane urea resin of the formula (1) comprising the following steps (a) to (d): (a) number average molecular weight of 500 to 5000, functional groups number of 1.8 to 2.2 and weight average molecular weight / An organic polyol having a number average molecular weight (M _W / W _n ) of 1.5 to 2.5 and an excess of an aromatic organic diisocyanate having a functional group of 1.8 to 2.2 are reacted at a ratio of 1.5 to 2.5 in an aromatic organic diisocyanate / organic polyol equivalent ratio. A process for preparing a prepolymer having an isocyanate group, (b) Amination of a part of the isocyanate group formed at the sock end of the polymer, (c) Reaction of the amine group of the prepolymer with the residual isocyanate group of the prepolymer to form a urea functional group Obtaining a product in which the two prepolymers are combined, and (d) linearly polymerizing the product of step (c). The method of claim 5, wherein the prepolymer and H ₂ O in the step (b) of the NCO / H ₂ O equivalent ratio of the prepolymer of the molten spinning thermoplastic linear polyurethane urea resin, characterized in that Manufacturing method The method of claim 5, wherein the aromatic organic diisocyanate is at least one member selected from the group consisting of aromatic, aromatic aliphatic, cycloaliphatic and aliphatic diisocyanates having a molecular weight of 500 or less. Manufacturing method The aliphatic polyester polyol according to claim 5, wherein the organic polyol has a number average molecular weight of 500 to 5,000, a functional group number of 1.8 to 2.2, and a weight average molecular weight / number average molecular weight ratio (M _W / M _n ) of 1.5 to 2.5. A method for producing a molten spinning thermoplastic linear polyurethane urea resin, characterized in that at least one selected from the group consisting of polyether polyols, aliphatic polycaprolactone polyols, aliphatic carbonate polyols, and aliphatic siloxane polyols. The melt-spun thermoplastic linear polyurethane urea according to claim 5, wherein the number average molecular weight of the organic polyol is 1,000 to 2,000, and the weight average molecular weight / number average molecular weight ratio (M _W / M _n ) is 1.8 to 2.2. Method for producing a resin.