JPH083261A - Method for reaction-molding polyurethane urea - Google Patents

Abstract

PURPOSE:To prepare a polyurethane elastomer which has excellent mechanical properties and can be molded simultaneously with a reaction in a continuous manner without use of any polymn. catalyst by feeding a compsn., prepd. by reacting an asymmetric diamine with a carbonyl-contg. compd., and a prepolymer having an isocyanate at its both end into a mixing equipment and discharging the resultant product from the equipment in a continuous manner. CONSTITUTION:A compsn. (A) prepd. by reacting an asymmetric diamine compd. (A1) represented by formula I (wherein R<1> and R<2> are each H or a 1-5C aliph. hydrocarbon residue; and X is a direct bond or a 1-6C aliph. hydrocarbon residue) with a ketone compd. and/or an aldehyde compd. (A2) represented by formula II (wherein R<3> and R<4> are each H or a 1-10C hydrocarbon residue) in a molar ratio of (1:1) to (1:10), and a composition comprising, 40 to 95mol% compd. represented by formula III (wherein the meanings of the abbreviations are as defined above in connection with the formulae I and II), based on the component A1, and 100mol% water is mixed with a bi- or higher functional isocyanate-terminal prepolymer (B) in such a manner that the amt. of the isocyanate group is 0.8 to 1.5 times, by equivalent, the stoichiometric amount. The reaction temp. within the mixing equipment is 50 to 80 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for reaction-molding a polyurethane urea elastic body having excellent properties without using a solvent. Further, the present invention relates to a novel method capable of molding a polyurethaneurea elastic body which is conventionally insoluble in a solvent, since no solvent is used.

[0002]

2. Description of the Related Art Generally, a polyurethaneurea elastic body is prepared by synthesizing a prepolymer having isocyanate at both ends from a polymer diol and a diisocyanate in a solvent such as dimethylacetamide, and then linking the prepolymer with a diamine compound to increase the molecular weight. Is obtained by

The main reasons why a solvent is necessary are as follows. One is that the polyurethaneurea elastic body does not exhibit thermoplasticity, and therefore must be molded from a polymer solution by a method such as dry spinning or wet spinning. Secondly, a reaction between a prepolymer and a diamine compound. Is very fast and only heterogeneous polymers can be obtained without solvent.

In the production method using a solvent, a step of removing and recovering the solvent is indispensable, and therefore the step is complicated, consumes a large amount of energy, and may lead to a problem of environmental pollution. It has been known for a long time that the reaction with isocyanate groups in a prepolymer can be delayed by capping an amine compound with a ketone, as has been known for a long time as described in JP-A-47-34305. There are examples of the use of such ketone caps in the field of lacquering.

JP-A-60-161417 discloses a moisture-curable composition comprising a ketoimine compound which is a reaction product of an amine and a ketone and an isocyanate group-containing compound, which is long in the absence of water. It has a pot life, absorbs water by coating, and forms a cured film, but in this case, it contains a solvent. Further, JP-A-53-24396 discloses a method in which the reaction of the ketoimine compound and the isocyanate group is controlled at a rate suitable for coating by actively adding water.

By using a specific ketoimine compound, which is a reaction product of ethylenediamine and acetone, and adding a polymer diol to the ketoimine compound, the viscosity of the prepolymer having an isocyanate group can be approximated to facilitate mixing of the two. A method of continuously forming a thick filament or the like without using a solvent has been proposed (see JP-A-63-154719 and JP-A-1-210416). Japanese Patent Application No. Hei 5-167309 filed by the present applicant
JP-A No. 2004-242242 proposes a method for molding a polyurethane elastic body having fine filaments having good physical properties by using an aliphatic asymmetric diamine such as propylenediamine instead of ethylenediamine.

[0007]

In a solventless molding method using a ketoimine compound consisting of ethylenediamine and acetone, a polyurethane urea elastic yarn can be obtained, but it is limited to a thick filament. In fact, the homogeneity of polymerization was not yet sufficient to obtain thin filaments for clothing applications, and the mechanical properties of the obtained thick filaments were somewhat insufficient.

The method using an asymmetric diamine also uses an acid to regenerate the ketoimine, which results in a relatively high regeneration rate. As a result, mixing unevenness occurs when the ketoimine composition and the terminal isocyanate prepolymer are mixed. Occurs, and the physical properties of the obtained thin filaments fluctuate. Further, the method disclosed in Japanese Patent Laid-Open No. 53-24396 is applied to coating, but the method was applied to the production of elastic yarn, but the uniformity of polymerization for obtaining thin filaments is still insufficient. However, the amine compound in the present invention is actually an alicyclic diamine, and with these compounds, it is difficult to obtain a polyurethane urea elastic yarn having physical properties that can be put to practical use. is there.

As described above, a certain quality has been achieved so far.
That is, there has been no known method having excellent polymerization uniformity enough to obtain a polyurethane urea elastic body having fine filaments with few physical property irregularities. That is, it is an object of the present invention to provide a method of continuously polymerizing an elastic body having higher physical properties and higher homogeneity as compared with the conventional method and continuously molding without using a solvent.

[0010]

Means for Solving the Problems As a result of studies on various amine compounds, the present inventors selected and used an amine compound having a specific structure, and reacted a reaction mixture of the amine compound and a ketone compound with an isocyanate group. In, solvent-free, having an optimum speed for carrying out continuous polymerization molding, and the reaction has less side reactions than conventional ones, and the obtained polyuretaurea has very little fluctuation in physical properties and is very good. The present invention has been achieved by finding that it is a thing.

That is, in the present invention, the asymmetric diamine compound represented by the following structural formula (1) and the ketone compound and / or the aldehyde compound represented by the following structural formula (2) are used in a molar ratio of 1/1 to 1/10. A composition obtained by reacting at a ratio of (I) to the charged asymmetric diamine compound,
40 mol% or more and 95 mol% or less of the compound represented by the following structural formula (3), 100 mol% or less of H ₂ O,
The present invention relates to a method for reaction-molding polyurethaneurea, which comprises continuously supplying and discharging a contained composition and a bifunctional or higher functional terminal isocyanate prepolymer to a mixing device.

[0012]

[Chemical 6]

[0013]

[Chemical 7]

[0014]

Embedded image

Further, in that case, the composition containing the compound (II), which is further reacted with phenylisocyanate to obtain a compound represented by the following structural formula (4),
And a method for reaction-molding polyurethaneurea, which is a composition having the ability to generate a compound represented by the following structural formula (5) in an amount of 95 mol% or more based on the charged asymmetric diamine compound.

[0016]

[Chemical 9]

[0017]

[Chemical 10] Hereinafter, the present invention will be described in detail.

The amine compound used in the present invention is

[Chemical 11] It is an asymmetric diamine compound represented by.

Specific compounds include 1,2-propylenediamine, 1,3-butylenediamine, 1,2-butylenediamine, 1,4-pentenediamine, 1,5-hexenediamine, and isobutylenediamine. . From the viewpoint of the polymerization reaction rate and the mechanical properties of the obtained elastic body, a 1,2-diamine compound is preferable, and a specific compound is 1,2-propylenediamine.

Next, the ketone compound and / or aldehyde compound used in the present invention

[Chemical 12] Is a carbonyl-containing compound represented by.

Specific examples include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetophenone, penzophenone, acetaldehyde, butyraldehyde, benzaldehyde and the like. Aliphatic ketones are preferable, and specific examples of preferable compounds include acetone, methyl ethyl ketone, methyl butyl ketone, and methyl isobutyl ketone.

Next, the reaction composition comprising the asymmetric diamine compound and the carbonyl-containing compound will be described.
In the reaction composition of the present invention, the compound represented by the following structural formula (3) is added to the diamine compound used.
The content of H ₂ O is 100 mol% or less.

[0023]

[Chemical 13] The content of this compound in the composition is important for controlling the reaction rate with the isocyanate group, and needs to be within the above range.

A content of 40 mol% or less means that the amount of unreacted asymmetric diamine or ketoimine is large, and when the amount of unreacted diamine is large, the reaction becomes too fast and only a non-uniform polymer is obtained. On the other hand, if the number of ketoimine groups is too large, the reaction becomes too slow, which is not preferable, and if an acid is added to intentionally accelerate the reaction, the phenomenon that the mechanical characteristics of the reaction molded product deteriorates is not preferable.

There is no particular problem if the amount of dicarbinol represented by the structural formula (3) is too large, but since the compound is an equilibrium reaction, it is impossible to generate 100 mol%, and IR and IR The upper limit of the present invention was defined as 95 mol% of the upper limit production amount based on the analysis result of NMR. To obtain a molded product continuously at a more suitable reaction rate, 60 mol% or more and 95
It is desirable that the content is not more than mol%. H ₂ O
Is generated when a ketoimine group and / or an aldoimine group is formed from an amine group and a ketone group and / or an aldehyde group, and / or is added afterwards for controlling the polymerization rate, and water is added from these imine groups. It is essential for regenerating the amino group.

In the conventional method, the equilibrium was shifted toward the production of ketoimine, and the polymerization rate was controlled by adding an acid compound during amine regeneration. On the other hand, in the present invention, the carbinol group which is an intermediate thereof is controlled. It has been found that a polyurethane urea elastic body having a higher physical property than that of the conventional method can be obtained, though the reason is not clear, though there is a combination in which a larger amount of is produced and no acid compound is used. When a composition in which the amount of ketoimine produced by the reaction of an amine compound and a ketone compound is reduced and the amount of intermediates produced is increased, the amount of side reactions will be below a certain amount, and the mechanical properties of the resulting elastic body will be very large. It was found to be excellent.

Since it is difficult to quantify by-products in a composition consisting of the reaction of an amine compound and a carbonyl-containing compound, phenylisocyanate, a monofunctional isocyanate, is actually reacted with the composition of the present invention,
Obtained compound

Embedded image as well as

[0028]

[Chemical 15] Was generated as 95% by mole or more with respect to the diamine compound used to obtain the composition, which was used as one measure for the determination of the side reaction product. Since the reaction between water and the isocyanate group present during the polymerization reaction is also fairly fast, the compounds (4) and (5)
Here, the sum of the production amounts of is defined as the amount of the main reactant.

The reaction was carried out by adding 2.0 times the molar amount of phenylisocyanate to the diamine compound used at 50 ° C., allowing it to stand for 30 minutes, and adding H ₂ O to 1.
After adding 0 mol, the mixture was left at 50 ° C. for another 2 hours to decompose excess phenylisocyanate, and then the reaction product was quantified by NMR using an internal standard. Next, a method for producing the composition of the present invention by reacting an asymmetric diamine compound with a carbonyl-containing compound will be described.

The asymmetric diamine compound and the carbonyl-containing compound are mixed in a molar ratio range of 1/1 to 1/10. When the amount of carbonyl-containing compound is small, unreacted diamine increases, which is not preferable. Further, when the amount of the carbonyl-containing compound is large, a step of distilling unnecessary compounds is required, which is not preferable.

It is possible to use a solvent for mixing both compounds, but in that case, it is preferable to distill off the solvent after the reaction. The reaction temperature and the reaction time are the conditions under which the composition falls within the range of the present invention, usually 0 ° C. to 80 ° C. and 10 minutes to 50.
Time, preferably 20 to 60 ° C., 15
Minutes to 3 hours.

Next, the bifunctional or higher functional terminal isocyanate prepolymer used in the present invention (hereinafter referred to as "terminal isocyanate prepolymer") will be described. The terminal isocyanate prepolymer is synthesized by the reaction of a polyol and a diisocyanate. The polyol has a number average molecular weight of 800 to 6000, preferably 1000 to 3
It is a polyether polyol, a polyester polyol, a polylactone polyol, and a polycarbonate polyol having a melting point of 60 ° C. or less in the range of 000.
With a polyol having a number average molecular weight of less than 800, the resulting molded article has a low elongation, and the features of high elongation and high recoverability as a polyurethane urea elastic body are not utilized. Conversely, with a polyol having a number average molecular weight of more than 6000, The obtained molded product has a low elastic modulus. If you use a polyol with a high melting point,
The recoverability of the molded product is low, and the viscosity of the prepolymer is high, which is not preferable. Examples of such polyols include polyether polyols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxypentamethylene glycol and polyether polyols having a side chain,
1 of dibasic acid such as adipic acid, sebacic acid, maleic acid
Or two or more and ethylene glycol, propylene glycol, butanediol, hexamethylene glycol,
Glycol such as cyclohexanedimethanol, or glycerin, phloroglysinol, hexanetriol,
Polyester polyols obtained from one or more polyols such as trimethylolethane, trimethylolpropane and pentaerythritol, polylactone polyols such as polycaprolactone and polyvalerolactone, polyhexamethylene carbonate polyol, neopenti Examples include polycarbonate polyols such as len carbonate polyol. Use one or more of these polyols in combination with a polyol such as glycerin, phloroglysinol, hexanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, 3-methylpentane-1,3,5-triol. You can Among these polyols, the polyether polyols are preferable because the polyester polyols and the polylactone polyols are likely to be slightly embrittled, and the polycarbonates have a high melt viscosity and are complicated in handling. Among them, polyoxytetramethylene diol is particularly preferable. preferable.

Examples of the isocyanate compound include aliphatic di- and triisocyanates and aromatic di- and triisocyanates. Specific examples of the aliphatic isocyanate include ethylene diisocyanate and tetramethylene-1,4-
Diisocyanate, hexamethylene-1,6-dicyanate, dodecane-1,12-diisocyanate, 1,
6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane,
Examples thereof include lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate and bicyclotriisocyanate.

The aromatic di- and triisocyanates are preferably those in which the isocyanate group is directly linked to the benzene nucleus and the two isocyanate groups are mutually linked in the para position. Two
Even if an aromatic diisocyanate in which individual isocyanate groups are bonded at asymmetrical positions is used, uniform mixing and uniform molded products can be obtained, but the physical properties of the molded products are better than those from para-bonded aromatic diisocyanates. It is inferior and not preferable. As such an aromatic diisocyanate, phenylene-1,4-diisocyanate, diphenylmethane-
4,4'-diisocyanate, diphenyl ether-
4,4'-diisocyanate, naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, tolidine-4,4'-diisocyanate and the like can be mentioned. Of these aromatic diisocyanates, diphenylmethane-4,4'-diisocyanate is preferable from the viewpoint of physical properties. As the aromatic triisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate and the like can be used.

The ratio of the molar amount of the di- or triisocyanate compound to the molar amount of the polyol in synthesizing the prepolymer does not need to take into consideration the solubility in a solvent in the case of the present invention. It is possible to synthesize the prepolymer at a ratio higher than 1.4 to 1.8 carried out in 1. When the prepolymer is synthesized at a high ratio, the hard segment can be increased, so that a molded product excellent in elastic modulus, strength, heat resistance and the like can be obtained. If it is too high, it takes time to heat-cure, while if it is too low, the viscosity of the prepolymer becomes high and it becomes difficult to supply it to the mixing equipment.
The range is 2.2. In addition, in order to increase the amount of hard segment, an aromatic isocyanate can be further added to the prepolymer after the reaction.

Next, the mixing of the reaction composition of the asymmetric diamine compound and the carbonyl-containing compound (Liquid A) and the terminal isocyanate prepolymer (Liquid B) will be described. In the mixing to molding of the present invention, chemically, there is a polyaddition reaction between amino groups (including amino groups regenerated from ketoimino groups and / or carbinol groups) and isocyanate groups, so that both groups are equal. It must be the equivalence and the mixing ratio around it.

When the mixing ratio is such that both groups are chemically equivalent, the time required for the discharged mixture to become non-adhesive (hereinafter referred to as non-adhesion time) is shortened, and the equivalent group is deviated. When the mixing ratio is large, the non-adhesion time is long, but the physical properties of the molded product are excellent. On the contrary, when the mixing ratio is large, the equivalent amount is 1.5.
Although the non-adhesion time does not change significantly even if it is increased to about twice, the physical properties of the molded product are poor. In view of the balance between the physical properties of the molded product and the non-adhesion time, it is preferable to mix the liquids A and B in a range where the amount of isocyanate groups is 0.8 to 1.5 times the equivalent amount.

In the mixing of the present invention, since the polymerization reaction is controlled at a desired rate, a uniform molded product can be obtained regardless of the viscosity difference of the liquids (A) and (B). However, JP-A-63-154719 and JP-A-1-21041
As described in Japanese Patent Publication No. 6, it is also possible in the present invention to add a polymer polyol or the like to the liquid (A) to increase the viscosity and facilitate mixing.

The liquids (A) and (B) to be mixed can be mixed with usual additives as long as the effects of the present invention are not impaired. For example, phenyl-based or hindered amine-based antioxidants, pigments and silicones. Examples include an internal release agent such as a system or a fluorine system, a molecular weight modifier such as diethylamine, a surfactant for improving the mixing stability of the liquid (A), an oil agent, a dye improving agent, and the like.

The mixing device in the present invention is a device having a volume provided with a supply port for the supply liquid and a discharge port for discharging the mixture liquid, and is a device in which mixing is carried out in the volume portion, Means for mixing include mechanical mixing with a stirrer, filling and mixing with a filler known as a static mixer, and impingement mixing with a jet stream of a feed liquid.

In the mixing equipment, a reaction occurs between the liquids A and B to be supplied, and a mixed liquid having a viscosity higher than that of the liquids to be supplied is produced. Therefore, if the mixing of the liquids A and B is slow, the reaction is non-uniform. Progresses and is discharged as a mixture having uneven viscosity, resulting in a non-uniform molded product. Therefore, mixing in the mixing equipment should be fast. The polymerization temperature varies depending on the production amount and the residence time in the mixer, but is usually in the range of 40 to 150 ° C. and 50 to 50 ° C.
The range of 80 ° C. is preferable, and although it is not clear for any reason, side reactions increase at both low and high temperatures, which is not preferable.

One method is to further propagate ultrasonic waves to the mixing equipment in order to make the mixing uniform. As a means for propagating ultrasonic waves to the mixing device, there is a direct method in which an ultrasonic vibrator is directly attached to the mixing device, or an ultrasonic wave is placed by placing the vibrator in a medium such as water, silicone oil, lower alcohol, or lower glycol. It is possible to use the indirect method, in which ultrasonic waves are generated and propagated to the mixing device through the medium, but the oscillator heats up due to vibration, so it is necessary to cool it, and the vibration occurs in the cooling medium outside the mixing device. The latter indirect method is preferable, in which a child is provided to simultaneously cool the mixing device and the vibrator, and further ultrasonic waves can be propagated to the mixing device with a simple structure.

The generation frequency of the ultrasonic vibrator used to apply ultrasonic vibration to the mixing device varies depending on the type and size of the mixing device, the method of transmitting ultrasonic waves to the mixing device, etc.
Usually, the range of 10 to 100 KHz is practical, and if the frequency is less than 10 KHz, it is not preferable in terms of noise, while the use of an ultrasonic vibrator having a frequency higher than 100 KHz is a mixing device by an indirect method via a medium. The ultrasonic wave is weakly propagated to the device, and a high output is required to prevent clogging by the reaction mixture in the mixing device, which is not preferable because the electric energy cost becomes high. It is preferable to use an ultrasonic vibrator that generates a high frequency of 15 to 50 KHz, which is often used for emulsification, dispersion and washing, because it is available at a low cost.

The mixture thoroughly mixed by a mixing device is passed through a spinneret in a desired form, for example, a filament, tape, film or the like, and discharged to a roll, a moving belt, a heating bath, a heating water bath or the like. Since the mixture immediately after discharge still has tackiness, it is preferable that the surface of the support is release-treated with a release agent, for example, a silicon-based or fluorine-based substance. Then, the mixture on the support is heated and cured. As a heating source, hot air, infrared rays, ordinary heating methods such as far-infrared rays can be adopted, but if the heating temperature is too high, the resulting polyurethane urea molded article will be unfavorably softened. It takes time,
Although it depends on the heating method, it is usually good to carry out at 40 to 80 ° C. The heating time varies depending on the type and composition of the raw materials of the liquids A and B, the mixing conditions, the heating system and the temperature, and therefore is determined by measuring the degree of polymerization and physical properties of the molded product after heating.

[0045]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. The measurement items described in the following examples are values measured by the following method. 1) ηsp / e: in a dimethylacetamide solvent
It was measured at a concentration of 0.5 g / 100 cc and 25 ° C. 2) Breaking strength / elongation: Tensilon UTM-III (manufactured by Toyo Baldwin Co., Ltd.) was used for measurement at a sample length of 50 mm, a tensile speed of 1000% / min, and a temperature of 20 ° C. 3) Mol% of composition: determined by using IR and NMR. 4) Mn of isocyanate-terminated prepolymer at both ends: Measured using GPC (gel permeation chromatography) after reacting the synthesized isocyanate-terminated prepolymer at both ends with ethanol.

Example 1 (1) Preparation of Composition of Diamine / Carbonyl-Containing Compound Each compound having a predetermined molar ratio shown in Table 1 was weighed and reacted in a reactor under stirring at 50 ° C. for 1 hour. 13C-NM
Using R, the content of the carbinol compound was calculated as a molar ratio conversion value of the charged diamine using trimethylsilane as an internal standard. (2) Isocyanate prepolymer at both ends Polytetramethylene glycol [number average molecular weight (Mn)
1800] 18.0 kg and 4.25 kg of methylene diphenyl diisocyanate (MDI) were placed in a reactor equipped with a stirrer and reacted at 80 ° C. for 4 hours. The amount of diisocyanate group was determined by titration to be 0.62 equivalent / kg. there were. (3) Mixing and molding Using the apparatus shown in FIG. 1, liquid (A): diamine / carbonyl-containing compound (B) liquid: isocyanate prepolymers at both ends and the number of moles of liquid (A) in terms of amino groups. (B) Liquid was continuously supplied to a mixer so that the ratio of the number of moles of isocyanate groups in the liquid was 1: 1.1, and the discharge amount of the liquid (B) was 30 to 70 g from a spinning port having a diameter of 0.1 mm. It was discharged so that it would be / min. The discharged product was passed through a heating cylinder, further passed through hot water, and then wound up. The physical properties of the formed yarns are summarized in Table 1.

(Examples 2, 4 to 6) Molding was carried out in the same manner as in Example 1 except that the composition of the diamine / carbonyl-containing compound shown in Table 1 and diisocyanate at both ends were used. The results are summarized in Table 1. However, the polyester glycol used in Example 6 was adipic acid and ethylene glycol / propylene glycol (7: 3, molar ratio).
The number average molecular weight (Mn) obtained from the above is 1800.

Example 3 (1) Preparation of Composition of Diamine / Carbonyl-Containing Compound The same preparation as in Example 1 was carried out. (2) Isocyanate prepolymer at both ends Polytetramethylene glycol [number average molecular weight (Mn)
1800] 15.2 kg and methylenediphenyl diisocyanate (MDI) 4.25 kg were put into a reactor equipped with a stirrer, reacted at 80 ° C. for 2.5 hours, and then added with trimethylolpropane (TMP) 0.12 kg, Furthermore, the reaction was carried out at 80 ° C. for 1.5 hours. (3) Mixing and molding The same as in Example 1.

Example 7 (1) Preparation of Composition of Diamine / Carbonyl-Containing Compound The same preparation as in Example 1 was carried out. (2) Both-end isocyanate prepolymer adipic acid and ethylene glycol / glycerin (8:
2, a polyester polyol obtained from (molar ratio) [having a number average molecular weight (Mn) of 1800. Polytetramethylene glycol [number average molecular weight (Mn) 180
0] 15.2 kg and methylene diphenyl diisocyanate (MDI) 3.17 kg were put into a reactor equipped with a stirrer,
The reaction was carried out at 80 ° C for 3 hours. (3) Mixing and molding The same as in Example 1.

(Comparative Example 1) As diamine, ethylenediamine which is outside the scope of the present invention was used, and acetone and 50 were used.
Molding was carried out in the same manner as in Example 1 except that the reaction was carried out at 0 ° C. for 10 hours, and the acids and diisocyanates at both ends shown in Table 1 were used.

[0051]

[Table 1]

[0052]

As described above, according to the present invention,
By continuously molding at the same time as the reaction without using a polymerization solvent, a polyuretaurea elastic body excellent in breaking strength, breaking elongation and physical property unevenness was obtained.

[Brief description of drawings]

FIG. 1 is a schematic view of a reaction molding machine.

Claims (2)

[Claims] 1. An asymmetric diamine compound represented by the following structural formula (1) and a ketone compound and / or an aldehyde compound represented by the following structural formula (2) are contained in 1/1 to 1/10.
40 mol% or more and 95 mol% of the compound represented by the following structural formula (3) with respect to the asymmetric diamine compound charged in (I).
Hereinafter, a method for reaction-molding polyurethane urea, which comprises continuously supplying and discharging a composition containing 100 mol% or less of H ₂ O and a bifunctional or higher functional terminal isocyanate prepolymer to a mixing device. Embedded image Embedded image Embedded image 2. A composition containing, further comprising (I
I) A compound represented by the following structural formula (4) obtained when reacted with phenyl isocyanate and a compound represented by the following structural formula (5) are produced in an amount of 95 mol% or more based on the charged asymmetric diamine compound. The method for reaction-forming polyurethane urea according to claim 1, which is a composition having the ability to do so. [Chemical 4] Embedded image