JPH09157348A - Novel polyester polyurethane and molded article thereof - Google Patents

Abstract

(57) Abstract: 2,7-dimethyl-1,8-octanediol and / or 2,8-dimethyl-1,9-nonanediol-based aliphatic diol having 2 to 10 carbon atoms A polyester diol having a hydroxyl group at the terminal and having a number average molecular weight of 700 to 3500, a diisocyanate compound, and a low molecular weight compound having at least two active hydrogen atoms as a chain extender. Polyurethane and its molded products. [Effect] A polyester polyurethane having excellent elasticity at low temperature, excellent flexibility, hydrolysis resistance, heat resistance, abrasion resistance, and the like and having excellent moldability is provided. In addition, a polyester polyurethane molded article that is excellent in elasticity, bending resistance, and water resistance and is also excellent in texture is provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polyester polyurethane and a molded product thereof.

[0002]

2. Description of the Related Art Polyurethane is molded into a molded product such as a sheet, a film or a fiber and is used in a wide variety of fields. Polyurethane has a wet coagulation method, a dry coagulation method,
It may be impregnated or applied to various molded products such as woven fabrics and fiber entangled nonwoven fabrics by a melt molding method or the like. By carrying out such a treatment with polyurethane, polyurethane is imparted to various molded articles, and molded articles with various new characteristics and high added value can be obtained.

Polyester polyurethanes, polyether polyurethanes, polycarbonate polyurethanes, etc. are known as polyurethanes, and they are appropriately selected and used in consideration of the desired performance depending on the application. For example, polyether-based polyurethane is used in applications requiring hydrolysis resistance, polyester-based polyurethane is used in applications requiring mechanical performance, oil resistance, and abrasion resistance, and polycarbonate-based polyurethane is used in the same way as polyester-based polyurethane. It is used for applications requiring mechanical performance, oil resistance, and wear resistance, and also for applications requiring durability.

[0004]

It has been pointed out that conventional polyester-based polyurethanes have problems such as poor low-temperature properties and flexibility, and improvements thereof are desired. Further, it is required that the molding processability is excellent in obtaining various molded products.

The present inventors have conducted extensive research to provide a polyester-based polyurethane excellent in low-temperature characteristics and flexibility,
Polyurethane starting from a polyester diol consisting of a diol having a side chain and an aliphatic dicarboxylic acid as a raw material, ie, a polyester diol consisting of 3-methyl-1,5-pentanediol and a dicarboxylic acid as a raw material (JP-A-47- 34494, JP-A-48-1
No. 01496, JP-A No. 61-207675, etc.), Polyurethane using polyester diol composed of 2-methyl-1,3-propanediol and dicarboxylic acid as a raw material (see JP-A No. 3-115418), 2- Polyurethane made from a polyester diol consisting of methyl-1,8-octanediol and dicarboxylic acid as a raw material (JP-A-3-115417, JP-A-3-18)
See Japanese Laid 8121), -O- in the molecule _{(CH2) 2 -CH (-CH 3} ) -C
H ₂ —CO— group-containing number average molecular weight of 800 to 3000
As the polymer diol, the poly (β-methyl-δ-valerolactone) diol or a polyester diol mixture containing the same is used as a polyurethane (Japanese Patent Laid-Open No. Sho 60-62).
-199981)), and has already applied for a patent.

These polyester polyurethanes are excellent in physical properties such as hydrolysis resistance and mechanical performance, and can solve the problems pointed out above. However, even with these polyurethanes, room for further improvement was recognized in terms of low-temperature properties, especially elastic properties at low temperatures. An object of the present invention, therefore, is to provide a new polyester polyurethane having excellent elastic properties at low temperatures and a molded product thereof.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have found that a polyurethane prepared from a polyester diol composed of a specific aliphatic diol having a plurality of side chains and an aliphatic dicarboxylic acid as a raw material can solve the above problems. Find out that
As a result of further study, the present invention has been completed.

That is, the present invention relates to 2,7-dimethyl-
2 to 8 carbon atoms mainly composed of 1,8-octanediol and / or 2,8-dimethyl-1,9-nonanediol
A number average molecular weight of 700 to 3 composed of an aliphatic diol of 10 and an aliphatic dicarboxylic acid and having a hydroxyl group at the terminal.
A polyester polyurethane obtained from 500 polyester diol, a diisocyanate compound or a diisocyanate compound and a low molecular weight compound having at least two active hydrogen atoms as a chain extender (hereinafter, this may be abbreviated as a low molecular weight compound). .

Further, according to the present invention, there are provided a molded product made of the above polyester polyurethane and a molded product obtained by applying the above polyester polyurethane to various molded products. According to the present invention, it is possible to obtain a polyurethane having excellent elastic properties at low temperatures. The polyurethane obtained by the present invention is also excellent in flexibility, hydrolysis resistance, heat resistance, abrasion resistance and the like. Furthermore, the polyurethane obtained by the present invention has good moldability.

In the present invention, "2,7-dimethyl-
"The main component is 1,8-octanediol and / or 2,8-dimethyl-1,9-nonanediol" means that 55 mol% or more of the aliphatic diol having 2 to 10 carbon atoms that constitutes the polyester diol. Is 2,7-dimethyl-
It means 1,8-octanediol and / or 2,8-dimethyl-1,9-nonanediol.
2,7-Dimethyl-1,8-octanediol and / or 2,8 in an aliphatic diol having 2 to 10 carbon atoms
When the content of -dimethyl-1,9-nonanediol is less than 55 mol%, the elastic properties of the resulting polyurethane at low temperature are impaired.

2,7-Dimethyl-1,8-octanediol is, for example, 2-methyl-1,2 derived from 2,7-octadiene-1-ol which is mass-produced and easily available.
It can be industrially produced by hydrogenating a product obtained by reacting 8-octanediol with formalin. In addition, 2,8-dimethyl-1,9-nonanediol is, for example, 2,7-, which is mass-produced and easily available.
It can be industrially produced by hydrogenating the product obtained by reacting 1,9-nonanedial derived from octadien-1-ol with formalin.

The aliphatic diol constituting the polyester diol in the present invention is 2,7-dimethyl-1,8-
Octanediol and / or 2,8-dimethyl-
In addition to 1,9-nonanediol, another diol having 2 to 10 carbon atoms can be contained. Examples of such diols include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4
-Butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol,
1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-
1,8-octanediol, 1,10-decanediol, diethylene glycol, dipropylene glycol,
Examples thereof include tetraoxyethylene glycol. These diols may be used alone or in combination of two or more.

Further, the aliphatic dicarboxylic acid constituting the polyester diol in the present invention is not particularly limited, and examples thereof include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. Saturated aliphatic dicarboxylic acid and the like.
These aliphatic dicarboxylic acids may be used alone or in combination of two or more. These aliphatic dicarboxylic acids can also be used in the form of ester derivatives.

The polyester diol in the present invention is 7
It is necessary to have a number average molecular weight of 00-3500. When the number average molecular weight of the polyester diol is less than 700, the resulting polyurethane has poor elastic properties at low temperatures, while when the number average molecular weight of the polyester diol is more than 3500, the resulting polyurethane has poor mechanical performance. .

The polyester diol in the present invention is
It can be produced by utilizing a conventionally known polyester polycondensation reaction. For example, 2,7-dimethyl-1,8
-Octanediol or 2,8-dimethyl-1,9-
Nonanediol or a mixture of 2,7-dimethyl-1,8-octanediol and 2,8-dimethyl-1,9-nonanediol, or 2,7-dimethyl-1,8-octanediol and / or 2,8 -Dimethyl-1,
A mixture of an aliphatic diol having 9 to 10 carbon atoms containing 9-nonanediol and an aliphatic dicarboxylic acid or an ester thereof are charged at a desired ratio, esterification or transesterification reaction is carried out, and the resulting reaction product is polycondensed. A polyester diol can be produced by further polycondensation under vacuum at high temperature in the presence of a catalyst.

Further, as the diisocyanate compound which is the raw material of the polyester polyurethane in the present invention,
For example, aliphatic diisocyanate compounds such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate and other alicyclic diisocyanate compounds, 4,4 ′ -Diphenylmethane diisocyanate,
Examples thereof include aromatic diisocyanate compounds such as tolylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate and 1,5-naphthalene diisocyanate. These diisocyanate compounds may be used alone or in combination of two or more.

If desired, a diisocyanate compound may be mixed with a triisocyanate compound before use. As such a triisocyanate compound,
For example, triphenylmethane triisocyanate, 1,
6,11-undecane triisocyanate, 1,3,6
-Isocyanate compounds such as hexamethylene triisocyanate. The amount of the triisocyanate compound used is 0.05 based on the total amount of the isocyanate compound from the viewpoints of flex resistance and elongation elasticity of the resulting polyurethane.
It is desirable to be in the range of 2 mol%.

The low molecular weight compound having at least two active hydrogen atoms which is a chain extender includes, for example, ethylene glycol, 1,3-propylene glycol, 1,
2-propylene glycol, 1,4-butanediol,
1,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,4
-Butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,1
0-decanediol, diethylene glycol, dipropylene glycol, tetraoxyethylene glycol,
Diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, α, α'-dihydroxy-m-xylene, α, α'-dihydroxy-p-xylene, hydrazine hydrate, succinic acid dihydrazito, adipic acid dihydrazito , Hydrazides such as isophthalic acid dihydrazito, terephthalic acid dihydrazito, piperazine, 2-methylpiperazine, 1,4-diaminopiperazine, ethylenediamine, 1,3-propylenediamine, 1,2-propylenediamine, 1,4-tetramethylenediamine , 1,6-hexamethylenediamine, 1,
3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine,
4,4′-dicyclohexylmethanediamine, isophoronediamine, m-phenylenediamine, p-phenylenediamine, α, α′-diamino-m-xylene, α, α ′
-Diamino-p-xylene, 4,4'-diaminodiphenylmethane, difunctional compounds such as diamines such as 1,5-diaminonaphthalene, and the like. These low molecular compounds may be used alone or in combination of two or more.

As the low molecular weight compound which is a chain extender, for example, glycerin, trimethylolpropane,
It is also possible to use trifunctional compounds such as 1,2,6-hexanetriol and trimethylolpropane. The amount of the trifunctional compound used is determined from the viewpoints of flex resistance and elongation elastic properties of the obtained polyester polyurethane.
It is desirable to set it in the range of 0.01 to 3 mol% with respect to all low molecular weight compounds.

The polyester polyurethane in the present invention can be obtained by mixing the above-mentioned polyester diol, diisocyanate compound and low molecular weight compound as a chain extender in a predetermined molar ratio and reacting them. Here, the amount of each component used is as follows. That is, when diols are used as the low molecular weight compound, the diisocyanate compound is 2 per 1 mol of the polyester diol.
It is preferable to use ˜13 mol, and it is preferable to use 1 to 12 mol of the low molecular weight compound per 1 mol of the polyester diol. Then, in this case, from the viewpoint of elastic properties at low temperature of the obtained polyurethane, bending resistance and molding processability, the polyester diol is 35 to 65% by weight based on the total amount of the polyester diol, the diisocyanate compound and the low molecular weight compound. Is desirable.

On the other hand, when hydrazides or diamines are used as the low molecular weight compound, it is preferable to use 2 to 4 moles of the isocyanate compound per 1 mole of the polyester diol, and the low molecular weight compound per 1 mole of the polyester diol. It is preferable to use 1 to 3 mol. Further, if desired, as a reaction modifier or a side reaction inhibitor, for example, monohydric alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and isobutyl alcohol; dimethylamine, diethylamine, diamine Monofunctional compounds such as secondary amines such as butylamine and diisopropylamine are used. The amount of the monofunctional compound used is preferably 0.05 to 0.2 mol% with respect to the low molecular weight compound.

Further, in the production of the polyester polyurethane of the present invention, a catalyst, a reaction accelerator, a filler, a reinforcing agent, which has been conventionally used in the production of polyurethane,
Any ingredients such as stabilizers can be used if desired.

In the production of the polyester polyurethane of the present invention, a known urethanization reaction technique can be used. As a specific example, a method of charging a polyester polyurethane solvent, a polyester diol and a diisocyanate compound into a polymerization apparatus and reacting them to produce a prepolymer, and then adding a chain extender to perform polymerization (solution polymerization method), A method in which a polyester diol, a diisocyanate compound, a chain extender, a polymerization reaction accelerator, and, if necessary, 5 to 30% by weight of the total weight of a solvent are charged and polymerized under heating (bulk polymerization method), and has a mixing function. A method in which a polyester diol, a diisocyanate compound and a chain extender are continuously supplied to an extruder such as a screw type extruder and melt polymerization is performed (melt polymerization method).

The polyester polyurethane thus obtained has a polyurethane concentration of 10% by weight of N, N-.
As a dimethylformamide (hereinafter abbreviated as DMF) solution, the solution viscosity (hereinafter sometimes abbreviated as solution viscosity) when measured at 30 ° C. is preferably 0.8 poise or more. The polyester polyurethane obtained in the present invention is, for example, a polyurethane solution dissolved in a solvent such as DMF or dimethyl sulfoxide, or a polyurethane dispersion liquid dispersed in these solvents, and then the polyurethane solution or polyurethane dispersion liquid is poured. A film-shaped molded product can be obtained by subjecting the film to expansion molding. Further, a filamentous molded body can be produced by discharging the above polyurethane solution or polyurethane dispersant through the pores. Furthermore, the polyester polyurethane obtained by the present invention is a film-shaped molded product, a thread-shaped molded product, a non-woven fabric in which the thread-shaped molded product is directly integrated by melt-molding with a melt extrusion molding machine or a blow molding machine, a tubular molding, a rod-shaped molding. It is also possible to mold bodies, shoes and soles, and other injection molded products.

If necessary, a colorant, an antistatic agent, a flame retardant, a light resistance stabilizer, and other additives are added to the above polyurethane solution or polyurethane dispersion, and then woven fabric,
By impregnating a fiber molding such as a knitted cloth, a web-like sheet, paper, a fiber entangled non-woven fabric, or a three-dimensional fiber aggregate, and solidifying the polyester polyurethane by a dry coagulation method or a wet coagulation method, these fiber moldings are formed. Polyester polyurethane can be applied.

Further, the above polyurethane solution or polyurethane dispersion is impregnated with an elastic polymer such as the above-mentioned fiber molded body; polyurethane, acrylic synthetic rubber, acrylonitrile-butadiene synthetic rubber, styrene-butadiene synthetic rubber or the like. Polymer-containing fiber moldings; applied to the surface of wood moldings, plastics moldings, metal moldings, glass moldings, etc., and solidify the polyester polyurethane by dry coagulation or wet coagulation Polyester polyurethane may be added to the molded product. The polyester polyurethane of the present invention can also be used in applications where conventional polyurethane is used such as coating agents and base materials for paints.

[0027]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, "part" and "%" in an Example represent a "weight part" and "weight%", respectively.

Reference Examples 1 to 5 [Synthesis of Polyester Diol] 2,7-Dimethyl-1,8-octanediol (hereinafter referred to as
This was abbreviated as DMOD) and adipic acid (hereinafter abbreviated as AD) were charged into the reactor with the composition shown in Table 1 and heated to about 170 ° C. under normal pressure and nitrogen atmosphere. Esterification reaction is carried out while distilling off the produced water to the outside of the reaction system.
The pressure in the reactor was reduced to 5 mmHg and the temperature in the reactor was raised to about 210 ° C. to complete the reaction. The hydroxyl value of the obtained polyester diol was measured by a conventional method, and the number average molecular weight was calculated. (Hereinafter, the polyester diols obtained in Reference Examples 1 to 5 are abbreviated as PDO1 to 5, respectively)

[0029]

[Table 1]

Reference Examples 6 to 9 [Synthesis of polyester diol] DMOD and 1,4-butanediol (hereinafter referred to as BD
A polyester diol was obtained by carrying out an esterification reaction in the same manner as in Reference Example 1 except that a mixed diol obtained by mixing the above-mentioned abbreviations) was used in the ratio shown in Table 2. The number average molecular weight of the obtained polyester diol is also shown in Table 2. (Hereinafter, the polyester diols obtained in Reference Examples 6 to 9 are abbreviated as PDO 6 to 9)

[0031]

[Table 2]

Reference Examples 10 to 14 [Synthesis of polyester diol] Mixing of DMOD and 2,8-dimethyl-1,9-nonanediol (hereinafter abbreviated as DMND) in a ratio shown in Table 3. An esterification reaction was performed in the same manner as in Reference Example 1 except that a diol was used to obtain a polyester diol. The number average molecular weight of the obtained polyester diol is also shown in Table 3. (Hereinafter, Reference Examples 10 to 1
The polyester diol obtained in No. 4 was added to PDO10-14.
Abbreviation)

[0033]

[Table 3]

Examples 1-5 and Comparative Examples PDO1-5 and PDO9 obtained in Reference Examples 1-5 and Reference Example 9 and diphenylmethane-4,4'-diisocyanate (hereinafter abbreviated as MDI) and Ethylene glycol (hereinafter abbreviated as EG) having the composition shown in Table 4 was charged in a polymerization apparatus, DMF was added in an amount such that the concentration of polyurethane was 30%, and the mixture was stirred under a nitrogen atmosphere at about 70 ° C. While reacting. Methanol was added when the viscosity of the reaction mixture reached 70 ° C. and about 500 to 700 poises, and when the solution viscosity was stable and the solution viscosity was stable, a polyurethane solution having a concentration of 30% was taken out. A part of this solution was taken out and the concentration of DMF was 10%.
The solution viscosity at 30 ° C. was measured as a solution.

[0035]

[Table 4]

The polyurethane solution having a concentration of 30% obtained above was cast on a glass plate to prepare a polyurethane film having a thickness of about 0.11 mm. About the obtained polyurethane film, +2 at a pulling speed of 50 cm / min using an Instron universal testing machine (manufactured by Instron)
Measure the tensile strength and elongation at 0 ° C and -20 ° C,
Young's modulus was calculated from those values. Table 5 shows the results. Table 5 also shows the content of polyester diol in the polyester polyurethane [hereinafter, this is abbreviated as SS value].

[0037]

[Table 5]

As is clear from Table 5, the polyurethanes obtained in Examples 1 to 5 have Young's moduli at + 20 ° C. and −20 ° C. smaller than those of the conventional polyurethanes of Comparative Examples, respectively, and have elastic properties at low temperatures. It turns out to be excellent.

Examples 6 to 8 1 mol of PDO 6 to 8 obtained in Reference Examples 6 to 8 and B
D4 mol was charged into a storage tank equipped with a stirrer, which was kept at 70 ° C., and mixed under a nitrogen atmosphere to obtain a mixed diol. On the other hand, 5 mol of MDI was charged into a storage tank kept at 50 ° C. and stored in a nitrogen atmosphere. Next, regarding the cylinder part, the inlet temperature is 80 ° C., the outlet temperature is 195 ° C., 120 ° C., 180 ° C., 220 ° C. from the inlet to the outlet direction
Using a twin-screw extruder whose temperature is set so as to have three temperature regions, the above-mentioned mixed diol is continuously supplied to the inlet of the cylinder by a metering pump, while a predetermined amount of MDI is continuously supplied by the metering pump. To the cylinder at 120 ℃
Is melted by screw-mixing, and the melt viscosity of the polyurethane produced is monitored by an automatic measuring viscometer provided in the temperature range of 220 ° C.
Melt polymerization was carried out by adjusting the extrusion speed so as to obtain poise.

The resulting polyurethane was extruded into water from the extrusion port of a twin-screw type extruder in the form of a strand,
After cooling, polyurethane pellets were obtained. The obtained pellets were aged at 120 ° C. for about 3 hours and then dissolved in DMF to obtain a DMF solution having a polyurethane concentration of 20%. The solubility of polyurethane in DMF was good, and the insoluble content was 0.15% or less. A film having a thickness of 0.11 mm was prepared from this polyurethane solution in the same manner as in Example 1, and the obtained polyurethane film was measured for tensile strength and elongation at + 20 ° C. and −20 ° C. to calculate Young's modulus. Table 6 shows the results. Table 6 also shows the data of the comparative example. The SS value of the polyurethanes obtained in Examples 6 to 8 was about 55%. Table 6
The viscosity value inside is a solution viscosity value measured at 30 ° C. by using a part of the above DMF solution of polyurethane as a DMF solution having a concentration of 10%.

[0041]

[Table 6]

As is clear from Table 6, the polyurethanes prepared from the polyester diols composed of PDO6-8 and BD in Examples 6-8 have the Young's modulus at + 20 ° C. and −20 ° C. of the comparative examples. It can be seen that it is smaller than conventional polyurethane and has excellent elastic properties at low temperatures.

Examples 9 to 13 In the same manner as in Example 1 except that 1 mol of PDO10 to 14 obtained in Reference Examples 10 to 14 were used, 5 mol of MDI and 4 mol of BD (chain extender) were used. A DMF solution having a polyurethane concentration of 25% was obtained by a conventional method. The obtained polyurethane solution was measured as a DMF solution having a polyurethane concentration of 10% at a solution viscosity at 30 ° C. A thickness of 0.11 mm was obtained from this polyurethane solution in the same manner as in Example 1.
The film was prepared, the tensile strength and the elongation at + 20 ° C. and −20 ° C. of the obtained polyurethane film were measured, and the Young's modulus was calculated. Table 7 shows the results. Table 7 also shows the data of the comparative example. The SS value of the polyurethanes obtained in Examples 9 to 13 was about 5.
7%.

[0044]

[Table 7]

As is clear from Table 7, Examples 10 to 1
The polyurethane obtained in No. 4 is + 20 ° C and -20 ° C.
It can be seen that the Young's modulus in is smaller than that of the conventional polyurethane of the comparative example and is excellent in elastic properties at low temperature.

Example 14 1080 g (0.5 mol) of PDO3 obtained in Reference Example 3 and isophorone diisocyanate (hereinafter referred to as IPO
Abbreviated as DI) 223 g (1 mol) and DMF25
00g was charged in a polymerization apparatus, and the temperature was about 70 ° C in a nitrogen atmosphere.
The mixture was reacted for about 3.5 hours with stirring. DMF205
After adding 2 g, a chain extender solution prepared by dissolving 85 g (0.5 mol) of isophoronediamine (hereinafter abbreviated as IPDA) in 1000 g of DMF was added dropwise to the reaction mixture, and the mixture was reacted at 70 ° C. The viscosity of the reaction mixture is 50
Methanol was added at a temperature of about 400 to 450 poises at a temperature of aging, and when the solution viscosity was stabilized and the solution viscosity became stable, the polyurethane solution was taken out.

Then, a film having a thickness of 0.11 mm was prepared from the obtained polyurethane solution in the same manner as in Example 1, and the obtained polyurethane film was + 20 ° C.
When the tensile strength and elongation at -20 ° C. were measured, calculation of Young's modulus were respectively 0.8 kg / mm ² and 2.1 kg / mm ^2. Also, this polyurethane film is 100 at + 20 ° C and -20 ° C.
The operation of% elongation to release was repeated 10 times, and the residual strain was measured and found to be 9% and 14%, respectively. From these facts, it can be seen that the polyurethane obtained has excellent elastic properties at low temperatures.

Example 15 Using a melt blown spinning apparatus in which nozzles having a diameter of 0.3 mm are arranged in a line at intervals of 1 mm in a row at the discharge port of an extruder, and slits for heating gas injection are arranged on both sides, obtained in Example 6. The polyurethane pellets thus obtained were melted at a melting temperature of 245 ° C. and discharged at a rate of 0.2 g / min per nozzle. Air heated to approximately 250 ° C is used with a gauge pressure of 1.5 kg /
Sprayed from both side slits at cm ² , finely divided polyurethane fine fibers are collected on a wire mesh conveyor installed under the nozzle, sandwiched by rollers and pulled while fixing the contact points between the fibers, average basis weight 59 g / m ² A polyurethane nonwoven fabric having a thickness of 0.3 mm and an apparent density of 0.197 g / cm ³ was obtained. This non-woven fabric was excellent in stretchability, air permeability and moisture permeability, and was suitable for use as a patch or bandage for ship agents.

Example 16 In the same manner as in Example 1 except that 1080 g (0.5 mol) of PDO3 obtained in Reference Example 3, 558 g (2.5 mol) of IPDI and 196 g (2 mol) of BD were used. A DMF solution of polyurethane (polyurethane concentration 25%) was obtained by the solution polymerization method, and this was used as a stock solution. This stock solution was used as a DMF solution having a polyurethane concentration of 10%, and the solution viscosity at 30 ° C. was measured and found to be 4.4 poise. A film having a thickness of 0.11 mm was prepared from the above-mentioned stock solution in the same manner as in Example 1, and the obtained polyurethane film was measured for tensile strength and elongation at + 20 ° C. and −20 ° C. to calculate Young's modulus. By the way, 0.92 each
^They were kg / mm ² and 5.3 kg / mm ² . Moreover, about the obtained polyurethane film, +20 degreeC and -20
At 100C, the operation of 100% elongation to release was repeated 10 times, and the residual strain was measured to be 11% and 18%, respectively.
%Met. From this, it can be seen that the polyurethane obtained has excellent elastic properties at low temperatures.

DMF1963 was added to 3000 g of the above stock solution.
g, stearyl alcohol 22.5 g, sorbitan monostearate 7.5 g and a beige colorant 7.5 g were added to prepare a DMF mixed solution having a polyurethane concentration of 15%. On the other hand, a unit weight of 233g /
m ² , thickness 2.9 mm, apparent density 0.08 g / cm ³
The fiber-entangled non-woven fabric of (3) was fixed between the fibers with a polyvinyl alcohol paste to stabilize the morphology. Then, by impregnating the non-woven fabric with the polyurethane mixed solution by impregnating the polyurethane mixed solution with a pair of rolls provided with a gap, the polyurethane is coagulated by immersing in the DMF 30% aqueous solution at 45 ° C. Let Then, it was immersed in hot water at 85 ° C. to dissolve and remove the sizing agent, and dried to obtain a fibrous sheet.

Polyurethane showed good coagulation properties and formed a clean sponge structure between the non-woven fibers. The obtained fibrous sheet has a basis weight of 611 g / m ² and a thickness of 2.0 m.
m, and the apparent density was 0.306 g / cm ³ , which was flexible. This fibrous sheet is divided into two parts so that its thickness is halved, and the surface of the obtained sheet-shaped material is napped and styled, and then dyed with a beige metal complex salt dye, and further water repellent. Finishing treatment such as treatment was applied to obtain a suede-like sheet having a thickness of 1.8 mm. This fibrous suede-like sheet was flexible, showed almost no change in texture even at a low temperature of -20 ° C, was excellent in water resistance, and was a useful fabric for cold weather shoes.

Example 17 The fibrous sheet obtained in Example 16 was divided into pieces having a thickness of 1.1.
mm sheet material was obtained. On the other hand, to 3000 g of the stock solution obtained in Example 16, 1970 g of DMF, 22.5 g of stearyl alcohol and 7.5 g of a metal complex brown colorant were added to prepare a DMF composition liquid having a polyurethane concentration of 15%. This DMF composition liquid was applied to one surface of the sheet-like material having a thickness of 1.1 mm obtained above by the slit coating method, and then immersed in a DMF 45% aqueous solution at 50 ° C. to solidify the polyurethane. Then, it was washed with hot water and dried to obtain a sheet-like material having a coating layer having an average thickness of 0.14 mm and having a fine sponge structure. The surface of this sheet material was colored and embossed to obtain a leather-like sheet material. The obtained leather-like sheet is flexible, shows almost no change in flexibility even at a low temperature of -20 ° C, and is excellent in flex resistance and water resistance. Especially, men's shoes and boots, bags, volleyballs, and soccers. It was a useful material for many purposes such as balls.

[0053]

EFFECTS OF THE INVENTION According to the present invention, there is provided a polyester polyurethane having excellent elasticity at low temperature, flexibility, hydrolysis resistance, heat resistance, abrasion resistance and the like, and good moldability. It The polyester polyurethane provided by the present invention is excellent in elastic properties, flex resistance, and water resistance, and also gives a molded article excellent in texture and the like.

Claims (3)

[Claims] 1. An aliphatic diol having 2 to 10 carbon atoms and an aliphatic dicarboxylic acid mainly containing 2,7-dimethyl-1,8-octanediol and / or 2,8-dimethyl-1,9-nonanediol. A polyester polyurethane obtained from a polyester diol having a hydroxyl group at the end and having a number average molecular weight of 700 to 3500, a diisocyanate compound and a low molecular weight compound having at least two active hydrogen atoms as a chain extender. 2. A molded body made of the polyester polyurethane according to claim 1. 3. A molded article obtained by applying the polyester polyurethane according to claim 1 to a fiber molded body, a plastic molded body, a metal molded body, a wood molded body or an elastic polymer-containing fiber molded body.