JPH0827248A - Production of molded article comprising modified thermoplastic polyurethane - Google Patents

Abstract

PURPOSE:To simply obtain the subject molded article useful for tubes, sheets, etc., having excellent heat resistance, mechanical strength and chemical resistance by molding an isocyanate compound, a long-chain polyol, a chain extender and a prescribed polyisocyanate compound by a twin-screw extruder. CONSTITUTION:(A) An isocyanate compound such as hexamethylene diisocyanate, (B) a long-chain polyol such as polytetramethylene ether glycol, (C) a chain extender such as 1,4-butanediol and (D) a polyisocyanate compound containing a uretdione group and an isocyanurate group obtained by adding a catalyst to hexamethylene diisocyanate, in an amount to give the molar ratio of NCO/active hydrogen of the components A and D the components B and C of 1.0--1.3, are molded by a twin-screw extruder to give the objective molded article.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyurethane sheet and a tube using a modified thermoplastic polyurethane by using a twin-screw extruder. More specifically, it relates to a method for producing a molded article from a modified thermoplastic polyurethane using a polyisocyanate compound containing a uretdione group and an isocyanurate group and / or a polyol compound containing a uretdione group and an isocyanurate group.

[0002]

2. Description of the Related Art Thermoplastic polyurethane resins are excellent in physical properties such as rubber elasticity, abrasion resistance, chemical resistance, and cold resistance, and a molded product can be easily obtained by a usual thermoplastic resin molding process. It is a material with excellent workability that can do things. For example, injection molding is performed using thermoplastic polyurethane resin pellets as a raw material to mold complicated molded products such as watch bands and packings, and in molding tubes and sheets having a simple shape, uniaxial Extrusion molding using a twin-screw extruder or the like is performed. However, the usable temperature of the obtained molding is limited due to its thermoplasticity. For example, in the case of a thermoplastic polyurethane resin having a hardness (HsA) of about 80, the plateau region of the storage elastic modulus seen from the viscoelasticity measurement is not clear, and the behavior of the storage elastic modulus observed from around room temperature decreases with increasing temperature. Tend to do. This phenomenon is because the thermoplastic polyurethane resin has a linear structure, the hydrogen bonding force of the hard segment portion is relaxed as the temperature rises, and a pseudo crosslinked structure is less likely to exist in the molecule. That is, a molded product obtained from the thermoplastic polyurethane resin has a limit in heat resistance, and it was impossible to develop it into an application requiring heat resistance.

As a technique for improving these, Japanese Unexamined Patent Publication No. 6-1
0211, Japanese Patent Publication No. 1-34539, Japanese Patent Publication No. 64
-8746 and Japanese Patent Publication No. 60-43445 are proposed. In all of these, a polyisocyanate compound having an NCO group at the molecular end is added to a molten thermoplastic polyurethane resin to form a crosslinked structure such as an allophanate bond between molecules forming a linear thermoplastic polyurethane resin. It is a technique of forming a molded product having excellent heat resistance and mechanical properties, which has properties close to those of a thermosetting polyurethane resin. The problem with these technologies is that
Since the polyisocyanate compound added as a modifier is an aromatic polyisocyanate (difelmethane diisocyanate derivative), the NCO group has a large influence on humidity and when stored for a long period of time, the NCO group reacts with water to react with water, and There is concern that the NCO content will decrease and the raw material will become cloudy. Therefore, when storing these polyisocyanate compounds, sufficient nitrogen purging is required.

[0004]

Means for Solving the Problems As a result of intensive studies to solve such conventional problems, the present inventors have found that a polyisocyanate compound containing an uretdione group and an isocyanurate group and / or an uretdione group. A thermosetting elastomer-like performance is imparted to the thermoplastic polyurethane by adding a polyol compound containing an isocyanurate group and a T-die for forming a sheet or a tube for forming a tube at the tip of a twin-screw extruder. The inventors have found that a molded product can be produced directly from a urethane raw material by installing a die, and have completed the present invention.

That is, the present invention comprises (A) an isocyanate compound, (B) a long chain polyol, (C) a chain extender, and (D).
A polyisocyanate compound containing a uretdione group and an isocyanurate group (A), (D) component: (B),
Component (C) has a molar ratio of NCO group / active hydrogen group = 1.0 to
When obtaining a molded product using a twin-screw extruder in 1.3,
The component (D) is a polyisocyanate compound containing a uretdione group and an isocyanurate group by adding a catalyst to hexamethylene diisocyanate, which is a method for producing a molded article of a modified thermoplastic polyurethane.

Further, in the present invention, when the molded article described above is obtained, the component (D) is obtained by adding a polyol having a molecular weight of 62 to 4000 to hexamethylene diisocyanate, and then adding a catalyst to form a uretdione group and an isocyanurate group. It is a method for producing a molded article made of a modified thermoplastic polyurethane, which is a polyisocyanate compound containing

According to the present invention, when the above-mentioned molded product is obtained, the component (D) is modified by adding a catalyst to hexamethylene diisocyanate to modify it into uretdione groups and isocyanurate groups, and then adding a polyol having a molecular weight of 62 to 4000. And a polyisocyanate compound and / or a polyol compound.

Further, the present invention is a method for producing a polyurethane sheet and a polyurethane tube, characterized in that the modified thermoplastic polyurethane is produced by using a twin-screw extruder. In addition, the hexamethylene diisocyanate compound as the component (D) may be reacted with a polyol having a molecular weight of 62 to 4000 by adding a catalyst to cause urethanization and simultaneously contain a uretdione group and an isocyanurate group.

Examples of the (A) isocyanate compound used in the present invention include diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate and 1,5-naphthalene diisocyanate. Aromatic isocyanate, hexamethylene diisocyanate,
Examples thereof include alicyclic or aliphatic isocyanate such as isophorone diisocyanate and hydrogenated xylene diisocyanate. A preferred isocyanate compound is hexamethylene diisocyanate.

The long-chain polyol (B) used in the present invention has a molecular weight of 500 to 6000, preferably 85.
0-5000 ester type, ether type, lactone type,
Examples thereof include carbonate-based polyols. Examples of the ester-based polyol include ethylene glycol,
Propylene glycol, 1,4-butanediol, 1,
3-butanediol, 1,4-butenediol, 1,3
-Polyhydric alcohols such as butenediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentylglycol, 1,5-pentanediol and adipic acid, sebacic acid, azelaic acid, terephthalate Fatty acids such as acids, isophthalic acid, maleic acid,
Alternatively, a polyester diol obtained from an aromatic carboxylic acid may be used. Examples of ether-based polyols include polyalkylene ether diols such as polyethylene glycol, polypropylene ether glycol, polytetramethylene ether glycol, and polyhexamethylene ether glycol. Examples of the lactone-based polyol include polycaprolactone glycol, polypropiolactone glycol, polyvalerolactone glycol and the like. Examples of the carbonate-based polyol include ethylene glycol,
Propylene glycol, 1,4-butanediol, 1,
3-butanediol, 1,5-pentanediol, methylpentanediol, methyloctanediol, 1,9
-Polycarbonate diol obtained by dealcoholation reaction of polyhydric alcohol such as nonanediol with diethyl carbonate, dipropylene carbonate and the like.

The chain extender (C) used in the present invention has a molecular weight of less than 500, preferably 62 to 250. For example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 3-methyl-1,5-
Pentanediol, 1,4-bis (β-hydroxyethoxy) benzene, neopentyl glycol, methyloctanediol, 1,9-nonanediol and the like can be mentioned.

The polyisocyanate compound (D) containing a uretdione group and an isocyanurate group used in the present invention is synthesized from a polyisocyanate or a partially urethanized polyisocyanate compound and a catalyst. The reaction temperature is
It is usually performed in the range of 50 to 90 ° C. The polyol compound containing uretdione groups is obtained from the reaction of the above polyisocyanate with an excess equivalent of the polyol compound. In the case of partial urethane formation, 30% by weight or less of the total NCO groups is preferable. If it is made more urethane than this, the thickening of the liquid will be severe and it will be harmful to use.

The isocyanate compound constituting the polyisocyanate compound containing a uretdione group and / or the polyol compound containing a uretdione group is
For example, diphenylmethane diisocyanate, 2,4-
Tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, 1,5-
Examples thereof include aromatic isocyanates such as naphthalene diisocyanate, alicyclic or aliphatic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated xylene diisocyanate.

As a catalyst effective for obtaining a polyisocyanate compound containing a uretdione group and an isocyanurate group, for example, triethylphosphine, dibutylethylphosphine, tri-n-propylphosphine,
Triisopropylphosphine, tri-n-butylphosphine, triamylphosphine, tribenzylphosphine,
Phosphorus compounds such as benzylmethylphosphine are preferred.

The contents of the dimer having an uretdione group and the trimer having an isocyanurate group are determined by gel permeation chromatography (hereinafter abbreviated as GPC) detection by a differential refractometer. Calculated as a percentage. In the present invention, the preferred content of the dimer having an uretdione group and the trimer having an isocyanurate group is 10% or more for the dimer having an uretdione group and 60% or less for the trimer having an isocyanurate group. Is more preferable, and more preferably, the dimer having an uretdione group is 15 to 40%, and the trimer having an isocyanurate group is 15 to 40%.

The active hydrogen-containing compound partially used for urethanization has a molecular weight of 62 to 4000, preferably 90.
˜3000 and the number of functional groups is 2 to 3. For example, 1,4-
Short-chain glycols such as butanediol, 1,3-butanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, 3-methyl-1,5-pentanediol, neopentyl glycol, bisphenol, trimethylolpropane, or Examples of relatively long-chain glycols include long-chain polyols that constitute common thermoplastic polyurethane resins such as polyethylene adipate glycol, polybutylene adipate glycol, polycaprolactone glycol, and polytetramethylene ether glycol. The uretdione group-containing polyol compound can be easily synthesized by the reaction with the active hydrogen compound. It is known that the uretdione group is dissociated by heating to generate an active NCO group, and its dissociation temperature is about 150 ° C.

In the method for producing a polyurethane sheet and a tube of the present invention, an isocyanate compound, a long chain polyol, a chain extender, and NCO are fed from a hopper port of a twin-screw extruder.
/ OH molar ratio = 0.90 to 1.10, more preferably adjusted to 0.95 to 1.05 and charged. Outside of this range, the smoothness of the molded product may be impaired.
The cylinder temperature of the twin-screw extruder is preferably 150 to 220 ° C., a polymer urethane reaction is carried out in a temperature-controlled cylinder system, and then a polyisocyanate compound containing a uretdione group and / Alternatively, it is a method of quantitatively feeding a polyol compound containing a uretdione group. NCO component / OH after generation of active NCO group by dissociation of uretdione group
The molar ratio of the components is selected from the range of 1.00 to 1.3, and more preferably 1.05 to 1.25.

Or, from a hopper port of a twin-screw extruder, an isocyanate compound, a long chain polyol, a chain extender, a polyisocyanate compound containing a uretdione group and / or
Alternatively, a polyol compound containing a uretdione group may be added to N
The CO component / OH component molar ratio is adjusted to 0.90 to 1.1, and more preferably adjusted to 0.95 to 1.05. Molar ratio of NCO component / OH component after generation of active NCO group by dissociation of uretdione group = 1.00
It is selected from the range of 1.30 to 1.30, and more preferably 1.05 to 1.25. The cylinder temperature of the twin-screw extruder is preferably 150 to 220 ° C., and the molar ratio of NCO component / OH component accompanying the polymer urethane reaction and dissociation of the uretdione group in the temperature-controlled cylinder system is 1.00 to 1 It is selected from the range of 0.30, more preferably 1.05 to 1.25. It is selected from the range of the molar ratio of NCO component / OH component after generation of active NCO group by dissociation of uretdione group = 1.00 to 1.3, and more preferably 1.
It is 05-1.25. Further, a polyurethane sheet and a tube having thermosetting elastomeric properties can be obtained by an allophanate bond formed by a reaction between an active NCO group and a urethane group due to dissociation of a uretdione group.

[0019]

INDUSTRIAL APPLICABILITY The polyurethane sheet and tube obtained by the present invention are excellent in heat resistance, mechanical strength and chemical resistance as compared with a molded article obtained by a conventional thermoplastic polyurethane resin, and are excellent in thermosetting polyurethane elastomer. Molded products with similar performance can be obtained. In addition, the productivity is accompanied by the simplification of the process because the molded product can be obtained in a batch without going through the step of resin pelletization by the component constituting the thermoplastic polyurethane resin and the component containing the uretdione group. Cost reduction is possible.

[0020]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not construed as being limited thereto. In the examples and comparative examples, all parts mean parts by weight, and% means% by weight.

The raw materials used in the present invention are shown below. Hexamethylene Diisocyanate (HDI): Nippon Polyurethane Industry Diphenylmethane Diisocyanate (MDI): Nippon Polyurethane Industry Trioctylphosphine: Kishida Chemicals Triamylphosphine: Kishida Chemicals Phosphoric Acid: Kishida Chemicals Methyl paratoluenesulfonate: Kishida Chemicals Propylene Glycol Methyl Ether Acetate: Kishida Chemicals Dibutylamine: Kishida Chemicals 1,4-Butanediol: Tosoh 1,3-Butanediol: Tosoh Polybutylene adipate glycol (Average molecular weight 1000): Nippon Polyurethane Industry polybutylene adipate Glycol (average molecular weight 2000): manufactured by Nippon Polyurethane Industry Polytetramethylene ether glycol (average molecular weight 1000): manufactured by Hodogaya Chemical Industry

[Synthesis of Polyisocyanate Compound] Example 1 A reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser was charged with 3000 parts of HDI and 6.0 parts of trioctylphosphine, and the stirrer was operated. Heat to 55 ° C for 8
After reacting for a period of time, 1.9 parts of phosphoric acid, which is a termination catalyst, was added to terminate the reaction to obtain a pale yellow liquid having an NCO content of 42.1%. Unreacted HDI was removed by thin film distillation to remove NC
A reaction product liquid having an O content of 23.2% was obtained. The reaction product is G
As a result of analysis by PC, the content of the dimer having the uretdione group was 32% and the content of the trimer having the isocyanurate group was 44%. In addition, by infrared absorption spectrum, nuclear magnetic resonance spectrum, the reaction product solution,
The presence of NCO group, uretdione group and isocyanurate group was confirmed. This reaction product liquid is referred to as a polyisocyanate compound (a).

[Manufacture of Urethane Sheet] The temperature near the hopper of the extruder is 160 ° C., the intermediate part is 180 ° C., and the tip part is 200.
Twin-screw extruder (Toshiba Kikai: TEM-
50), polybutylene adipate (average molecular weight 1000) 292 g / min from the hopper mouth,
1,4-butanediol 35 g / min, MDI 17
5g / min quantitatively supplied, screw rotation speed 20
At 0 rpm, a polymer urethane reaction was carried out in the cylinder system of the extruder, and 3 g / min of polyisocyanate compound (a) was supplied from the vicinity of the tip of the cylinder, and the thickness of the belt die attached to the tip was 1 mm and the width was 1 mm. 300m
A urethane sheet of m was obtained. The performance test results of this sheet are as follows. 100% modulus (Kgf / cm ² ) 60 300% modulus (Kgf / cm ² ) 97 Tensile strength (Kg / cm ² ) 450 Elongation (%) 500 Hardness (JIS A) 80 Vicat softening point (° C) 120 Sheet Appearance Smooth and transparent

[Synthesis of Polyisocyanate Compound] Example 2 A reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser was charged with 2987.4 parts of HDI and 12.6 parts of 1,3-butanediol. The reaction was carried out at 65 ° C. for 3 hours with stirring to obtain a pale yellow reaction product liquid having an NCO content of 49.3%. Next, 6.0 parts of triamylphosphine as a catalyst was charged to this reaction product solution, the stirrer was operated and the mixture was heated to 55 ° C. and reacted for 22 hours, and then 5.5 parts of methyl paratoluenesulfonate as a termination catalyst was added and reacted Was stopped to obtain a pale yellow liquid having an NCO content of 30.3%. Unreacted HDI was removed by thin film distillation to obtain a reaction product liquid having an NCO content of 18.7%. As a result of analyzing the reaction product solution by GPC, the content of the dimer having a uretdione group was 20.
%, The content of the trimer having an isocyanurate group is 2
It was 0%. Further, the presence of NCO group, uretdione group and isocyanurate group was confirmed in the reaction product solution by infrared absorption spectrum and nuclear magnetic resonance spectrum.
This reaction product liquid is referred to as a polyisocyanate compound (b).

[Synthesis of Polyol Compound] Example 3 A reactor equipped with a stirrer, a thermometer and a nitrogen seal tube was charged with 100 parts of polyisocyanate compound (a) and 393 parts of polybutylene adipate (average molecular weight 1000), and a uretdione content of 1 0.62%, hydroxyl value 26.4 KOHmg /
g of a polyol compound was obtained. This polyol compound is referred to as a polyol compound (a). Example 4 A reactor equipped with a stirrer, a thermometer and a nitrogen seal tube was charged with 100 parts of polyisocyanate compound (a) and 786 parts of polybutylene adipate (average molecular weight 2000), and the uretdione content was 0.91% and the hydroxyl value was 14. 6 KOHmg
/ G of polyol compound was obtained. This polyol compound is referred to as a polyol compound (b).

Example 5 A reactor equipped with a stirrer, a thermometer and a nitrogen seal tube was charged with 100 parts of polyisocyanate compound (a) and 393 parts of polytetramethylene ether glycol (average molecular weight 1000), and a uretdione content of 1.63%. Hydroxyl value 26.
A polyol compound of 3 KOH mg / g was obtained. Let this polyol compound be a polyol compound (c).

Example 6 A reactor equipped with a stirrer, a thermometer and a nitrogen seal tube was charged with 100 parts of polyisocyanate compound (b) and 311 parts of polybutylene adipate (average molecular weight 1000), and a uretdione content of 1.49% and a hydroxyl value. 24.1 KOHmg /
g of a polyol compound was obtained. This polyol compound is referred to as a polyol compound (d).

Example 7 A reactor equipped with a stirrer, a thermometer, and a nitrogen seal tube was charged with 100 parts of polyisocyanate compound (b) and 621 parts of polybutylene adipate (average molecular weight 2000), and uretdione content was 0.85% and hydroxyl group was added. Value 13.5KOHmg
/ G of polyol compound was obtained. This polyol compound is referred to as a polyol compound (e).

Example 8 A reactor equipped with a stirrer, a thermometer and a nitrogen seal tube was charged with 311 parts of polyisocyanate compound (II) and polytetramethylene ether glycol (average molecular weight 1000).
Part is charged and uretdione content is 1.51%, hydroxyl value is 2
A polyol compound of 3.8 KOHmg / g was obtained. This polyol compound is referred to as a polyol compound (f).

[Production of Urethane Sheet] Examples 9 to 14 Urethane sheets were obtained in the same manner as in Example 1. However, the polyol compound (a) obtained from Examples 3 to 7
~ (F) was used and 40 g / min of the polyol compound was supplied. The performance test results of this sheet are shown in Tables 1-2.

Example 15 The temperature near the hopper of the extruder is 160 ° C. and the middle part is 180.
C., a twin-screw extruder (TEM-50 manufactured by Toshiba Machine Co., Ltd.) whose temperature was adjusted to 200.degree. C. at the tip, and 362 g / min of polybutylene adipate (average molecular weight 2000) and 1,4-butane from the hopper port 25 g / diol
min, MDI of 116 g / min, and 40 g / min of the polyol compound (b) obtained from Example 2 were quantitatively supplied from the hopper port, and the screw rotation speed was 200 rpm.
At the same time, a polymer urethane reaction and a cross-linking reaction were simultaneously performed in the cylinder system of the extruder, and a urethane sheet having a thickness of 1 mm and a width of 300 mm was obtained from a belt die attached at the tip. Table 2 shows the performance test results of this sheet.

Examples 16 to 19 Extruder hopper neighborhood temperature 160 ° C., middle part 180
C., a twin-screw extruder (TEM-50 manufactured by Toshiba Machine Co., Ltd.) whose temperature was adjusted to 200.degree. C. at the tip, and 362 g / min of polybutylene adipate (average molecular weight 2000) and 1,4-butane from the hopper port 25 g / diol
Min and MDI are quantitatively supplied at 116 g / min,
The polymer urethane reaction was carried out in the cylinder system of the extruder at a screw rotation speed of 200 rpm, and the polyol compounds (a), ( b), (d), (e)
Was supplied at a rate of 40 g / min, and a urethane sheet having a thickness of 1 mm and a width of 300 mm was obtained from a belt die attached to the tip. The performance test results of this sheet are shown in Tables 2-3.

Examples 20 to 21 Temperature near the hopper of the extruder 150 ° C., middle part 170
C., a twin-screw extruder (Toshiba Kikai: TEM-50) whose temperature was adjusted to 190.degree. C. was used, and polytetramethylene ether glycol (average molecular weight 1000) was added at 307 g / min. -Butanediol (30 g / min) and MDI (165 g / min) were quantitatively supplied, and a polymer urethane reaction was carried out in the cylinder system of the extruder at a screw rotation speed of 200 rpm. 40 g / min of the polyol compounds (c) and (f) obtained from Nos. 5 and 8
1m thicker than the belt die attached to the
A urethane sheet having a width of m and a width of 300 mm was obtained. The performance test results of this sheet are shown in Table 3.

[Production of Urethane Sheet] Comparative Example 1 Temperature near hopper of extruder, 160 ° C., 180 in middle part
C., using a twin-screw extruder (TEM-50 manufactured by Toshiba Kikai) whose temperature is adjusted to 200.degree. C. at the tip, from the hopper port, polybutylene adipate (average molecular weight 1000) 2
92 g / min, 1,4-butanediol 35 g / mi
n, MDI 175 g / min was quantitatively supplied from the hopper port, and the polymer urethane reaction was performed in the cylinder system of the extruder at a screw rotation speed of 200 rpm, and the belt die attached at the tip had a thickness of 1 mm and a width of 300 m.
A urethane sheet of m was obtained. Table 4 shows the performance test results of this sheet.

Comparative Example 2 A urethane sheet was obtained in the same manner as in Comparative Example 1 using polybutylene adipate (average molecular weight 2000) as in Example 15. Table 4 shows the performance test results of this sheet.

Comparative Example 3 Polytetramethylene ether glycol (average molecular weight 1000) was used as in Examples 20 to 21, and Comparative Example 1
A urethane sheet was obtained in the same manner as in. Table 4 shows the performance test results of this sheet.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

[Manufacture of Urethane Tube] Example 22 A temperature near the hopper of the extruder is 160 ° C., and an intermediate portion is 180
C., using a twin-screw extruder (TEM-50 manufactured by Toshiba Kikai) whose temperature is adjusted to 200.degree. C. at the tip, from the hopper port, polybutylene adipate (average molecular weight 1000) 2
92 g / min, 1,4-butanediol 35 g / mi
n, MDI 175 g / min was quantitatively supplied, and the polymer urethane reaction was carried out in the cylinder system of the extruder at a screw rotation speed of 200 rpm, and the polyol compound obtained in Example 3 from the vicinity of the tip of the cylinder. 40 g / min of (a) was supplied, and a urethane tube having an inner diameter of 6.5 mm and an outer diameter of 10 mm was obtained from a tube die attached to the tip. The performance test of the burst pressure and the appearance at each temperature of this tube was performed. The results are shown in Table 5.

Example 23 A urethane tube was obtained in the same manner as in Example 22. However, the polyol compound (d) obtained in Example 4
Was used to supply 40 g / min of the polyol compound. The performance test of the burst pressure and the appearance at each temperature of this tube was performed. The results are shown in Table 5.

Example 24 The temperature near the hopper of an extruder is 160 ° C., and the middle part is 180
C., a twin-screw extruder (TEM-50 manufactured by Toshiba Machine Co., Ltd.) whose temperature was adjusted to 200.degree. C. at the tip, and 362 g / min of polybutylene adipate (average molecular weight 2000) and 1,4-butane from the hopper port 25 g / diol
min, MDI at 116 g / min and screw rotation speed at 200 rpm, the polymer urethane reaction and the crosslinking reaction were simultaneously carried out in the cylinder system of the extruder to obtain 40 g / mol of the polyol compound (b) obtained in Example 4. min
Is quantitatively supplied from the hopper port, and the screw rotation speed is 2
At 00 rpm, a polymer urethane reaction and a cross-linking reaction were simultaneously carried out in a cylinder system of an extruder, and a urethane tube having an inner diameter of 6.5 mm and an outer diameter of 10 mm was obtained from a tube die attached to the tip. The performance test of the burst pressure and the appearance at each temperature of this tube was performed. The performance test of the burst pressure and the appearance at each temperature of this tube was performed.
The results are shown in Table 5.

Example 25 The temperature near the hopper of an extruder is 150 ° C., the middle part is 170
C., a twin-screw extruder (Toshiba Kikai: TEM-50) whose temperature was adjusted to 190.degree. C. was used, and polytetramethylene ether glycol (average molecular weight 1000) was added at 307 g / min. -Butanediol (30 g / min) and MDI (165 g / min) were quantitatively supplied, and a polymer urethane reaction was carried out in the cylinder system of the extruder at a screw rotation speed of 200 rpm. 40 g / min of the polyol compound (c) obtained from Example 5 was supplied, and a urethane tube having an inner diameter of 6.5 mm and an outer diameter of 10 mm was obtained from a tube die attached to the tip. The performance test of the burst pressure and the appearance at each temperature of this tube was performed. The results are shown in Table 5.

[Production of Urethane Tube] Comparative Example 4 In the same manner as in Comparative Example 1, a tube die was attached instead of the belt die attached to the tip end, and the inner diameter was 6.5 m.
A urethane tube having a diameter of m and an outer diameter of 10 mm was obtained. The performance test of the burst pressure and the appearance at each temperature of this tube was performed. The results are shown in Table 6.

Comparative Example 5 In the same manner as in Comparative Example 2, a tube die was attached instead of the belt die attached to the tip portion, and the inner diameter was 6.5 m.
A urethane tube having a diameter of m and an outer diameter of 10 mm was obtained. The performance test of the burst pressure and the appearance at each temperature of this tube was performed. The results are shown in Table 6.

Comparative Example 6 In the same manner as in Comparative Example 3, a tube die was attached instead of the belt die attached to the tip portion, and the inner diameter was 6.5 m.
A urethane tube having a diameter of m and an outer diameter of 10 mm was obtained. The performance test of the burst pressure and the appearance at each temperature of this tube was performed. The results are shown in Table 6.

[0048]

[Table 5]

[0049]

[Table 6]

Performance test 100% modulus, 300% modulus, tensile strength, elongation, hardness test: conducted in accordance with JIS K6301. Softening temperature: 1 kg load according to the Vicat softening point measurement method
I went in. Appearance: Surface roughness and transparency were visually observed. Burst pressure: A tube molded to have an inner diameter of 6.5 mm and an outer diameter of 10 mm was left at a predetermined temperature for 1 hour, compressed air was injected from both ends, and the pressure at the time of bursting was measured.

Claims (5)

[Claims] 1. A component (A) or (D) containing (A) an isocyanate compound, (B) a long-chain polyol, (C) a chain extender, or (D) a polyisocyanate compound containing a uretdione group and an isocyanurate group. : (B) and (C) components are N
When a molded product is obtained using a twin-screw extruder with a CO group / active hydrogen group molar ratio of 1.0 to 1.3, the component (D) is a hexamethylene diisocyanate with a catalyst added to produce a uretdione group and an isocyanurate group. A method for producing a molded article composed of a modified thermoplastic polyurethane, which is a polyisocyanate compound containing: 2. When obtaining the molded product, the component (D) is hexamethylene diisocyanate having a molecular weight of 62 to 40.
A molded article according to claim 1, which is a modified thermoplastic polyurethane characterized in that it is a polyisocyanate compound containing a uretdione group and an isocyanurate group after addition of a polyol of 00. Method. 3. A polyisocyanate prepared by adding a catalyst having a component (D) to hexamethylene diisocyanate to modify it into a uretdione group and an isocyanurate group, and then adding a polyol having a molecular weight of 62 to 4000 to the molded product. The method for producing a molded article according to claim 1, comprising a modified thermoplastic polyurethane, which is a compound and / or a polyol compound. 4. The method for producing a polyurethane sheet according to claim 1, wherein the modified thermoplastic polyurethane is used in a twin-screw extruder. 5. The method for producing a polyurethane tube according to claim 1, wherein the modified thermoplastic polyurethane is used in a twin-screw extruder.