JP3187135B2 - Isocyanate compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel isocyanate compound, and more particularly to an isocyanate compound capable of improving the heat-softening resistance of a urethane resin.

[0002]

2. Description of the Related Art It has been known that isocyanates are easily subjected to an addition reaction by a hydroxyl group and an amino group to form a urethane bond and a urea bond, respectively. Utilizing this reaction, urethane resins are produced from diisocyanates and diols. Urethane resins are widely used because of their excellent abrasion resistance, impact resistance and creep resistance ("thermoplastic elastomers", page 30; see Chemical Daily Co., Ltd. (1991)).

[0003] In the urethane resin thus obtained, physical cross-linking points are formed by hydrogen bonds between urethane bonds, thereby exhibiting material strength. Therefore, the heat-softening resistance of the urethane resin is not so high, affected by the thermal stability of hydrogen bonds. Conventionally, in order to improve the heat-softening resistance of the urethane resin, a method of increasing the amount of urethane bonds introduced or introducing a chemical cross-linking point using a monomer having three or more functional groups has been used. When the number of crosslinking points is increased, there is a problem that flexibility at room temperature and low temperature is reduced. In the case of a thermoplastic elastomer, there is a limit in terms of moldability in increasing the number of chemically crosslinked points.

[0004]

SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned problems, and an object thereof is to provide a urethane resin,
In particular, it is an object of the present invention to provide a novel isocyanate compound capable of improving the heat softening resistance while maintaining the excellent properties of a thermoplastic elastomer.

[0005]

Means for Solving the Problems The isocyanate compound of the present invention is a compound represented by the following general formula [I] or the following general formula [II], thereby achieving the above object.

[0006]

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Wherein R ¹ and R ² independently represent an alkylene group, and R ³ and R ⁴ independently represent an aliphatic group, an alicyclic group, an aromatic group, a substituted aliphatic group or a substituted aromatic group. Represents a group, p is 3 or 4, q and r independently represent 0 or an integer of 1 or more, and s represents 0 or 1.)

[0008]

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Wherein R ⁵ represents an alkylene group, R ⁶ represents an aliphatic group, an alicyclic group, an aromatic group, a substituted aliphatic group or an aromatic group, and t is 2 or 3. , M represents 0 or an integer of 1 or more).

Next, the present invention will be described in detail.

In the isocyanate compound represented by the general formula [I], R ¹ and R ² are each preferably an ethylene group or a propylene group, and q and r are each preferably 0 or 1. R ³ and R ⁴ are an aliphatic group, an alicyclic group, an aromatic group, a substituted aliphatic group, or a substituted aromatic group. Examples of the aliphatic group include a methylene group, an ethylene group, and 1,3.
-Propylene group, 1,4-butylene group, 1,5-pentamethylene group, 1,6-hexamethylene group, 1,7-heptamethylene group, 1,8-octamethylene group and the like. Examples of the alicyclic group include a 1,4-cyclohexyl group, a 1,1-cyclohexyl group, a bis (4-cyclohexyl) methylene group, and a 2,2-bis (4-cyclohexyl) propylidene group. Examples of the aromatic group include 1,4-phenylene group, 1,3-phenylene group, 2,4-tolylene group, 2,6-tolylene group,
4′-p-biphenyl group, bis (4-phenyl) methylene group, 2,2-bis (4-phenyl) propylidene group,
Bis (3-methyl-4-phenyl) methylene group, bis-
And a (3,5-dimethyl-4-phenyl) methylene group.

In the isocyanate compound represented by the general formula [II], the alkylene group R ⁵ is preferably an ethylene group or a propylene group, and m is preferably 0 or 1. As R ⁶ , those described for the above general formula [I] R ³ and R ⁴ can be mentioned.

The isocyanate compounds according to the present invention include p-terphenyl-4,4 ″ -diyl-bis (oxycarbonyl) bis (N-6-isocyanatohexyl) amide and p-terphenyl-4,4 ′ '-Diyl-
Bis (oxycarbonyl) bis (4-methyl-5-isocyanato) anilide, p-terphenyl-4,4 ″
-Diyl-bis (oxycarbonyl) bis (4- (4-
Isocyanatophenyl) methylphenyl)) amide,
p-quarterphenyl-4,4 ′ ″-diyl-bis (oxycarbonyl) bis (N-6-isocyanatohexyl) amide, p-quarterphenyl-4,
4 ″ ′-diyl-bis (oxycarbonyl) bis (4
-Methyl-5-isocyanato) anilide, p-quarterphenyl-4,4 ""-diyl-bis (oxycarbonyl) bis (4- (4-isocyanatophenyl)
Methylphenyl)) amide, p-terphenyl-4-yloxycarbonyl (N-6-isocyanatohexyl) amide, p-terphenyl-4-yloxycarbonyl (4-methyl-5-isocyanato) anilide, p
-Terphenyl-4-yloxycarbonyl (4- (4
-Isocyanatophenyl) methylphenyl)) amide, p-quarterphenyl-4-yloxycarbonyl (N-6-isocyanatohexyl) amide, p-quarterphenyl-4-yloxycarbonyl (4-methyl-5-isocyanate Nate) anilide, p-quarterphenyl-4-yloxycarbonyl (4- (4-isocyanatophenyl) methylphenyl)) amide, p-
Quarterphenyl-4,4 ′ ″-diyl-bis (oxyethyleneoxycarbonyl) bis (N-6-isocyanatohexyl) amide, p-quarterphenyl-
4,4 ""-diyl-bis (oxyethyleneoxycarbonyl) bis (4-methyl-5-isocyanato) anilide, p-quarterphenyl-4,4 ""-diyl-bis (oxyethyleneoxycarbonyl) Screw (4
-(4-isocyanatophenyl) methylphenyl))
Amide, p-terphenyl-4,4 ''-diyl-bis (oxyethyleneoxycarbonyl) bis (N-6
Isocyanatohexyl) amide, p-terphenyl-
4,4 "-diyl-bis (oxyethyleneoxycarbonyl) bis (4-methyl-5-isocyanato) anilide, p-terphenyl-4,4" -diyl-bis (oxyethyleneoxycarbonyl) bis ( 4- (4-
Examples thereof include isocyanatophenyl) methylphenyl)) amide, but the isocyanate compound of the present invention is not limited to these.

The isocyanate compound of the present invention is obtained by reacting at least one of a dihydroxy compound having a p-terphenyl skeleton or a p-quarterphenyl skeleton and a monohydroxy compound with a diisocyanate compound.

The above dihydroxy compound or monohydroxy compound is represented by the following general formulas [III] and [IV], respectively.
It is represented by

[0016]

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(In the formula, R ¹ and R ² , p, q and r are the same as described above.)

[0018]

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(In the formula, R ⁵ , t and m are the same as described above.) The dihydroxy compound [III] is a liquid crystal low molecular weight compound, for example, 4,4 ″ -dihydroxy-p- Terphenyl, 4,4 '''-dihydroxy-
and p-quarterphenyl and 4,4 ′ ″-di (2-hydroxyethoxy) -p-quarterphenyl. The dihydroxy compounds may be used alone or in combination.

Liquid crystal molecules generally have high crystallinity, and the above 4,4 ″ -dihydroxy-p-terphenyl,
Since 4 ""-dihydroxy-p-quarterphenyl and 4,4 ""-di (2-hydroxyethoxy) -p-quarterphenyl have high melting points, these dihydroxy compounds [III] are contained in the polymer chain. When incorporated into, the polymer exhibits unique properties. That is,
Since the dihydroxy compound [III] exhibits crystallinity and has a high melting point, even when the content of the dihydroxy compound [III] is small, a strong and highly heat-resistant physical crosslink is formed. As a result, it is presumed that a thermoplastic elastomer having high heat resistance can be obtained without impairing the flexibility derived from the soft segment.

The monohydroxy compound [IV] is a rigid low-molecular compound having a paraphenylene skeleton,
The melting points of these compounds are extremely high, reflecting their characteristic molecular structure. Furthermore, it is known that the paraphenylene skeleton is effective as a mesogen of a low-molecular liquid crystal compound, which means that the skeleton has a strong cohesive force not only in a solid state but also in a high temperature state (molten state). It shows. Therefore, the above monohydroxy compound [I
When V] is incorporated at the polymer end, a very strong and highly heat-resistant physical crosslink is produced, and a thermoplastic elastomer having excellent heat resistance is produced.

Examples of the monohydroxy compound include 4-hydroxy-p-terphenyl, 4-hydroxy-p-quarterphenyl, 4- (2-hydroxyethoxy) -p-terphenyl and 4- (2-hydroxy Ethoxy) -p-quarterphenyl and the like. The monohydroxy compounds [IV] may be used alone or in combination.

As the diisocyanate, any of aliphatic diisocyanate, aromatic diisocyanate and alicyclic diisocyanate can be used.

Examples of the aliphatic diisocyanate include 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate, and 1,6-hexamethylene diisocyanate. Examples of the alicyclic diisocyanate include 1,4-cyclohexane diisocyanate,
1'-cyclohexane diisocyanate and the like. Further, as the aromatic diisocyanate, for example,
4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, and the like.

The reaction for synthesizing the isocyanate compound of the present invention is carried out in a suitable solvent in which the dihydroxy compound [III] or the monohydroxy compound [IV] and the diisocyanate are dissolved. Examples of such a solvent include N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like. When the isocyanate compound is obtained using the dihydroxy compound [III], the dihydroxy compound [III] may be added to the diisocyanate solution by using the diisocyanate in an amount of 5 mol or more per 1 mol of the dihydroxy compound [III]. desirable. At this time,
An isocyanate compound of dihydroxy compound [III]: diisocyanate 1: 2 is produced in a molar ratio of the contents.
The reaction is performed in a dilute solution, and the diisocyanate is used in an amount of 1 to 1 mol per mol of the dihydroxy compound [III].
When 1.2 mol is used, an isocyanate compound having a molar ratio of dihydroxy compound [III]: diisocyanate of 1: 1 is produced.

When the above monohydroxy compound [IV] is used, it is preferable to use 1 to 1.2 mol of the above diisocyanate per 1 mol of the monohydroxy compound [IV].

The dihydroxy compound [II
I]: When a 1: 2 diisocyanate isocyanate compound is used in the polymerization reaction, the isocyanate compound acts as a chain extender.

On the other hand, when an isocyanate compound having a molar ratio of dihydroxy compound [III]: diisocyanate of 1: 1 is used for the polymerization reaction, the isocyanate compound can be used as a terminal blocking agent or a chain extender. Works.

Further, the above monohydroxy compound [IV]
When an isocyanate compound using is used in a polymerization reaction, the isocyanate compound acts as a terminal blocking agent.

The reaction temperature for synthesizing these isocyanate compounds is usually from 0 to 100 ° C., preferably from room temperature to 50 ° C.

In this reaction, a catalyst generally used for a urethanization reaction of isocyanate can be used. For example, di-n-butyltin dilaurate, stannas octoate, triethylenediamine, diethylenediamine, triethylamine, a metal salt of naphthenic acid, a metal salt of octylic acid and the like can be mentioned.

The isocyanate compound produced by this reaction is recovered by crystallization or precipitation with a poor solvent.
As the poor solvent used here, those which are inactive with respect to the generated isocyanate compound and which dissolve the diisocyanate used in the reaction are used. For example, toluene, acetone, methyl ethyl ketone and the like can be mentioned.
N, N-dimethylformamide as a crystallization solvent,
N, N-dimethylacetamide, dimethylsulfoxide and the like are used.

[0033]

The present invention will be described below with reference to examples and comparative examples.

Example 1 33.8 g (0.1 mol) of 4,4 '''-dihydroxy-p-quarterphenyl (hereinafter abbreviated as DHQ)
Was dissolved at 45 ° C. in 3000 ml of dry N, N-dimethylformamide (hereinafter abbreviated as DMF). Also, 250 g (1 mol) of 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) is 2,500
Dissolved in 45 ml of dry DMF at 45 ° C. While maintaining the temperature at 45 ° C., the DMF solution of DHQ was added dropwise to the vigorously stirred DMF solution of MDI over 30 minutes, and thereafter, stirring was continued for 1 hour. Thereafter, DMF was distilled off under reduced pressure at 45 ° C., and the reaction solution was concentrated about 10-fold and returned to room temperature. A white precipitate that precipitated during concentration was collected by filtration. 1000 ml of this
Was washed with toluene three times, dried under reduced pressure, and recrystallized from dry DMF to obtain an MDI adduct of DHQ (yield: 74).
%). IR spectrum and ¹ H-NMR of this compound
The spectrum is shown below. Table 1 shows the results of elemental analysis.
Shown in

IR spectrum 2280 cm ^-1 (-N = C = O structure) 1710 cm ^-1 (-O- (C = O) -NH- structure) 820 cm ^-1 (p-quarter phenyl structure) ¹ H-NMR spectrum ( 270 MHz, (CD ₃ ) ₂ S
In O) δ 7.83 (8H, benzene ring) δ 7.56 (4H, benzene ring) δ 7.18 (8H, benzene ring) δ 7.07 (4H, benzene ring) δ 6.90 (8H, benzene ring) δ 3. 85 (4H, methylene group)

[0036]

[Table 1]

Example 2 33.8 g (0.1 mol) of DHQ was dissolved at 45 ° C. in 3000 ml of dry DMF. 174 g of 2,4-tolylene diisocyanate (hereinafter abbreviated as TDI)
(1 mol) was dissolved in 2500 ml of dry DMF at 45 ° C. While maintaining at 45 ° C., the DMF solution of DHQ was
The solution was added dropwise to the vigorously stirred TDI DMF solution over 30 minutes, and then stirred for 1 hour. After this, DMF is added to 45
The reaction solution was concentrated to about 10 times, returned to room temperature, and 3 times the volume of toluene was added. The white precipitate deposited during concentration and addition of toluene was recovered by filtration. This was washed three times with 1000 ml of toluene, dried under reduced pressure, and recrystallized from dry DMF to obtain a TDI adduct of DHQ (yield 68%). The IR spectrum and ¹ H-NMR spectrum of this compound are shown below. Table 2 shows the results of the elemental analysis.

IR spectrum 2280 cm ^-1 (-N = C = O structure) 1710 cm ^-1 (-O- (C = O) -NH- structure) 820 cm ^-1 (p-quarter phenyl structure) ¹ H-NMR spectrum ( 270 MHz, (CD ₃ ) ₂ S
In O) δ 7.83 (8H, benzene ring) δ 7.56 (4H, benzene ring) δ 7.32 (4H, benzene ring) δ 6.88 (6H, benzene ring) δ 2.30 (6H, methyl group)

[0039]

[Table 2]

Example 3 33.8 g (0.1 mol) of DHQ was dissolved at 40 ° C. in 3000 ml of dry DMF. In addition, 1,6-hexamethylene diisocyanate (hereinafter abbreviated as HDI) 1
68 g (1 mol) and 0.168 g of di-n-butyltin dilaurate were dissolved in 2500 ml of dry DMF at 40 ° C. While maintaining the temperature at 40 ° C., the DMF solution of DHQ was dropped into the vigorously stirred DMF solution of HDI over 30 minutes, and then the stirring was continued for 1 hour. Thereafter, DMF was distilled off under reduced pressure at 45 ° C., and the reaction solution was concentrated about 20 times and returned to room temperature. A white precipitate that precipitated during concentration was collected by filtration. This is washed three times with 1000 ml of toluene,
After drying under reduced pressure and recrystallization from dry DMF, DHQ HDI
An adduct was obtained (64% yield). The IR spectrum and ¹ H-NMR spectrum of this compound are shown below. Table 3 shows the results of the elemental analysis.

IR spectrum 2280 cm ^-1 (-N = C = O structure) 1710 cm ^-1 (-O- (C = O) -NH- structure) 820 cm ^-1 (p-quarter phenyl structure) ¹ H-NMR spectrum ( 270 MHz, (CD ₃ ) ₂ S
In O) δ 7.83 (8H, benzene ring) δ 7.56 (4H, benzene ring) δ 7.32 (4H, benzene ring) δ 7.05 (4H, benzene ring) δ 6.90 (2H, benzene ring) δ 4. 10 (4H, methylene group) δ 3.75 (4H, methylene group) δ 2.30 (2H, methyl group)

[0042]

[Table 3]

Example 4 4,4 '''-di (2-hydroxyethoxy) -p-quarterphenyl (hereinafter abbreviated as DHEQ) 42.7
g (0.1 mol) in 45 ml of dry DMF.
Dissolved at ° C. In addition, 174 g (1 mol) of TDI was dissolved in 2500 ml of dry DMF at 45 ° C. 45
The DHEQ DMF solution was added dropwise to the vigorously stirred TDI DMF solution over 30 minutes while maintaining the temperature at 1 ° C.
Stirring was continued for hours. Thereafter, DMF was distilled off under reduced pressure at 45 ° C., the reaction solution was concentrated about 10-fold, returned to room temperature, added with 3-fold volume of toluene, and the precipitated white precipitate was collected by filtration. This was washed three times with 1000 ml of toluene, dried under reduced pressure, recrystallized from dry DMF, and treated with TDI of DHEQ.
An adduct was obtained (yield 72%). The IR spectrum and ¹ H-NMR spectrum of this compound are shown below. Table 4 shows the results of the elemental analysis.

IR spectrum 2280 cm ^-1 (-N = C = O structure) 1710 cm ^-1 (-O- (C = O) -NH- structure) 820 cm ^-1 (p-quarter phenyl structure) ¹ H-NMR spectrum ( 270 MHz, (CD ₃ ) ₂ S
In O) δ 7.83 (8H, benzene ring) δ 7.56 (4H, benzene ring) δ 6.90 (4H, benzene ring) δ 3.20 (4H, methylene group) δ 3.05 (4H, methylene group) δ1. 90 (4H, methylene group) δ 1.40 (4H, methylene group) δ 1.12 (4H, methylene group)

[0045]

[Table 4]

Example 5 (Synthesis of Polyester (A)) Dimethyl adipate 87
1 g (5 mol), ethylene glycol 620 g (10
mol), and 84.6 g (0.25 mol) of DHQ
In a monomer mixture of 0.1 g of antimony trioxide as a catalyst.
2 g and calcium acetate 0.4 g, and 1,3,5-trimethyl-2,4,6-tris (3,5
-Di-t-butyl-4-hydroxybenzyl) benzene 1 g and tris (2,4-di-tert-butylphenyl)
1 g of phosphite was added, the reaction system was kept at 200 ° C. for 4 hours under nitrogen, and transesterification was performed while distilling off methanol. Next, the temperature of the reaction system was raised to 300 ° C., the reaction was performed for 30 minutes while distilling ethylene glycol, and then the reaction was performed for 1 hour under reduced pressure of 3 mmHg. After cooling, the product was taken out. The number average molecular weight of the produced polyester (A) was 5000 (molecular weight in terms of polystyrene by gel filtration chromatography; mobile phase chloroform / o-chlorophenol = 4/1).

(Synthesis of Polyurethane) 8.38 g of the DHQ MDI adduct synthesized in Example 1 was added to 50 g of the above polyester (A), and this was added to a plastomill for 24 hours.
Melt kneading was performed at 0 ° C. for 3 minutes and at 260 ° C. for 3 minutes. When the IR spectrum of this sample was measured, an absorption based on a urethane group was observed at 1710 cm ^-1 , but no absorption based on an isocyanate group was observed. From this sample, 5mm thick, 10mm × 10mm by press molding
Was formed. The bigat softening temperature of this molded product measured at a load of 1 kg was 219 ° C. Further, the obtained polyurethane had flexibility at room temperature.

Comparative Example 1 500 g (0.1 mol) of the polyester (A)
50.1 g (0.2 mol) of MDI was dissolved in 3000 ml of dry DMF. After replacing the inside of the system with nitrogen, 0.02 g of di-n-butyltin laurylate was added as a catalyst and reacted at 90 ° C. for 4 hours.

Next, 9.0 g of 1,4-butanediol as a chain extender was added to the above solution, and stirring was continued at 110 ° C. for 4 hours. After the completion of the reaction, the solution is returned to room temperature, and 1000
A precipitate was obtained by adding dropwise to ml of methanol. The polyurethane thus obtained was thoroughly dried. With respect to this polyurethane, the Vigat softening point was measured in the same manner as in Example 5, and it was 128 ° C.

Example 6 (Synthesis of Polyester (B)) Dimethyl adipate 87
1 g (5 mol), ethylene glycol 620 g (10
mol), and 126.8 g of DHQ (0.375 mol
l) in a monomer mixture, 0.2 g of antimony trioxide and 0.4 g of calcium acetate as a catalyst, and 1,3,5-trimethyl-2,4,6-tris (3,
1 g of 5-di-t-butyl-4-hydroxybenzyl) benzene and 1 g of tris (2,4-di-tert-butylphenyl) phosphite are added, and the reaction system is set to 200 g under nitrogen.
The mixture was maintained at a temperature of 4 ° C. for 4 hours, and a transesterification reaction was performed while distilling off methanol. Next, the temperature of the reaction system was raised to 300 ° C.
After reacting for 30 minutes while distilling off ethylene glycol, the reaction was conducted for 1.5 hours under reduced pressure of 3 mmHg. After cooling, the product was taken out. The number average molecular weight of the produced polyester (B) was 6,500 (molecular weight in terms of polystyrene by gel filtration chromatography; mobile phase chloroform / o-chlorophenol = 4/1).

(Synthesis of Polyurethane) To 50 g of the above polyester (B) was added 5.3 g of the TDI adduct of DHQ synthesized in Example 2, and this was added to a plastmill to give 240 g.
The mixture was melt-kneaded at 4 ° C. for 4 minutes and at 260 ° C. for 4 minutes. When the IR spectrum of this sample was measured, an absorption based on a urethane group was observed at 1710 cm ^-1 , but no absorption based on an isocyanate group was observed. The bigat softening point of this sample was measured in the same manner as in Example 5, and it was 210 ° C. Further, the obtained polyurethane had flexibility at room temperature.

Comparative Example 2 The above polyester (B) was used instead of polyester (A)
A polyurethane was obtained in the same manner as in Comparative Example 1, except that 650 g (0.1 mol) was used and 34.8 g (0.2 mol) of TDI was used instead of MDI. This polyurethane was measured for bigat softening point in the same manner as in Example 5 and found to be 137 ° C.

Example 7 (Synthesis of Polyester (C)) Dimethyl adipate 34
8.4 g (2 mol), 298 g ethylene glycol
(2.4 mol), and 67.7 g (0.18
mol) of a monomer mixture, 200 mg of antimony trioxide and 440 mg of calcium acetate as a catalyst, and 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4- as a stabilizer). 400 mg of hydroxybenzyl) benzene and tris (2,4-di-t
(Butylphenyl) phosphite (400 mg) was added, the reaction system was kept at 200 ° C. for 2 hours under nitrogen, and transesterification was performed while distilling off methanol. Next, the temperature of the reaction system was raised to 320 ° C. in 30 minutes, and maintained at normal pressure in this state for 20 minutes, then lowered to 300 ° C., and the polycondensation reaction was performed for 30 minutes in a state of reducing the pressure to 1 mmHg. A gray resin was obtained. The number average molecular weight of the produced polyester (C) is 39000 (molecular weight in terms of polystyrene by gel filtration chromatography; mobile phase chloroform /
o-chlorophenol = 4/1).

(Synthesis of Polyurethane) 0.87 g of the HDI adduct of DHQ synthesized in Example 3 was added to 50 g of the above polyester (C), and this was added to 25 g by using a plastmill.
The mixture was melt-kneaded at 0 ° C. for 4 minutes. When the IR spectrum of this sample was measured, the absorption based on the urethane group was 171.
Although observed at 0 cm ^-1 , no absorption based on isocyanate groups was observed. From this sample, a molded product having a thickness of 2 mm and a size of 150 mm × 15 mm was formed by press molding. After heat treating this molded body at 100 ° C. for 12 hours,
When the IR spectrum was measured, absorption based on a urethane group was observed at 1710 cm ^-1 , but no absorption based on an isocyanate group was observed. When a dumbbell piece was taken from this molded body and its tensile strength was measured, it was 148 kg.
f / cm ² . Further, the obtained polyurethane had flexibility at room temperature.

Comparative Example 3 The tensile breaking strength of the polyester (C) was measured in the same manner as in Example 6, and the result was 118 kgf / cm.
^{Was 2} .

The IR spectrum was measured by a KBr tablet method using a 270-30 Infrared Spectrometer manufactured by Hitachi, using ¹ H-NM.
The R spectrum is JNM-Gx270 manufactured by JEOL Ltd., and the elemental analysis is 240C Elemen manufactured by PerkinElmer.
tal Analyzer, Vigat softening temperature is JI
In accordance with SK7206, the tensile strength at break
Shimadzu Autograph AG-500 based on K6301
It was measured at zero.

[0057]

As is apparent from the above description, by using the isocyanate compound of the present invention, a thermoplastic polyurethane having excellent heat resistance and mechanical strength and excellent flexibility at room temperature and low temperature can be obtained. . This thermoplastic polyurethane can be suitably used for various members as an excellent thermoplastic elastomer.

Continuation of the front page (72) Inventor Daishiro Kishimoto 2-11-20 Mishimaoka, Ibaraki-shi, Osaka (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 271/28 C07C 271/52 CA (STN ) CAOLD (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] [Claim 1] The following general formula [I] or the following general formula [I
An isocyanate compound represented by the formula [I] (Wherein R ¹ and R ² independently represent an alkylene group;
R ³ and R ⁴ are each independently an aliphatic group, an alicyclic group,
Represents an aromatic group , p is 3 or 4, q and r independently represent 0 or an integer of 1 or more, and s represents 0 or 1. (Wherein, R ⁵ represents an alkylene group, R ⁶ represents an aliphatic group,
Represents a cyclic group or an aromatic group , t is 2 or 3, and m represents 0 or an integer of 1 or more).