JP3452563B2 - Method for producing polyesteramide - Google Patents

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 polyesteramide having excellent creep resistance and chemical resistance, and having excellent mechanical strength in a temperature range from room temperature to high temperature.

[0002]

2. Description of the Related Art In recent years, materials having excellent oil resistance, chemical resistance and flexibility have been desired in the fields of automobiles and industry. In particular, there is a strong demand for materials for hoses or tubes having excellent oil resistance and gasoline resistance.

Currently, butadiene is used for such applications.
Vulcanized rubber such as acrylonitrile copolymer rubber (NBR) and plasticized nylon are used. However, in recent years, environmental problems have become more serious, and recyclable materials have been heavily used, and use of non-recyclable materials has been avoided. Therefore, it is not preferable to use a vulcanized rubber that may cause environmental pollution in the manufacturing and processing processes.

As a material to which flexibility is given to nylon, plasticized nylon can be mentioned. For example, JP-A-60
No. 1,730,047 discloses a resin composition in which a polyamide resin is mixed with an acid-modified olefin copolymer and a plasticizer. However, although this technique is effective in suppressing the extraction of the plasticizer in the oil by blending the acid-modified olefin, it is not possible to obtain a material as flexible as an elastomer having a Shore D hardness of 50 or less. Further, since plasticized nylon has a high glass transition temperature, there are essential problems such as poor low temperature properties such as low temperature impact resistance and elongation.

In Japanese Patent Laid-Open No. 61-247732, a polyether amide elastomer is proposed as a flexible nylon material that overcomes the above problems. The above-mentioned technique is to obtain a polyetheramide elastomer by polymerizing caprolactam in the presence of a polyether segment having a molecular weight of 800 to 5,000. Since it is contained in a ratio of 1, the chemical resistance originally possessed by nylon is lowered, and it cannot be used in applications where chemical resistance is required. Further, it has a low heat deterioration resistance and cannot withstand continuous use at 150 ° C.

Polyesteramide elastomer is used as a material for compensating for these drawbacks. Polyesteramide elastomers are known, and elastomers having excellent chemical resistance and softer than plasticized nylon can be obtained. However, since the above polyesteramide elastomer contains a polyester skeleton, the hydrolysis resistance is not sufficient. In order to take advantage of the excellent heat resistance, further improvement in heat deterioration resistance is required, but there is little knowledge about stabilization of polyesteramide and it has not been satisfactory so far.

A method for producing a polyesteramide is disclosed, for example, in Japanese Examined Patent Publication No. 61-36858. According to this method, it is necessary to use a saturated dimer fatty acid and the reaction time is long. However, it is not preferable as a method for industrially obtaining a polyesteramide elastomer.

Further, Japanese Patent Publication No. 46-2268 discloses that
A method of making a copolymer of a polyamide and a polyester formed from 2,2-dimethyl-1,3-propanediol and an aliphatic dicarboxylic acid is disclosed. However, when a polyester is formed from 2,2-dimethyl-1,3-propanediol and an aliphatic dicarboxylic acid, the reactivity is lowered and the polymerization takes a long time, so that the block property is lowered and the mechanical property is lowered. There was a defect such as inferior mechanical strength.

Further, most of the nylon used in this method is a low molecular weight substance, and when a polyesteramide elastomer is produced using such a low molecular weight nylon, it has a high temperature physical property, especially a mechanical property at high temperature. Lack of strength.

As described above, although the polyesteramide elastomer has attracted attention as a material excellent in mechanical strength, chemical resistance and flexibility, an efficient production method has not been established, and therefore, polyesteramide has not been established. Applications have not been developed that take advantage of the excellent properties of.

[0011]

SUMMARY OF THE INVENTION In view of the above, the present invention aims to increase the molecular weight without lowering the block property and is excellent in chemical resistance, moldability and heat resistance, and particularly in mechanical properties and resistance. It is an object of the present invention to provide a method for producing a polyesteramide having excellent creep properties.

[0012]

The gist of the present invention is a polyester constitution comprising at least one dicarboxylic acid represented by the general formula (1) and at least one diol represented by the general formula (2). Reduced viscosity of 1.8 to 7.0 (1 g / dL, 98% sulfuric acid solution, 20 parts by weight)
3) to 250 parts by weight of the polyamide constituent component having a molecular weight of 20,000 to 50,000, and then subjecting the polyester constituent component to an esterification reaction of 150 to 230 parts by weight.
C., and the resulting transparent homogeneous solution is treated under reduced pressure at 200-
Polymerized at 260 ° C., 0.1 to 5 parts by weight of a polycarbodiimide compound is added to 100 parts by weight of a resin composition having an intrinsic viscosity of 0.2 (Ubbelohde viscous tube, orthochlorophenol solution, 30 ° C.) or more. The present invention provides a method for producing a polyesteramide, which is characterized by extending the chain by HOOC-R in _{1 -COOH (1) HO-R} 2 -OH (2) formula, R ₁ represents an alkylene of 2 to 8 carbon atoms, R ₂ represents an alkylene having 2 to 6 carbon atoms.

The dicarboxylic acid used in the present invention is
For example, oxalic acid, malonic acid, succinic acid, glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Although mainly composed of sebacic acid, etc., within the range that does not impair the physical properties of the molded product obtained from the produced polyesteramide,
Various dicarboxylic acids can be used as appropriate.

Examples of the diol used in the present invention include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, butylene glycol, Examples thereof include neopentyl glycol and the like, and glycols and polyalkylene oxides shown below can be appropriately used as long as they do not impair the physical properties of the molded product obtained from the produced polyesteramide.

Examples of the glycol include 1,7
-Heptanediol, 1,8-octanediol, 1,
9-nonanediol, 1,10-decanediol, cyclopentane-1,2-diol, cyclohexane-1,
2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-
1,4-dimethanol and the like can be mentioned. Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyhexamethylene oxide and the like.

A branching agent such as a polyol, a polycarboxylic acid or an oxyacid may be added to the above polyester component for the purpose of increasing the molecular weight of the polyesteramide, increasing the viscosity and shortening the polymerization time.

Examples of the above-mentioned polyols include glycerin, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, sorbitol,
Examples include 1,1,4,4-tetrakishydroxymethylcyclohexane, tris (2-hydroxyethyl) isocyanurate, dipentaerythritol and the like.

Examples of the polycarboxylic acid include hemimellitic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,1,2,2-ethanetetracarboxylic acid and the like. Examples of the oxyacid include citric acid, tartaric acid, 3-hydroxyglutaric acid, trihydroxyglutaric acid, 4-β-hydroxyethyl phthalic acid and the like.

These branching agents are preferably used in an amount of 0.1 to 2.5 mol per 100 mol of dicarboxylic acid.
If it is less than 0.1 mol, the molecular weight of the obtained polyesteramide will not increase and an elastomer excellent in mechanical strength cannot be obtained. If it exceeds 2.5 mol, gelation will occur, which is not preferable.

The molar ratio of the dicarboxylic acid component and the diol component at the time of charging is preferably in the range of 1 / 1.2 to 1/3. If the diol component is less than 1.2 mol per 1 mol of the dicarboxylic acid component, the esterification reaction does not proceed efficiently, and if it exceeds 3 mol, an excess of the diol component is used, which is disadvantageous in terms of cost. However, the presence of excess diol component facilitates the cleavage reaction of the polyamide, resulting in a decrease in blockability and a decrease in heat resistance.

The polyamide used in the present invention has an amide bond in the polymer main chain, can be melted by heating, and has a reduced viscosity of 1.8 to 7.0 (1 g / d).
L, 98% sulfuric acid solution, 20 ° C.). Preferably, the degree of swelling in a mixed solvent of toluene / isooctane 1/1 (weight ratio) is 5.0% or less in terms of weight change rate.
The molecular weight of the above polyamide is limited to 20,000 to 50,000.

Examples of the polyamide include 4-nylon, 6-nylon, 6,6-nylon, 11-nylon, 12-nylon, 6,10-nylon, 6,12.
-Aliphatic nylon such as nylon; isophthalic acid, terephthalic acid, metaxylylenediamine, 2,2-bis (paraaminocyclohexyl) propane, 4,4'-diaminodicyclohexylmethane, 2,2,4-trimethylhexamethylenediamine, Examples thereof include polyamides obtained by polycondensing aromatic, alicyclic and side chain-substituted aliphatic monomers such as 2,4,4-trimethylhexamethylenediamine.

If the reduced viscosity is less than 1.8, the mechanical strength of the obtained resin at high temperature will be insufficient, and if it exceeds 7.0, the solubility of nylon in the polyester constituent components will decrease, making synthesis difficult. Therefore, it is limited to the above range.

The proportion of the polyamide used in the present invention is 3 to 25 with respect to 100 parts by weight of the polyester component.
0 parts by weight. If the charging ratio is less than 3 parts by weight, the mechanical strength of the molded product obtained from the resulting polyesteramide will be insufficient, and if it exceeds 250 parts by weight, it will be difficult to dissolve nylon and an elastomer having good rubber elasticity will be obtained. Cannot be obtained, so the above range is limited.

When neopentyl glycol is used as the diol component, the preferable amount of the neopentyl glycol is 20 to 90 mol% of the diol component. If it is less than 20 mol%, the polymerization rate will decrease, the polymerization time will increase, the blockability will decrease, the physical properties at high temperature will decrease, and the polyester component will crystallize, resulting in insufficient rubber-like properties. On the other hand, if it exceeds 90 mol%, the block property is deteriorated and the strength at high temperature becomes insufficient, which is not preferable.

In the method for producing a polyester amide of the present invention, 3 to 250 parts by weight of the polyamide constituent is dissolved in 100 parts by weight of the polyester constituent, and then the esterification reaction of the polyester constituent is carried out at 150 to 230. The resulting transparent homogeneous solution is polymerized at 200 to 260 ° C. under reduced pressure to obtain a resin composition 100 having an intrinsic viscosity of 0.2 (Ubbelohde viscous tube, orthochlorophenol solution, 30 ° C.) or higher. Chain extension is achieved by adding 0.1 to 5 parts by weight of a polycarbodiimide compound to parts by weight.

In the present invention, the intrinsic viscosity of the polyesteramide obtained by polycondensation before the chain extension reaction in o-chlorophenol at 30 ° C. is 0.2 or more. If it is less than 0.2, the resulting molded article will be inferior in high-temperature physical properties, and therefore it is limited to the above range.

In the polycondensation before the chain extension reaction, it is necessary to dissolve the polyamide in the polyester component to form a transparent homogeneous solution. The reaction does not proceed efficiently in a heterogeneous state. The melting temperature is 150 to 230 ° C. 1
If it is lower than 50 ° C., it is difficult to dissolve, and if it exceeds 230 ° C., decomposition reaction may occur, which is not preferable.

Polymerization of the obtained transparent homogeneous solution was carried out under reduced pressure.
It is preferably 1 mmHg or less and performed at 200 to 260 ° C. If the temperature is lower than 200 ° C, the reaction rate is low and the polymerization viscosity is high, so that efficient polymerization becomes difficult.
If it exceeds 60 ° C., decomposition reaction and coloring occur, so the content is limited to the above range.

In the polycondensation before the chain extension reaction, a catalyst generally used in producing a polyester may be used. As this catalyst, lithium, sodium,
Potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium,
Examples thereof include metals such as cobalt, germanium, tungsten, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese and zirconium, organic metal compounds thereof, organic acid salts, metal alkoxides, metal oxides and the like.

Particularly preferred catalysts are calcium acetate, diacyl stannous tin, tetraacyl stannic tin, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate,
Tin dioctanoate, tin tetraacetate, triisobutyl aluminum, tetrabutyl titanate, germanium dioxide, tungstic acid and antimony trioxide. Two or more kinds of these catalysts may be used in combination.

The following stabilizers may be used during the polymerization. 1,3,5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9-bis [2- [3- (3-t-butyl) -4-Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,
In addition to hindered phenolic antioxidants such as 10-tetraoxaspiro [5,5] undecane, tris (2,2
4-di-t-butylphenyl) phosphite, trilaurylphosphite, 2-t-butyl-α- (3-t-butyl-4-hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite, Dimyristyl-
3,3'-thiodipropionate, distearyl-3,
Examples thereof include heat stabilizers such as 3-thiodipropionate, pentaerystyryl tetrakis (3-lauryl thiopropionate), and ditridecyl-3,3'-thiodipropionate.

The polycarbodiimide compound used in the present invention is a polycarbodiimide having an average of two or more carbodiimides per molecule. These polycarbodiimides may be aliphatic, alicyclic or aromatic. Examples of the polycarbodiimide compound include poly (tricarbodiimide), poly (4,4′-diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (1,3,5- Triisopropylphenylene-2,4-carbodiimide), poly (1,3-diisopropylphenylene-2,4-carbodiimide) and the like. Two or more kinds of the above polycarbodiimide compounds may be used in combination.

The amount of the polycarbodiimide compound added varies depending on the required degree of polymerization of the polyesteramide, but is 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyesteramide having the above-mentioned specific structure. Is the range. If it is less than 0.1 parts by weight, the effect of increasing the degree of polymerization cannot be exerted, and if it exceeds 5 parts by weight, the mechanical strength of the molded product obtained from the polyesteramide will be insufficient, so it is limited to the above range. .

In the chain extension reaction of the polyesteramide of the present invention, the polymerization can be carried out in a kneader such as a kneader or an extruder. A reaction temperature of 130 ° C to 280 ° C is suitable.

A catalyst may be used during the above reaction. Preferred catalysts include, for example, diacyl stannous tin, tetraacyl stannic oxide, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate, tin dioctanoate, tin tetraacetate, stannas octoate, triethyleneamine, diethyleneamine, triethylamine, naphthene. Examples thereof include metal acid salts, metal octylates, triisobutylaluminum, tetrabutyl titanate, calcium acetate, germanium dioxide, and antimony trioxide. Two or more kinds of these catalysts may be used in combination.

In the method for producing a polyesteramide of the present invention 2, 100 parts by weight of a resin composition having an intrinsic viscosity of 0.2 (Ubbelohde viscosity tube, orthochlorophenol solution, 30 ° C.) or more obtained in the process of the present invention 1 is used. To 2 parts of polyfunctional polycarbodidiimide compound 0.3-2
0 parts by weight is blended, melt molding is performed at 130 to 280 ° C., and the obtained molded product is heated at a temperature of 50 ° C. or higher and lower than the melting point to produce a polyesteramide.

The amount of the polycarbodiimide compound added is 0.3 to 20 parts by weight based on 100 parts by weight of the resin composition. If the charging ratio is less than 0.3 parts by weight, crosslinking does not proceed in heating after molding and no improvement effect is observed in physical properties such as mechanical strength, and if it exceeds 20 parts by weight, it becomes a polyester amide of a carbodiimide compound. Since the reaction rate of (1) decreases and the crosslinking does not proceed efficiently, the mechanical strength of the obtained molded product is insufficient, so the range is limited to the above range.

A kneader such as a kneader or an extruder can be used for adding and mixing the polycarbolibodiimide compound of the present invention 2. A kneading temperature of 100 to 280 ° C is suitable.

The resin composition after mixing the polycarbodiimide compound of the second invention can be molded by a general molding method such as press molding, extrusion molding, injection molding or blow molding. The molding temperature varies depending on the melting point of the resin composition and the molding method, but is 130
~ 280 ° C. If it is lower than 130 ° C., the fluidity of the polyesteramide is low, so that a uniform molded product cannot be obtained.

The molded article obtained in Invention 2 needs to have a higher degree of crosslinking by heat treatment. The heating temperature is 50 ° C. or higher and lower than the melting point. If the temperature is lower than 50 ° C., the crosslinking reaction does not proceed, the effect of improving physical properties such as mechanical strength is not observed, and if the temperature is higher than the melting point, it becomes difficult to maintain the shape of the molded product, so the content is limited to the above range. The above heating step is preferably carried out under reduced pressure or in an inert gas atmosphere in order to avoid decomposition of the resin.

The polyesteramide obtained by the production method of the present invention can be subjected to molding methods such as press molding, extrusion molding, injection molding, blow molding, etc. for automobile parts, electric / electronic parts, industrial parts, sports goods, medical goods, etc. It is preferably used for.

Examples of automobile parts include constant velocity joint boots, boots such as rack and opinion boots, ball joint seals, safety belt parts, bumper fascias, emblems, moldings and the like.

Examples of the electric / electronic parts include electric wire coating materials, gears, rubber switches, membrane switches,
Examples include a tact switch and an O-ring. Examples of industrial parts include hydraulic hoses, coil tubes, sealing materials, packings, V-belts, rolls, anti-vibration / vibration materials,
Examples include shock absorbers, couplings, and diaphragms.

Examples of sports equipment include shoe soles and balls for ball games. As medical supplies,
Examples thereof include medical tubes, infusion bags, catheters and the like. In addition, it can be suitably used as an elastic fiber, an elastic sheet, a composite sheet, a hot melt adhesive, and a material for alloying with other resins.

[0046]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, various physical properties were measured by the following methods. Intrinsic viscosity [η]: Measured at 30 ° C in an o-chlorophenol solvent using an Ubbelohde viscosity tube. Surface hardness: The surface hardness was measured with a D type durometer and an A type durometer according to ASTM D2240. Melting point measurement: Using a differential scanning calorimeter (DSC), the temperature was raised at a rate of 10 ° C./min, and the peak temperature was taken as the melting point. Tensile breaking strength, tensile breaking elongation; injection molding (injection pressure 1500 kgf / c using the obtained resin
m ² , mold temperature 70 ° C., cylinder temperature 200 ° C.), No. 3 dumbbell was prepared and measured at room temperature (23 ° C.) according to JIS K 6301. The cylinder temperature at the time of injection molding was set to
Is 180 ° C., Comparative Example 11 is 120 ° C., Comparative Example 12
Is 240 ° C., Examples 13 and 14 and Comparative Example 13 are 22
Instead of 0 ° C. Compression set; blended with polycarbodiimide compound, J
After the cylindrical sample produced according to IS K-6301 was crosslinked by heating, the compression set was measured at 70 ° C. for 22 hours.

Examples 1 and 2 and Comparative Examples 1 and 2 146 parts of adipic acid, 108 parts of butylene glycol, 125 parts of neopentyl glycol (molar ratio of butylene glycol and neopentyl glycol 50/50) (adipic acid component / diol component) The charge ratio of is 1/2.
4) and 6-nylon T850 (manufactured by Toyobo Co., Ltd., 98
% Reduced sulfuric acid 3.5% at 20 ° C. in 150% sulfuric acid, 0.25 part of tetrabutoxy titanium as a catalyst, and 1,3,5-trimethyl-2,4,6-tris (3,3 as a stabilizer.
0.4 part of 5-di-t-butyl-4hydroxybenzyl) benzene, tris (2,4-di-t-butylphenyl)
0.4 parts of phosphite was added, and the reaction system was heated under nitrogen to 200
The temperature was raised to ° C. After heating for 10 minutes, nylon was dissolved and a transparent solution was obtained. The temperature was kept at this temperature for another hour to carry out the esterification reaction. The progress of the esterification reaction was confirmed by calculating the amount of water distilled. After the esterification reaction proceeded, the temperature was raised to 240 ° C. in 20 minutes, and the pressure was reduced. The polymerization system reached a degree of reduced pressure of 1 mmHg or less in 10 minutes. As a result of carrying out a polycondensation reaction for 1 hour in this state, a transparent resin was obtained. The intrinsic viscosity [η] of the polyesteramide obtained by melt polycondensation is 3 in orthochlorophenol.
The measurement result [η] = 0.95 at 0 ° C. This was designated as polyesteramide (I).

100 parts of the above polyesteramide (I) was mixed with poly (1,3-diisopropylphenylene-2,4-carbodiimide) in the amount shown in Table 1, and this was mixed using a Brabender Plastograph extruder. The mixture was extruded at 215 ° C., cooled with water, cut, and pelletized. The intrinsic viscosity of the obtained pellet was measured. Room temperature and 150 ° C
The breaking strength and breaking elongation in the above were measured. The measurement results are shown in Table 1.

Examples 3 and 4 and Comparative Examples 3 and 46 6-nylon A1050 (manufactured by Unitika Ltd., 98% sulfuric acid, reduced viscosity at 20 ° C.) 6 instead of 150 parts of 6-nylon T850 (manufactured by Toyobo). .2) A resin was obtained in the same manner as the polyesteramide (I) except that 150 parts was used. The intrinsic viscosity [η] of the polyesteramide obtained by melt polycondensation was measured in orthochlorophenol at 30 ° C. and was [η] = 0.90. This was designated as polyesteramide (II).

100 parts of the above polyesteramide (II) and poly (1,3-diisopropylphenylene-2,4-carbodiimide) in the amounts shown in Table 1 were mixed, and this was mixed using a Brabender Plastograph extruder. The mixture was extruded at 215 ° C., cooled with water, cut, and pelletized. The intrinsic viscosity of the obtained pellet was measured. Room temperature and 150
The breaking strength and breaking elongation at ° C were measured. The measurement results are shown in Table 1.

Examples 5 and 6 and Comparative Examples 5 and 6 161 parts of adipic acid, 119 parts of butylene glycol, 137 parts of neopentyl glycol (molar ratio of butylene glycol and neopentyl glycol 50/50), (adipic acid component / diol) The charge ratio of the components is 1/2.
4), 40 parts of 6-nylon T850 (manufactured by Toyobo Co., Ltd.),
0.45 parts of pentaerythritol as a branching agent (0.3 equivalents per 100 mol of adipic acid), 0.20 parts of tetrabutoxytitanium and 0.20 parts of tungstic acid as a catalyst, and 1,3,5-trimethyl as a stabilizer. -2, 4, 6
0.4 parts of tris (3,5-di-t-butyl-4hydroxybenzyl) benzene and 0.4 part of tris (2,4-di-t-butylphenyl) phosphite were added, and the reaction system was put under nitrogen. The temperature was raised to 200 degrees. After heating for 10 minutes, nylon was dissolved and a transparent solution was obtained. The temperature was kept at this temperature for another hour to carry out the esterification reaction. The progress of the esterification reaction was confirmed by calculating the amount of water distilled. After the esterification reaction proceeded, the temperature was raised to 240 ° C. in 20 minutes,
A depressurization operation was performed. The polymerization system reached a degree of reduced pressure of 1 mmHg or less in 10 minutes. As a result of carrying out a polycondensation reaction for 1 hour in this state, a transparent resin was obtained. The intrinsic viscosity [η] of the polyesteramide obtained by melt polycondensation was measured in orthochlorophenol at 30 ° C. and the result was [η] = 1.41. This was designated as polyesteramide (III).

Polyesteramide (III) 100
Parts and the amount of poly (1,3-diisopropylphenylene-2,4-carbodiimide) shown in Table 2 were mixed, and this was mixed with a Brabender Plastograph extruder at 200 ° C.
Was extruded, cooled with water and cut into pellets. The intrinsic viscosity of the obtained pellet was measured. Room temperature and 12
The breaking strength and breaking elongation at 0 ° C were measured. The measurement results are shown in Table 2.

Examples 7 and 8 and Comparative Examples 7 and 8 Resins were obtained in the same manner as the polyesteramide (III) except that the branching agent pentaerythritol was not added. The intrinsic viscosity [η] of the polyesteramide obtained by melt polycondensation was measured in orthochlorophenol at 30 ° C. and was [η] = 0.70. This was designated as polyesteramide (IV). The polyester amide (I
V) 100 parts and poly (1,3-diisopropylphenylene-2,4-carbodiimide) in the amounts shown in Table 2 were mixed, and this was extruded at 200 ° C. using a Brabender Plastograph extruder and cooled with water. It was post-cut and pelletized. The intrinsic viscosity of the obtained pellet was measured. Further, the breaking strength and breaking elongation at room temperature and 120 ° C. were measured. The measurement results are shown in Table 2.

Example 9 and Comparative Example 9 100 parts by weight of the polyesteramide (I) used in Example 1 and poly (1,3-diisopropylphenylene-2,4-carbodiimide) in the amounts shown in Table 3 were Brabender. Using a plastograph extruder, they were mixed at 190 ° C. for 2 minutes and extruded to obtain a resin composition. The obtained resin composition is used for injection molding according to JIS K-6.
According to No. 301, a No. 3 dumbbell and a cylindrical sample were prepared. The obtained test piece is 120 ° C. under a nitrogen atmosphere.
After heat treatment for 5 hours at room temperature, tensile rupture strength and elongation at room temperature and 150 ° C., and compression set at 70 ° C. were measured. The above results are shown in Table 3.

Example 10 and Comparative Example 10 Polyesteramide (II) 100 used in Example 2
Parts and the amount of poly (1,3-diisopropylphenylene-2,4-carbodiimide) shown in Table 3 were mixed, and this was mixed for 2 minutes at 195 ° C. using a Brabender Plastograph extruder and extruded to obtain a resin. A composition was obtained. Using the obtained resin composition, a test piece was manufactured in the same manner as in Example 9. The obtained test piece was heat-treated at 130 ° C. for 5 hours in a nitrogen atmosphere, and then the same test as in Example 9 was performed, and the results are shown in Table 3.

Example 11 Polyesteramide (III) 10 used in Example 3
0 parts by weight and the amount of poly (1,3-diisopropylphenylene-2,4-carbodiimide) shown in Table 3 were mixed for 2 minutes at 175 ° C. using a Brabender Plastograph extruder and extruded to obtain a resin composition. Obtained. Using the obtained resin composition, a test piece was manufactured in the same manner as in Example 9.
The obtained test piece was heat-treated at 110 ° C. for 5 hours in a nitrogen atmosphere, and then the same test as in Example 9 was performed. The results are shown in Table 3.

Comparative Example 11 Polyesteramide (III) 10 used in Example 3
0 parts by weight and the amount of poly (1,3-diisopropylphenylene-2,4-carbodiimide) shown in Table 3 were mixed for 2 minutes at 100 ° C. using a Brabender Plastograph extruder and extruded to obtain a resin composition. Got An attempt was made to make a test piece by injection molding using the obtained resin composition, but the test piece could not be obtained because the resin composition had low fluidity. The results are shown in Table 3.

Example 12 Polyesteramide (IV) 100 used in Example 4
Parts by weight and the amount of poly (1,3-diisopropylphenylene-2,4-carbodiimide) shown in Table 4 were used in Example 11.
A resin composition was obtained in the same manner as. Using the obtained resin composition, a test piece was prepared and tested in the same manner as in Example 11. The results are shown in Table 4.

Comparative Example 12 100 parts by weight of the above polyesteramide (IV) and the amount of poly (1,3-diisopropylphenylene) shown in Table 4 were used.
2,4-carbodiimide) was mixed for 2 minutes at 290 ° C. using a Brabender Plastograph extruder and extruded to obtain a resin composition. Since the obtained resin was gelled and had no fluidity, injection molding could not be performed.

Example 13 73 parts by weight of adipic acid, 60.8 parts by weight of butylene glycol, 51.3 parts by weight of 1,2-propanediol (the molar ratio of butylene glycol and 1,2-propanediol was 5).
0/50) (adipic acid component / diol component charging ratio is 1 / 2.7 in molar ratio), 6-nylon (T850 manufactured by Toyobo Co., Ltd., 98% sulfuric acid, reduced viscosity at 20 ° C. 3.5).
150 parts by weight, tetrabutoxy titanium 0.2 as a catalyst
5 parts by weight, 1,3,5-trimethyl-2, as a stabilizer,
0.4 parts by weight of 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (2,4
0.4 part by weight of -di-t-butylphenyl) phosphite was added, and the reaction system was heated to 200 ° C under nitrogen. Temperature rise 1
After 0 minutes, the nylon dissolved and became a transparent solution. The temperature was kept at this temperature for another hour to carry out the esterification reaction.
The progress of the esterification reaction was confirmed by calculating the amount of water distilled. 20 minutes after the esterification reaction has progressed to 2
The temperature was raised to 40 ° C., and the pressure was reduced. The polymerization system reached a degree of reduced pressure of 1 mmHg or less in 10 minutes. As a result of carrying out a polycondensation reaction for 2 hours in this state, a transparent resin was obtained. Intrinsic viscosity of polyesteramide obtained by melt polycondensation [η]
Is the measurement result in orthochlorophenol at 30 ° C [η]
Was 0.75. Polyesteramide (V)
And

100 parts by weight of the above polyesteramide (V), poly (1,3-diisopropylphenylene-2,4-carbodiimide) in the amounts shown in Table 4, and dibutyltin dilaurate as catalyst (0.5 of carbodiimide compound).
wt%) was mixed for 3 minutes at 210 ° C. using a Brabender Plastograph extruder, and the resin composition obtained by extrusion was used to prepare a test piece similar to that of Example 9 by injection molding. The obtained test piece was heat-treated at 150 ° C. for 5 hours in a nitrogen atmosphere, and then the same test as in Example 9 was performed. The results are shown in Table 4.

Comparative Example 13 The test piece obtained in Example 13 was subjected to 40% nitrogen atmosphere.
After performing the heat treatment at 5 ° C. for 5 hours, the same test as in Example 9 was performed. The results are shown in Table 4.

Example 14 Instead of butylene glycol, ethylene glycol 3
A resin was obtained in the same manner as the polyesteramide (V) except that 7.2 parts by weight was used. The intrinsic viscosity [η] of the polyesteramide obtained by melt polycondensation was measured in orthochlorophenol at 30 ° C. and was [η] = 0.78. This was designated as polyesteramide (VI). 100 parts by weight of the above polyesteramide (VI) and the amount of poly (1,3-diisopropylphenylene-2,4) shown in Table 4
-Carbodiimide) was mixed for 5 minutes at 210 ° C using a Brabender Plastograph extruder, and a resin composition obtained by extrusion was used to prepare a test piece in the same manner as in Example 13. The obtained test piece was heat-treated at 150 ° C. for 5 hours under a reduced pressure of 0.05 Torr or less, and then tested in the same manner as in Example 9. The results are shown in Table 4.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

[Table 4]

[0068]

EFFECTS OF THE INVENTION According to the present invention, a polyamide is dissolved in a polyester component containing a specific dicarboxylic acid and a diol as main components under a specific condition, polymerized in a uniform state, and subjected to a chain extension reaction. A polyesteramide excellent in mechanical strength at room temperature and high temperature can be easily obtained. Furthermore, a molded product is produced using a polycarbodiimide compound having two or more functional groups and then crosslinked by heating, whereby a polyesteramide having excellent mechanical strength and creep properties in a range from room temperature to high temperature can be easily obtained. .

Claims (2)

(57) [Claims] 1. A reduced viscosity is 100 parts by weight of a polyester constituent component comprising at least one dicarboxylic acid represented by the general formula (1) and at least one diol represented by the general formula (2). 1.8-7.0 (1 g / dL,
98% sulfuric acid solution, 20 ° C) with a molecular weight of 20000
3 to 250 parts by weight of the polyamide component of 50,000 is dissolved, and then the esterification reaction of the polyester component is performed at 150 to 230 ° C., and the obtained transparent homogeneous solution is polymerized at 200 to 260 ° C. under reduced pressure. Chain extension by adding 0.1 to 5 parts by weight of a polycarbodiimide compound to 100 parts by weight of the obtained resin composition having an intrinsic viscosity of 0.2 (Ubbelohde viscous tube, orthochlorophenol solution, 30 ° C.) or more. A method for producing a polyesteramide, comprising: HOOC-R in _{1 -COOH (1) HO-R} 2 -OH (2) formula, R ₁ represents an alkylene of 2 to 8 carbon atoms, R ₂ represents an alkylene having 2 to 6 carbon atoms. 2. A polycarbodiimide compound having a functionality of 0.3 or more per 100 parts by weight of the resin composition having an intrinsic viscosity of 0.2 (Ubbelohde viscous tube, orthochlorophenol solution, 30 ° C.) or more according to claim 1. 20 parts by weight are compounded and 1
A method for producing a polyesteramide, comprising melt-molding at 30 to 280 ° C., and heating the obtained molded product at a temperature of 50 ° C. or higher and lower than the melting point to crosslink.