JPH07165912A - Method for producing polyesteramide - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] High molecular weight is achieved without deteriorating blockability, and it has excellent chemical resistance, moldability, and heat resistance, and especially excellent mechanical properties and creep resistance. Method for producing polyesteramide. [Structure] Polyamide constituents 3 to 2 are added to 100 parts by weight of a polyester constituent composed of a dicarboxylic acid represented by the general formula (1) and a diol represented by the general formula (2).
After melting 50 parts by weight, the esterification reaction of the polyester constituents was carried out at 150 to 230 ° C., and 100 parts of the resin composition obtained by polymerizing the obtained transparent homogeneous solution at 200 to 260 ° C. under reduced pressure was used. Solid-phase polymerization is performed under a reduced pressure of 5 Torr or lower at a temperature between 30 ° C. lower and a melting point, or a difunctional or higher functional isocyanate compound 0.
A method for producing a polyesteramide, which comprises 1 to 10 parts by weight or 0.1 to 5 parts by weight of a polycarbodiimide compound. _{HOOC-R 1 -COOH (1)} HO-R 2 -OH (2)

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 process for making a copolymer of polyamide, 2,2-dimethyl-1,3-propanediol and a polyester formed from an aliphatic dicarboxylic acid is disclosed. However, when a polyester is formed with 2,2-dimethyl-1,3-propanediol, the reactivity is lowered and the polymerization takes time, so that the block property is lowered and the mechanical strength is deteriorated. There was a drawback.

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]

SUMMARY OF THE INVENTION The gist of the present invention is to provide a polyester component with at least one dicarboxylic acid represented by the general formula (1) and at least one diol represented by the general formula (2). A polyamide constituent component 3 to 250 having a reduced viscosity of 1.8 to 7.0 (1 g / dL, 98% sulfuric acid solution, 20 ° C.) per 100 parts by weight of this component.
Part by weight is dissolved, and then the esterification reaction of the polyester constituent components is performed at 150 to 230 ° C., and the obtained transparent homogeneous solution is polymerized at 200 to 260 ° C. under reduced pressure to obtain an intrinsic viscosity of 0.2. (Ubbelohde viscous tube, ortho-chlorophenol solution, 30 ° C.) or higher resin composition is solid-state polymerized under reduced pressure of 5 Torr or lower at a temperature between 30 ° C. lower than the melting point and the melting point to produce polyesteramide I'm there. 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, and dipentaerythritol.

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.), and 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 polyamide has a molecular weight of about 10,000 to 60,000, and particularly preferably 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.

The intrinsic viscosity (Ubbelohde viscous tube, orthochlorophenol solution, 30 ° C.) of the polyesteramide obtained before the solid phase polymerization is 0.2 or more. If it is less than 0.2, it takes a long time to carry out solid phase polymerization, and therefore it is limited to the above. In order to shorten the time of solid phase polymerization, it is preferably 0.5 or more.

In the present invention, it is necessary to dissolve the polyamide in the polyester component to form a transparent homogeneous solution. The heterogeneous state is not preferable because the reaction does not proceed efficiently. The melting temperature is 150 to 230 ° C.
When the temperature is lower than 150 ° C, dissolution becomes difficult, and when the temperature is higher than 230 ° C, a decomposition reaction occurs, so the content is limited to the above range.

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.

Solid-state polymerization is carried out by setting each polymerization sample to 3
It is carried out under a reduced pressure of 5 Torr or less at a temperature between 0 ° C. low and the melting point. When the solid-phase polymerization temperature is lower than the temperature lower than the melting point by 30 ° C., the polymerization rate is slow and the progress of the polymerization becomes difficult, and when the solid-phase polymerization temperature is higher than the melting point, the sample is melted. Preferably, the melting point is 15
It is a temperature from a temperature lower by ℃ to a temperature lower by 5 ℃ than the melting point. The solid phase polymerization is difficult to proceed under a pressure higher than 5 Torr, and therefore is limited to a reduced pressure of 5 Torr or less. It is preferably 1 Torr or less.

In the polymerization, the catalyst generally used in the production of polyester may be used. As the catalyst, lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tungsten, tin, lead, antimony, arsenic,
Examples include metals such as cerium, boron, cadmium, manganese, and zirconium, organometallic 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 polyesteramide obtained by the production method of the present invention can be used for automobile parts, electric / electronic parts, industrial parts, sports goods, medical goods, etc. by a molding method such as press molding, extrusion molding, injection molding and blow molding. 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 and moldings.

Examples of the electric / electronic parts include electric wire coating materials, gears, rubber switches, membrane switches,
A tact switch, 0-ring, etc. are mentioned. 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.

In the method for producing a polyesteramide of the present invention 2, the transparent homogeneous solution obtained in the process of the present invention 1 is polymerized at 200 to 260 ° C. under reduced pressure to obtain an intrinsic viscosity of 0.2 ( Uberode viscosity tube, ortho-chlorophenol solution, 30 ° C) 100 parts by weight or more of resin composition
Chain extension is achieved by adding 10 parts by weight. When the intrinsic viscosity is less than 0.2, it is preferable to obtain a desired product by chain extension using an isocyanate compound.

In the present invention 2, 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. 0.2
If it is less than the above range, the resulting molded article will be inferior in the physical properties at high temperature, 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 make 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.

Polycondensation of the obtained transparent homogeneous solution can be carried out in the same manner as in the present invention 1. In the polycondensation before the chain extension reaction, the same catalyst as in the polycondensation of the above Invention 1 may be used. In the polycondensation and chain extension reaction, the same stabilizer as in the polycondensation of the above Invention 1 may be used.

The structure of the isocyanate compound used in the present invention 2 is not limited as long as it has two or more isocyanate groups in the same molecule. It is preferable to use diisocyanate as a main component in order to avoid gelation of the polyesteramide and efficiently perform chain extension.

As the above-mentioned diisocyanate, both aromatic diisocyanate and aliphatic diisocyanate can be used. Examples of the aromatic diisocyanate include 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate and naphthalene diisocyanate.

Examples of the aliphatic diisocyanate include 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate, 1,6-hexamethylene diisocyanate,
1,4 cyclohexane diisocyanate, 4,4-cyclohexane diisocyanate and the like can be mentioned. Among the above-mentioned bifunctional or higher isocyanate compounds, examples of isocyanates other than diisocyanates include triphenylmethane-4,4 ′, 4 ″ -triisocyanate.

The amount of the above-mentioned isocyanate compound added varies depending on the required degree of polymerization of the polyesteramide, but the polyesteramide 1 having the above-mentioned specific structure is used.
It is in the range of 0.1 to 10 parts by weight with respect to 00 parts by weight. If it is less than 0.1 part by weight, the effect of increasing the degree of polymerization is not observed, and if it exceeds 10 parts by weight, the mechanical strength of the molded product obtained from the polyesteramide is insufficient, so the content is limited to the above range.

In the chain extension reaction of the polyesteramide of the present invention 2, 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. If the temperature is lower than 130 ° C., the fluidity of the polyesteramide is low, so that the reaction with the isocyanate compound is difficult to proceed. On the other hand, if the temperature exceeds 280 ° C, the polyesteramide and the isocyanate compound are decomposed and a polymer having sufficient strength cannot be obtained. The reaction temperature is 160 ° C to 2
60 ° C. is particularly preferred.

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 3, 0.1 to 5 parts by weight of a polycarbodiimide compound is used instead of 0.1 to 10 parts by weight of the bifunctional or higher functional isocyanate compound used in the present invention 2. To use.

The polycarbodiimide compound used in the present invention 3 is a polycarbodiimide having an average of 2 or more carbodiimides per molecule. These polycarbodiimides may be aliphatic, alicyclic or aromatic. Examples of the polycarbodiimide compound include poly (tricarbodiimide) and 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 method for producing a polyesteramide of the present invention 4, 100 parts by weight of a resin composition having an intrinsic viscosity of 0.2 (Ubbelohde viscous tube, orthochlorophenol solution, 30 ° C.) or more obtained in the process of the present invention 2 is used. 0.5 to 30 parts by weight of a bifunctional or higher isocyanate compound is added to the parts, and melt molding is performed at 130 to 280 ° C.
A polyester amide is produced by heating the obtained molded product at a temperature of 50 ° C. or higher and lower than the melting point.

The amount of the isocyanate compound added is 0.5 to 30 parts by weight based on 100 parts by weight of the resin composition. If the charging ratio is less than 0.5 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 30 parts by weight, a polyesteramide of an isocyanate compound is obtained. 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.

Addition of the isocyanate compound of the present invention 4,
In the mixing, a kneader such as a kneader or an extruder can be used. A kneading temperature of 100 to 280 ° C. is suitable. If the kneading temperature is less than 100 ° C., the isocyanate compound cannot be uniformly dispersed because the polyesteramide has low fluidity,
When the temperature exceeds 280 ° C, the polyesteramide and the isocyanate compound are decomposed and a polymer having sufficient strength cannot be obtained. Therefore, the content is limited to the above range. Preferably 1
20-240 degreeC.

The resin composition after mixing the isocyanate compound of the present invention 4 can be molded by a general molding method such as press molding, extrusion molding, injection molding and 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 the temperature is lower than 130 ° C., the fluidity of the polyesteramide is low, and a uniform molded product cannot be obtained.
When the temperature exceeds 80 ° C, the polyesteramide and the isocyanate compound are decomposed and a polymer having sufficient strength cannot be obtained. Therefore, the content is limited to the above range.

The molded article obtained in Invention 4 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.

In the method for producing a polyesteramide of the present invention 5, 100 parts by weight of a resin composition having an intrinsic viscosity of 0.2 (Ubbelohde viscous tube, orthochlorophenol solution, 30 ° C.) or more obtained in the process of the present invention 3 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.

[0057]

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
m2, mold temperature 70 ° C., cylinder temperature 200 ° C.), No. 3 dumbbell was prepared, and measured at room temperature (23 ° C.) according to JIS K6301. In addition, the cylinder temperature at the time of injection molding is set to
Was 180 ° C., Comparative Examples 36 and 37 were 120 ° C., Comparative Example 38 was 240 ° C., and Examples 43 to 46 and Comparative Examples 40 and 41 were 220 ° C. instead. Compression set: A cylindrical sample prepared by blending an isocyanate compound or a polycarbodiimide compound and produced according to JIS K-6301 was crosslinked by heating, and then the compression set was measured after 22 hours at 70 ° C.

Example 1 146 parts of adipic acid, 108 parts of butylene glycol, 125 parts of neopentyl glycol (molar ratio of butylene glycol and neopentyl glycol of 50/50), and
6-nylon (T850 manufactured by Toyobo Co., Ltd. in 98% sulfuric acid,
Reduced viscosity at 20 ° C. 3.5) 150 parts, tetrabutoxy titanium 0.25 part as a catalyst, stabilizer 1,3,3
5-trimethyl-2,4,6-tris (3,5-di-t
-Butyl-4-hydroxybenzyl) benzene 0.4
Part, tris (2,4-di-t-butylphenyl) phosphite (0.4 parts) were added, and the reaction system was heated to 200 ° C. under nitrogen. After heating for 10 minutes, nylon was dissolved and a transparent solution was obtained.

The esterification reaction was carried out at this temperature for another 1 hour. The progress of the esterification reaction was confirmed by measuring the amount of distilled water. 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. After crushing the obtained resin, 190
Solid phase polymerization was carried out at 0.5 ° C. and 0.5 Torr for 24 hours. Intrinsic viscosity of polyesteramide obtained by melt polycondensation [η]
Is the measurement result in orthochlorophenol at 30 ° C [η]
Was 0.95. In addition, the intrinsic viscosity [η] of the polyesteramide obtained by solid-phase polymerization was measured at 30 ° C. in orthochlorophenol [η] = 1.95. The Shore D hardness was 39. Furthermore, room temperature, 150 ℃
The tensile elongation at break was measured. The above results are shown in Table 1.

Example 2 The amount of 6-nylon added was 340 parts, and the solid phase polymerization was 20
Polymerization was carried out in the same manner as in Example 1 except that the reaction was carried out at 0 ° C. and 0.3 Torr for 24 hours to obtain a resin. The same test as in Example 1 was conducted on this resin. The results are shown in Table 1.

Example 3 161 parts of adipic acid, 119 parts of butylene glycol, 137 parts of neopentyl glycol (molar ratio of butylene glycol and neopentyl glycol 50/50), and
6-nylon (T850 manufactured by Toyobo Co., Ltd. in 98% sulfuric acid,
A resin was obtained in the same manner as in Example 1 except that the reduced viscosity at 20 ° C. was 3.5) 120 parts. The same test as in Example 1 was conducted on this resin. The results are shown in Table 1.

Example 4 A resin was obtained in the same manner as in Example 1 except that 64.8 parts of butylene glycol and 175 parts of neopentyl glycol (molar ratio 30/70 of butylene glycol and neopentyl glycol) were used. The same test as in Example 1 was conducted on this resin. The results are shown in Table 1.

Example 5 A resin was obtained in the same manner as in Example 1 except that 64.8 parts of butylene glycol and 175 parts of neopentyl glycol (molar ratio of butylene glycol and neopentyl glycol were 70/30). The same test as in Example 1 was conducted on this resin. The results are shown in Table 1.

Example 6 A resin was obtained in the same manner as in Example 1 except that 205 parts of butylene glycol and 12.5 parts of neopentyl glycol (molar ratio of butylene glycol and neopentyl glycol were 95/5). The same test as in Example 1 was conducted on this resin. The results are shown in Table 1.

Example 7 Polymerization was carried out using 10.8 parts of butylene glycol and 225 parts of neopentyl glycol (molar ratio of butylene glycol and neopentyl glycol of 10/90).
The polymerization rate was slow, and the polycondensation reaction was carried out for 2 hours under reduced pressure to obtain a resin. The obtained resin was solid-phase polymerized in the same manner as in Example 1. The same test as in Example 1 was conducted on this resin.
The results are shown in Table 1.

Example 8 150 parts of 6-nylon (T850 manufactured by Toyobo Co., Ltd.) was replaced with 150 parts of 6-nylon (A1050 manufactured by Unitika Co., 98% sulfuric acid, reduced viscosity 6.2 at 20 ° C.). A resin was obtained in the same manner as in Example 1 except for the above. The same test as in Example 1 was conducted on this resin. The results are shown in Table 1.

Example 9 Instead of 150 parts of 6-nylon (T850 manufactured by Toyobo), 6,6-nylon (MARANYL manufactured by Unitika) was used.
A226, 98% sulfuric acid, reduced viscosity at 20 ° C 2.6)
A resin was obtained in the same manner as in Example 1 except that 150 parts was used. The same test as in Example 1 was conducted on this resin. The results are shown in Table 1.

Example 10 Pentaerythritol of 0.34 was used as a polyol component.
Polymerization was carried out in the same manner as in Example 1 except that parts (0.25 mol% relative to adipic acid) were added to obtain a resin. The same test as in Example 1 was conducted on this resin. The results are shown in Table 1.
It was shown to.

Example 11 161 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 component charging ratio by molar ratio) 1/2.
4), 6-nylon (T850 manufactured by Toyobo Co., Ltd., 98% sulfuric acid, reduced viscosity at 20 ° C., 3.5) 40 parts, pentaerythritol 0.75 part (adipic acid 100) as a branching agent.
0.5 equivalent per mole), 0.20 part of tetrabutoxy titanium, 0.20 part of tungstic acid as a catalyst, and 1,3,5-trimethyl-2,4,6-tris (3,5- Di-t-butyl-4-hydroxybenzyl)
0.4 parts of benzene and 0.4 parts of tris (2,4-di-t-butylphenyl) phosphite were added, and the reaction system was heated to 200 ° C. under nitrogen, and after 10 minutes, nylon was dissolved and transparent. Became a solution.

The esterification reaction was carried out at this temperature for another 1 hour. The progress of the esterification reaction was confirmed by measuring the amount of distilled water. 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. After crushing the obtained resin, 170
Solid phase polymerization was carried out at 0.4 ° C. and 0.4 Torr for 24 hours. Intrinsic viscosity of polyesteramide obtained by melt polycondensation [η]
Is the measurement result in orthochlorophenol at 30 ° C [η]
= 1.51. Further, the intrinsic viscosity [η] of the polyesteramide obtained by solid phase polymerization was measured in orthochlorophenol at 30 ° C. and the result was [η] = 2.50. Shore A hardness was 67. The tensile elongation at break at room temperature and 70 ° C. was measured. The above results are shown in Table 1.

Example 12 6-Nylon (T850 manufactured by Toyobo Co., Ltd. in 98% sulfuric acid,
Polymerization was performed in the same manner as in Example 11 except that the amount of the reduced viscosity at 20 ° C. 3.5) added was 80 parts to obtain a resin. The same test as in Example 11 was conducted on this resin. The results are shown in Table 2.

Example 13 A resin was obtained by polymerizing in the same manner as in Example 11 except that 2.5 parts of glycerin (2.5 equivalents per 100 mol of adipic acid) was used as a branching agent. The same test as in Example 11 was conducted on this resin. The results are shown in Table 2.

Example 14 Polymerization was carried out in the same manner as in Example 11 except that 0.5 part of 3-hydroxyglutaric acid (0.8 equivalents per 100 mol of adipic acid) was used as a branching agent to obtain a resin. It was The same test as in Example 11 was conducted on this resin. The results are shown in Table 2.

Example 15 Example 11 was repeated except that 0.7 part of 1,1,2,2-ethanetetracarboxylic acid (1.6 equivalents per 100 mol of adipic acid) was used as a branching agent. Polymerization was performed to obtain a resin. The same test as in Example 11 was conducted on this resin. The results are shown in Table 2.

Example 16 82 parts of ethylene glycol as a diol component, 137 parts of neopentyl glycol (molar ratio of ethylene glycol and neopentyl glycol of 50/50), (adipic acid component / diol component charging ratio of 1 / molar ratio) 2.4)
A resin was obtained in the same manner as in Example 11 except that The same test as in Example 11 was conducted on this resin. The results are shown in Table 2.

Example 17 161 parts of adipic acid, 36 parts of butylene glycol, 233 parts of neopentyl glycol (molar ratio of butylene glycol and neopentyl glycol 15/85), (adipic acid component / diol component charging ratio by molar ratio) 1/2.
A resin was obtained in the same manner as in Example 11 except that 4) was used. The same test as in Example 11 was conducted on this resin. The results are shown in Table 2.

Example 18 161 parts of adipic acid, 178 parts of butylene glycol, 69 parts of neopentyl glycol (molar ratio of butylene glycol and neopentyl glycol 75/25), (charge ratio of adipic acid component / diol component by molar ratio) 1/2.
A resin was obtained in the same manner as in Example 11 except that 4) was used. The same test as in Example 11 was conducted on this resin. The results are shown in Table 2.

Comparative Example 1 The same polymerization operation as in Example 1 was carried out except that the amount of 6-nylon was changed to 1000 parts, but nylon was not dissolved in the polyester constituent components, and the nylon and polyester parts were separated to give a uniform composition. No elastomer resin could be obtained.

Comparative Example 2 A resin was obtained in the same manner as in Example 1 except that 216 parts of butylene glycol was used as the glycol component. The same test as in Example 1 was conducted on this resin. The results are shown in Table 1.

Comparative Example 3 A resin was obtained in the same manner as in Example 1 except that 150 parts of low molecular weight nylon having a reduced viscosity of 1.5 at 20 ° C. in 98% sulfuric acid was used. The same test as in Example 1 was performed on the obtained resin. The results are shown in Table 1.

Comparative Example 4 A polymerization operation was performed in the same manner as in Example 1 except that 202.25 parts of sebacic acid was used as the dicarboxylic acid and 250 parts of neopentyl glycol was used as the diol component. Due to poor compatibility between nylon and polyester constituents, the polymerization system became cloudy after a while after depressurization, and an elastic body could not be obtained.

Comparative Example 5 A resin was obtained in the same manner as in Example 1 except that solid phase polymerization was not carried out. The same test as in Example 1 was performed on the obtained resin. The results are shown in Table 1.

Comparative Example 6 A resin was obtained in the same manner as in Example 2 except that solid phase polymerization was not carried out. The same test as in Example 1 was performed on the obtained resin. The results are shown in Table 1.

Comparative Example 7 A resin was obtained in the same manner as in Example 3 except that solid phase polymerization was not carried out. The same test as in Example 1 was performed on the obtained resin. The results are shown in Table 1.

Comparative Example 8 The amount of 6-nylon was adjusted to 20 parts and solid phase polymerization was carried out at 150 ° C.
The same polymerization operation as in Example 11 was carried out except that the polymerization was carried out at 0.009 Torr for 100 hours, but no increase in viscosity was observed, and an elastomer having good elongation and strength could not be obtained. The same test as in Example 11 was conducted on this resin. The results are shown in Table 2.

Comparative Example 9 Polymerization was carried out in the same manner as in Example 11 except that 4.5 parts of pentaerythritol as a branching agent (3.0 equivalents per 100 mol of adipic acid) was added, but gelation occurred during the polymerization. Therefore, it was difficult to mold the obtained resin. The same test as in Example 11 was conducted on this resin. The results are shown in Table 2.

Comparative Example 10 Polymerization was performed in the same manner as in Example 11 except that only 238 parts of butylene glycol was used as the diol component, but the product was brittle and was inferior in rubbery properties. The same test as in Example 11 was conducted on this resin. The results are shown in Table 2.

Comparative Example 11 A resin was obtained in the same manner as in Example 11 except that solid phase polymerization was not carried out. The same test as in Example 11 was performed on the obtained resin. The results are shown in Table 2.

Comparative Example 12 A resin was obtained in the same manner as in Example 12 except that solid phase polymerization was not carried out. The same test as in Example 11 was performed on the obtained resin. The results are shown in Table 2.

Comparative Example 13 A resin was obtained in the same manner as in Example 11 except that the solid phase polymerization was carried out at 130 ° C. The same test as in Example 11 was performed on the obtained resin. The results are shown in Table 2.

Comparative Example 14 The same test as in Example 11 was carried out except that the polymerization time in the molten state was 5 hours and the solid phase polymerization was not carried out. The results are shown in Table 2.

Comparative Example 15 The same test as in Example 11 was conducted except that the solid phase polymerization was conducted at 6 Torr. The results are shown in Table 2.

Examples 19 and 20 and Comparative Examples 16 and 17 146 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
Ten minutes after the temperature was raised to 0 ° C., 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 ultimate clay [η] of polyesteramide obtained by melt polycondensation was 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) and 4,4'-diphenylmethane diisocyanate in the amounts shown in Table 3 were mixed, and this was extruded at 215 ° C. using a Brabender Plastograph extruder and cooled with water. It was cut and pelletized. The intrinsic viscosity of the obtained pellet was measured. Further, the breaking strength and breaking elongation at room temperature and 150 ° C. were measured. The measurement results are shown in Table 3.

Examples 21 and 22 and Comparative Examples 18 and 19 Instead of 150 parts of 6-nylon T850 (manufactured by Toyobo Co., Ltd.), 6-nylon A1050 (manufactured by Unitika, 98% sulfuric acid, reduced viscosity at 20 ° C. 6). .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 4,4'-diphenylmethane diisocyanate in the amounts shown in Table 3 were mixed, and this was extruded at 215 ° C. using a Brabender Plastograph extruder and cooled with water. It was cut and pelletized. The intrinsic viscosity of the obtained pellet was measured. Further, the breaking strength and breaking elongation at room temperature and 150 ° C. were measured. The measurement results are shown in Table 3.

Examples 23 and 24 and Comparative Examples 20 and 21 Adipic acid 161 parts, butylene glycol 119 parts, neopentyl glycol 137 parts (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. Ten minutes after the temperature was raised to 200 ° C., 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 limiting clay [η] of the polyesteramide obtained by melt polycondensation was measured at 30 ° C. in orthochlorophenol and the result was [η] = 1.41.
This was designated as polyesteramide (III).

Polyesteramide (III) 100
Parts and the amounts of tolylene diisocyanate shown in Table 4 were mixed, and this was extruded using a Brabender Plastograph extruder at 200 ° C., cooled with water, and then cut into pellets. 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 4.

Examples 25 and 26 and Comparative Examples 22 and 23 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 the amount of tolylene diisocyanate shown in Table 4 were mixed, and this was extruded at 200 ° C. using a Brabender Plastograph extruder, cooled with water, and then cut into pellets. 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 4.

Examples 27 and 28 and Comparative Examples 24 and 25 Polyesteramide (I) 100 used in Example 19
Parts and the amount of poly (1,3-diisopropylphenylene-2,4-carbodiimide) shown in Table 5 were mixed, and this was mixed with a Brabender Plastograph extruder at 215 ° C.
Was extruded, cooled with water and cut into pellets. The intrinsic viscosity of the obtained pellet was measured. Room temperature and 15
The breaking strength and breaking elongation at 0 ° C were measured. The measurement results are shown in Table 5.

Examples 29 and 30 and Comparative Examples 26 and 27 Polyesteramide (II) 10 used in Example 21
0 parts and poly (1,3-diisopropylphenylene-2,4-carbodiimide) in the amounts shown in Table 5 were mixed, and this was mixed with a Brabender Plastograph extruder at 215
The mixture was extruded at ℃, cooled with water and cut into pellets. The intrinsic viscosity of the obtained pellet was measured. Further room temperature and 1
The breaking strength and breaking elongation at 50 ° C. were measured. The measurement results are shown in Table 5.

Examples 31 and 32 and Comparative Examples 28 and 29 Polyesteramide (III) 1 used in Example 23
00 parts and the amount of poly (1,3-diisopropylphenylene-2,4-carbodiimide) shown in Table 6 were mixed, and this was mixed with a Brabender Plastograph extruder at 20
The mixture was extruded at 0 ° C., cooled with water, 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 6.

Examples 33 and 34 and Comparative Examples 30 and 31 Polyesteramide (IV) 10 used in Example 25
0 part and the amount of poly (1,3-diisopropylphenylene-2,4-carbodiimide) shown in Table 6 were mixed, and this was mixed with a Brabender Plastograph extruder at 200
The mixture was extruded at ℃, cooled with water and cut into pellets. The intrinsic viscosity of the obtained pellet was measured. Further room temperature and 1
The breaking strength and breaking elongation at 20 ° C. were measured. The measurement results are shown in Table 6.

Example 35 and Comparative Example 32 Polyesteramide (I) 100 used in Example 19
Parts by weight and 4,4′-diphenylmethane diisocyanate in the amounts shown in Table 7 were mixed at 190 ° C. for 2 minutes using a Brabender Plastograph extruder and extruded to obtain a resin composition. Using the obtained resin composition, a No. 3 dumbbell and a cylindrical sample were produced by injection molding according to JIS K-6301. The obtained test piece was heat-treated at 120 ° C. for 5 hours in a nitrogen atmosphere, and then the tensile rupture strength and rupture elongation at room temperature and 150 ° C., and the compression set at 70 ° C. were measured. The above results are shown in Table 7.

Example 36 and Comparative Example 33 Polyesteramide (I) 100 used in Example 19
Parts by weight and poly (1,3-diisopropylphenylene-2,4-carbodiimide) in the amounts shown in Table 7 were mixed for 2 minutes at 190 ° C. using a Brabender Plastograph extruder and extruded to obtain a resin composition. It was Using the obtained resin composition, a test piece was prepared and tested in the same manner as in Example 35. The results are shown in Table 7.

Example 37 and Comparative Example 34 Polyesteramide (II) 10 used in Example 21
0 parts and the amount of 4,4'-diphenylmethane diisocyanate shown in Table 7 were mixed with poly (1,3-diisopropylphenylene-2,4-carbodiimide), and this was mixed with a Brabender Plastograph extruder at 195 ° C. For 2 minutes and extruded to obtain a resin composition. A test piece was produced in the same manner as in Example 35 using the obtained resin composition. The obtained test piece was heated at 130 ° C under a nitrogen atmosphere for 5
After the heat treatment for an hour, the same test as in Example 35 was performed and the results are shown in Table 7.

Example 38 and Comparative Example 35 100 parts by weight of the above polyesteramide (II) and the amount of poly (1,3-diisopropylphenylene) shown in Table 7 were used.
2,4-carbodiimide) was obtained in the same manner as in Example 37 to obtain a resin composition. Example 3 of the obtained resin composition
Test pieces were prepared and tested in the same manner as in 7. The results are shown in Table 7.

Example 39 Polyesteramide (III) 1 used in Example 23
OO parts by weight and the amount of tolylene diisocyanate shown in Table 7 were measured using a Brabender Plastograph extruder for 175
The resin composition was obtained by mixing at 2 ° C. for 2 minutes and extruding. A test piece was produced in the same manner as in Example 35 using the obtained resin composition. The obtained test piece was subjected to 110 in a nitrogen atmosphere.
After performing heat treatment at 5 ° C. for 5 hours, the same test as in Example 35 was performed. The results are shown in Table 7.

Comparative Example 36 Polyesteramide (III) 1 used in Example 23
00 parts by weight and the amount of tolylene diisocyanate shown in Table 7 were applied to 10 parts using a Brabender Plastograph extruder.
The mixture was mixed at 0 ° C. for 2 minutes and extruded to obtain a resin composition. 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 7.
It was shown to.

Example 40 Polyesteramide (III) 1 used in Example 23
A resin composition was obtained in the same manner as in Example 39 except that 00 parts by weight and the amount of poly (1,3-diisopropylphenylene-2,4-carbodiimide) shown in Table 7 were used. Using the obtained resin composition, a test piece was prepared and tested in the same manner as in Example 39. The results are shown in Table 7.

Comparative Example 37 Polyesteramide (III) 1 used in Example 23
A resin composition was obtained in the same manner as in Comparative Example 36 except that 00 parts by weight and the amount of poly (1,3-diisopropylphenylene-2,4-carbodiimide) shown in Table 7 were used. 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 7.

Example 41 Polyesteramide (IV) 10 used in Example 25
A resin composition was obtained in the same manner as in Example 39 except that 0 part by weight and the amount of tolylene diisocyanate shown in Table 7 were used. Using the obtained resin composition, test pieces were prepared and tested in the same manner as in Example 39. The results are shown in Table 8.

Comparative Example 38 100 parts by weight of the above polyesteramide (IV) and the amount of tolylene diisocyanate shown in Table 8 were mixed for 2 minutes at 290 ° C. using a Brabender Plastograph extruder,
An attempt was made to make a test piece by injection molding using the resin composition obtained by extrusion, but the test piece could not be obtained because the fluidity of the resin composition was low. The results are shown in Table 8.

Example 42 100 parts by weight of the above polyesteramide (IV) and the amount of poly (1,3-diisopropylphenylene) shown in Table 8 were used.
2,4-carbodiimide) was obtained in the same manner as in Example 39 to obtain a resin composition. Example 3 using the obtained resin composition
A test piece was prepared and tested in the same manner as in No. 9. The results are shown in Table 8.

Comparative Example 39 100 parts by weight of the above polyesteramide (IV) and the amount of poly (1,3-diisopropylphenylene) shown in Table 8 were used.
2,4-carbodiimide) was obtained in the same manner as in Comparative Example 38 to obtain a resin composition. Since the obtained resin was gelled and had no fluidity, injection molding could not be performed.

Example 43 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, and 10 minutes later, 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 proceeds, 240 ° C in 20 minutes
The temperature was raised to, and depressurization was performed. Polymerization system is 1m in 10 minutes
The degree of vacuum was reached below mHg. As a result of carrying out a polycondensation reaction for 2 hours in this state, a transparent resin was obtained. The intrinsic viscosity [η] of the polyesteramide obtained by melt polycondensation was measured at 30 ° C. in orthochlorophenol [η] = 0.
It was 75. This was designated as polyesteramide (V).

100 parts by weight of the polyesteramide (V), 1,6-hexamethylene diisocyanate in the amounts shown in Table 8 and dibutyltin dilaurate (0.5 wt% of the isocyanate compound) as a catalyst were charged in a Brabender Plastograph extruder. Using the resin composition obtained by mixing for 3 minutes at 210 ° C. and extruding, a test piece similar to that of Example 35 was produced 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 35 was performed. The results are shown in Table 8.

Comparative Example 40 The test piece obtained in Example 43 was subjected to 40
After performing the heat treatment at 5 ° C. for 5 hours, the same test as in Example 35 was performed. The results are shown in Table 8.

Example 44 100 parts by weight of the above polyesteramide (V) and the amount of poly (1,3-diisopropylphenylene) shown in Table 8 were used.
A resin composition was obtained in the same manner as in Example 43 except that 2,4-carbodiimide) was used. Example 4 of the obtained resin composition
A test piece was prepared and tested in the same manner as in 3. The results are shown in Table 8.

Comparative Example 41 The test piece obtained in Example 44 was tested in the same manner as in Comparative Example 40. The results are shown in Table 8.

Example 45 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 4,4'-diphenylmethane diisocyanate in the amounts shown in Table 8 were used at 5 ° C at 210 ° C in a Brabender Plastograph extruder.
Mixing for minutes, using the resin composition obtained by extrusion,
A test piece was prepared in the same manner as in Example 43. 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 35. The results are shown in Table 8.

Example 46 Example 46 was repeated except that the amount of poly (1,3-diisopropylphenylene-2,4-carbodiimide) shown in Table 8 was used in place of 4,4'-diphenylmethane diisocyanate. The test was conducted. The results are shown in Table 8.

[0123]

[Table 1]

[0124]

[Table 2]

[0125]

[Table 3]

[0126]

[Table 4]

[0127]

[Table 5]

[0128]

[Table 6]

[0129]

[Table 7]

[0130]

[Table 8]

[0131]

According to the present invention, polyamide is dissolved in a polyester component containing a specific dicarboxylic acid and a diol as main components under specific conditions and polymerized in a uniform state to carry out solid phase polymerization and chain extension reaction. By applying it, a polyesteramide having excellent mechanical strength at room temperature and high temperature can be easily obtained. Further, after producing a molded article using a bifunctional or higher functional isocyanate compound and a bifunctional or higher functional polycarbodiimide compound, by crosslinking by heating,
It is possible to easily obtain a polyesteramide having excellent mechanical strength and creep characteristics in a range from room temperature to high temperature.

Claims (5)

[Claims] 1. A reduced viscosity with respect to 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,
Polyamide component 3 which is a 98% sulfuric acid solution, 20 ° C.)
˜250 parts by weight is dissolved, and then the esterification reaction of the polyester constituent components is performed at 150 to 230 ° C., and the obtained transparent homogeneous solution is polymerized at 200 to 260 ° C. under reduced pressure to obtain an intrinsic viscosity of 0. .2 (Ubbelohde viscous tube, ortho-chlorophenol solution, 30 ° C.) or higher, solid-phase polymerized under reduced pressure of 5 Torr or lower at a temperature between 30 ° C. lower than the melting point and the melting point. A method for producing a polyesteramide. 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 transparent homogeneous solution according to claim 1, which is polymerized under reduced pressure at 200 to 260 ° C. to obtain an intrinsic viscosity of 0.
2 (Ubbelohde viscosity tube, orthochlorophenol solution,
(30 ° C.) or higher, and 100 parts by weight of the resin composition is added with 0.1 to 10 parts by weight of a bifunctional or higher functional isocyanate compound to extend the chain, which is a method for producing a polyesteramide. 3. A transparent homogeneous solution according to claim 1, which is polymerized under reduced pressure at 200 to 260 ° C. to obtain an intrinsic viscosity of 0.
2 (Ubbelohde viscosity tube, orthochlorophenol solution,
(30 ° C.) or more, and 0.1 to 5 parts by weight of the polycarbodiimide compound is added to 100 parts by weight of the resin composition to extend the chain, thereby producing a polyesteramide. 4. A bifunctional or higher functional isocyanate compound 0.5 to 30 relative to 100 parts by weight of a resin composition having an intrinsic viscosity of 0.2 (Ubbelohde viscous tube, orthochlorophenol solution, 30 ° C.) or higher according to claim 2. 130 parts by weight
Melt-molding at ~ 280 ° C.,
A method for producing a polyesteramide, which comprises heating at a temperature of ℃ or higher and lower than a melting point to crosslink the polyesteramide. 5. A polycarbodiimide compound having a functionality of 0.3 or more with respect 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 according to claim 3. 20 parts by weight are compounded and 1
A method for producing a polyesteramide, which comprises 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.