JPH0931191A - Polyester amide and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a polyester amide which is excellent in flexibility, mechanical properties, chemical resistance and the like by using a polyester amide, possessing particular properties, comprising a particular polyester moiety and a particular polyamide moiety. SOLUTION: A polyamide component, in an amt. of 1 to 250 pts.wt., having a reduced viscosity (1g/dL soln. thereof in 98% sulfuric acid soln., 20 deg.C) of 0.5 to 0.7 is dissolved in 100 pts.wt. polyester component comprising (1) a dicarboxylic acid represented by formula I (R<1> represents a 2-8 C alkylene group), (2) a diol represented by formula II (wherein R<2> represents a 2-5 C unbranched alkylene group), and (3) a diol represented by formula III (R<3> represents a 3-5 C alkylene group having at least one alkyl group as a branch), the molar ratio of the dicarboxylic acid to the diol being (1.0:1.0) to (1.0:3.5), followed by esterification of the polyester component at 150 to 220 deg.C. The resultant transparent soln. is polymerized with the polyamide component at 170 to 220 deg.C under reduced pressure to prepare a polyester amide having an intrinsic viscosity (at 30 deg.C) of 0.1 to 0.5.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyesteramide and a method for producing the same.

[0002]

2. Description of the Related Art Vulcanized rubber moldings are used in a variety of applications in electric appliances, automobiles, industrial fields, etc. by taking advantage of their excellent properties such as rubber elasticity, flexibility, creep resistance and flexibility. in use. However, the production of vulcanized rubber requires a vulcanization step, and thus has the drawback of low production efficiency.

On the other hand, a thermoplastic elastomer exhibiting good physical properties as a rubber material at room temperature can be subjected to thermoforming such as extrusion molding and injection molding at a high temperature like a general resin, and its manufacturing process is Since it does not require a sulfurizing process, it has been attracting attention as a product having excellent productivity, energy saving property, recyclability and the like. As such a thermoplastic material, a nylon material having flexibility has been proposed.

For example, Japanese Patent Application Laid-Open No. 60-173047 discloses a technique relating to plasticized nylon in which a polyamide resin is blended with an acid-modified olefin copolymer and a plasticizer to impart flexibility. Since this plasticized nylon is blended with an acid-modified olefin, the extraction of the plasticizer in oil is suppressed, but the flexibility is Shore D.
It is inferior to elastomers having a hardness of 50 or less, and has a high glass transition point, so that it also has problems such as inferior low temperature impact resistance and low temperature properties such as elongation.

Japanese Unexamined Patent Publication (Kokai) No. 61-247732 discloses a technique relating to a polyether amide obtained by polymerizing caprolactam in the presence of a polyether segment having a molecular weight of 800 to 5000, as a nylon material which has solved such a problem. Is disclosed. However, since this polyether amide contains a high proportion of polyether segments, it does not have sufficient chemical resistance and cannot be used in applications where excellent chemical resistance originally possessed by nylon is required. Further, the heat deterioration resistance is low, for example, 1
Unable to withstand continuous use at 50 ° C.

On the other hand, the polyesteramide elastomer has been variously studied as a nylon material which is excellent in chemical resistance and is softer than plasticized nylon. Japanese Patent Publication No. 61-36858 discloses a technique of producing a polyesteramide elastomer from a dicarboxylic acid and a diol. However, this production method requires the use of a saturated dimer fatty acid as the dicarboxylic acid, and the reaction time is long, so it is not suitable for industrial production.

Japanese Patent Publication No. 46-2268 discloses a technique for producing a polyesteramide elastomer by copolymerizing polyamide and polyester. This production method requires a long time for polymerization, and since sebacic acid is the main component, it easily swells in solvents such as oil and gasoline, and has a problem that chemical resistance is reduced. ing.

Further, since the polyamide used in this production method is a low molecular weight substance, the polyesteramide elastomer obtained from such a polyamide lacks high-temperature properties and, particularly, has high mechanical strength at high temperatures. It also has problems such as not having it.

As a method for producing a polyesteramide elastomer, there is a method in which a polyesteramide having a specific composition and a molecular weight and a diisocyanate are used as constituents to increase the molecular weight without lowering the blocking property.

However, this method is not sufficient as an efficient production method, and although polyesteramide elastomers are attracting attention as a material excellent in mechanical strength, chemical resistance, flexibility, etc., they are excellent. Applications have not been developed that take advantage of the characteristics.

[0011]

SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to provide a polyesteramide having excellent flexibility, mechanical properties, chemical resistance and the like, and a method for producing the same.

[0012]

Means for Solving the Problems The gist of the present invention is that a polyesteramide is represented by at least one dicarboxylic acid represented by the following general formula (1) and the following general formula (2). At least one selected from diols
And at least one selected from the diols represented by the following general formula (3), and the molar ratio of the dicarboxylic acid and the diol is 1.0: 1.0 to 1.0: 3.5. 100 parts by weight of polyester component, reduced viscosity (1 g / d
L98% sulfuric acid solution, 20 ° C.) 1 to 250 parts by weight of a polyamide component having a concentration of 0.5 to 7.0 are dissolved, and then the polyester component is subjected to an esterification reaction at 150 to 220 ° C., and then obtained. Clear transparent homogeneous solution under reduced pressure
It is obtained by polymerizing with the above-mentioned polyamide component at 0 to 220 ° C, and has an intrinsic viscosity (Ubbelohde viscous tube, orthochlorophenol solution, 30 ° C) of 0.1 to 0.5.

[0013] ^{HOOC-R 1 -COOH (1)} ( wherein R ¹ represents an alkylene group having 2 to 8 carbon ^{atoms.) HO-R 2 -OH (} 2) ( wherein R ² is 2 carbon atoms represents a 5 unbranched alkylene ^{group.) HO-R 3 -OH (} 3) ( wherein R ³ represents an alkylene group having 3 to 8 carbon atoms and having at least one alkyl group as a branch.)

The dicarboxylic acid represented by the above general formula (1) used in the present invention is preferably an aliphatic dicarboxylic acid such as succinic acid, glutaric acid, adipic acid,
Examples thereof include pimelic acid, suberic acid, azelaic acid and sebacic acid. Adipic acid is more preferable because it has high reactivity and is inexpensive. In the present invention, a dicarboxylic acid other than the above aliphatic dicarboxylic acid may be used as long as it does not impair the physical properties of the molded product obtained from the polyesteramide of the present invention.

The diol represented by the general formula (2) used in the present invention is preferably an aliphatic diol,
Examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and the like. Ethylene glycol is particularly preferable because it is highly reactive and has a high polymerization rate to prevent thermal deterioration and can reduce the polymerization cost.

The diol represented by the above general formula (3) used in the present invention is preferably an aliphatic diol,
For example, 1,2-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1-
Methyl-2-methyl-1,2-ethanediol, 1,1
-Dimethyl-1,2-ethanediol, 1-ethyl-
1,2-ethanediol, 2,2-dimethyl-1,3-
Examples include propane diol and neopentyl glycol. 1,2-Propanediol is particularly preferable because it is highly reactive and can prevent thermal deterioration due to a high polymerization rate and can reduce the polymerization cost.

The polyester component used in the present invention is
At least one selected from the dicarboxylic acids represented by the general formula (1), at least one selected from the diols represented by the general formula (2), and the general formula (3). At least one selected from diols
It consists of seeds.

The diol represented by the general formula (3) is
Since it has at least one alkyl group as a branch, crystallization of the polyester component is suppressed, and the polyesteramide of the present invention has improved flexibility. When the diol represented by the general formula (3) is not added, the polyester component is crystallized, so that the polyesteramide of the present invention has high hardness and poor elastomer properties.

The molar ratio of dicarboxylic acid to diol in the above polyester component is 1.0: 1.0 to 1.0:
3.5. When the amount of the diol is less than 1.0 mol with respect to 1.0 mol of the dicarboxylic acid, the esterification reaction does not proceed efficiently, and 3.5 mol of the diol with respect to 1.0 mol of the dicarboxylic acid. If it exceeds, the cleavage reaction of polyamide tends to occur due to excess diol component,
The polyester amide of the present invention has a reduced block property, is inferior in heat resistance, and is also disadvantageous in terms of cost. Therefore, it is limited to the above range. Preferably, 1:
It is 1.2 to 1: 3.

In the present invention, a branching agent such as a polyol, a polycarboxylic acid or an oxyacid is added to the above polyester component to increase the molecular weight of the polyesteramide of the present invention, increase its viscosity, shorten the polymerization time, etc. May be planned.

The above-mentioned polyol is not particularly limited,
For example, glycerin, trimethylolpropane, pentaerythritol and the like can be mentioned. These may be used alone or in combination of two or more.

The polycarboxylic acid is not particularly limited, and examples thereof include hemimellitic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,1,2,2-ethanetetracarboxylic acid and the like. These may be used alone or in combination of two or more.

The oxyacid is not particularly limited, and examples thereof include citric acid, tartaric acid, 3-hydroxyglutaric acid,
4-β-hydroxyethylphthalic acid and the like can be mentioned. These may be used alone or in combination of two or more.

The amount of the branching agent added is preferably 0.1 to 2.5 mol per 100 mol of the dicarboxylic acid component. When the amount is less than 0.1 mol, the molecular weight of the polyesteramide of the present invention does not increase, so that the desired mechanical strength cannot be obtained, and when it exceeds 2.5 mol, gelation occurs.

The polyamide component used in the present invention has a reduced viscosity (1 g / dL 98% sulfuric acid solution, 20 ° C.) of 0.5.
Is ~ 7.0. If it is less than 0.5, the polyesteramide of the present invention will have insufficient mechanical strength at high temperatures, and if it exceeds 7.0, the solubility for the above-mentioned polyester component will decrease and synthesis will be difficult. Is limited to the above range.

The polyamide component has an amide bond in the polymer main chain, can be melted by heating, and has a weight ratio of (toluene) / (isooctane) = 1/1 as a swelling degree in a mixed solvent. Weight change rate is 0-5.
It is preferably 0%. The molecular weight of the polyamide component is preferably 10,000 to 60,000, and more preferably
It is 20,000 to 50,000.

The polyamide used for the above polyamide component is not particularly limited, and examples thereof include 4-nylon and 6
-Nylon, 6,6-Nylon, 11-Nylon, 12
-Aliphatic nylons such as nylon, 6,10-nylon and 6,12-nylon; acids such as isophthalic acid and terephthalic acid and metaxylylenediamine, 2,2-bis (paraaminocyclohexyl) propane, 4,4 ' -Polycondensation with amine compounds such as aromatic amines such as diaminodicyclohexylmethane, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, aliphatic amines and side chain-substituted aliphatic amines Examples include the polyamides.

The polyester amide of the present invention comprises 100 parts by weight of the above polyester component and 1 to 1 parts of the above polyamide component.
After dissolving 250 parts by weight, the polyester component is subjected to an esterification reaction at 150 to 220 ° C., and then,
The obtained transparent homogeneous solution is 170-220 degreeC under reduced pressure.
It is obtained by polymerizing with the above polyamide component.

In the present invention, when the blending amount of the above polyamide component is less than 1 part by weight relative to 100 parts by weight of the above polyester component, polyamide crystals are not formed in the polyesteramide of the present invention, and the present invention When the polyesteramide of (1) is further polymerized to obtain a molded product, mechanical strength is insufficient, and when it exceeds 250 parts by weight, it becomes difficult to dissolve in the above polyester component, and the polyesteramide of the present invention is excellent. Since it does not become an elastomer having rubber elasticity, it is limited to the above range. Preferably,
3 to 18 relative to 100 parts by weight of the polyester component
Parts by weight.

The polyesteramide of the present invention has an intrinsic viscosity (Ubbelohde viscosity tube, orthochlorophenol solution, 3
0 degreeC) is 0.1-0.5. When it is less than 0.1, for example, a molded product obtained from the above polyester amide when chain extension is performed using an isocyanate compound, a polycarbodiimide compound or the like to increase the molecular weight and further improve mechanical strength, heat resistance and the like. Is inferior in high-temperature physical properties, and if it exceeds 0.5, the chain extension reaction does not proceed quantitatively, so it is limited to the above range.

The above-mentioned isocyanate compound is not particularly limited as long as it has two or more isocyanate groups in the same molecule, and chain extension can be efficiently carried out while avoiding gelation of the polyesteramide. Preferably, diisocyanate and the like can be mentioned.

The amount of the above isocyanate compound added is 0.1 to 3 with respect to 100 parts by weight of the above polyesteramide.
0 parts by weight is preferred. 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 30 parts by weight, the flexibility of the molded product obtained by further polymerizing the polyesteramide of the present invention is lowered.

The amount of the polycarbodiimide compound added is 0.
1 to 20 parts by weight is preferred. 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 20 parts by weight, the flexibility of the molded product obtained by further polymerizing the polyesteramide of the present invention decreases.

In the present invention, since the reaction proceeds efficiently, it is preferable to dissolve the above polyamide component in the above polyester component at 150 to 220 ° C. to obtain a transparent homogeneous solution and then carry out the above esterification reaction. .

The reaction temperature of the ester reaction is 150 to
It is 220 ° C. When the temperature is lower than 150 ° C, it becomes difficult to dissolve the polyamide component, and when the temperature is higher than 220 ° C, the polyamide component is affected by thermal deterioration such as coloring. Since there are applications in which coloring is avoided, it is preferable to reduce coloring as much as possible.

In the present invention, after the ester reaction proceeds and the reaction solution becomes a transparent homogeneous solution, the transparent homogeneous solution is polymerized with the polyamide component at 170 to 220 ° C. under reduced pressure. If the temperature is lower than 170 ° C, the reaction rate is low and the polymerization viscosity is high, which makes efficient polymerization difficult. If the temperature is higher than 220 ° C, thermal deterioration such as coloring is affected. . The polymerization reaction is 0 to
It is preferably performed at 5 mmHg.

In the present invention, when carrying out the above-mentioned polymerization reaction, a catalyst generally used in producing polyester may be added. The catalyst is not particularly limited, for example, lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tungsten, tin, lead, antimony, arsenic,
Metals such as cerium, boron, cadmium, manganese and zirconium; organometallic compounds thereof; organic acid salts thereof; metal alkoxides thereof; metal oxides thereof and the like. These may be used alone or in combination of two or more.

Preferably, tetrabutoxy titanium, calcium acetate, diacyl first tin, tetraacyl second tin, dibutyl tin oxide, dibutyl tin dilaurate, dimethyl tin maleate, tin dioctanoate, tin tetraacetate, triisobutyl aluminum, tetrabutyl titanate, Tetrapropoxy titanate,
Examples thereof include titanium (oxy) acetylacetonate, germanium dioxide, tungstic acid, antimony trioxide and the like. These may be used alone or in combination of two or more.

In the present invention, a stabilizer may be added when the above polymerization reaction is carried out. The stabilizer is not particularly limited and includes, for example, 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]
Hindered phenolic antioxidants such as 2,4,8,10-tetraoxaspiro [5,5] undecane; tris (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-
Examples of the heat stabilizer include 3,3'-thiodipropionate, pentaerythyryltetrakis (3-laurylthiopropionate), and ditridecyl-3,3'-thiodipropionate. These may be used alone,
Two or more kinds may be used in combination.

The polyesteramide of the present invention may be increased in molecular weight by solid phase polymerization to further improve mechanical strength, heat resistance and the like. The solid phase polymerization temperature is preferably (temperature lower than the melting point of the polyesteramide by 30 ° C.) to (melting point of the polyesteramide). When the polymerization temperature is lower than (temperature lower than the melting point of the polyesteramide by 30 ° C.), the polymerization rate is slow and progress of the polymerization becomes difficult, and when higher than (melting point of the polyesteramide), the polyesteramide has Melting occurs. More preferably, the temperature is (15 ° C lower than the melting point of the polyesteramide) to (5 ° C lower than the melting point of the polyesteramide).

The polymerization pressure of the above polymerization reaction is 0 to 5 Tor.
r is preferred. When it exceeds 5 Torr, the progress of polymerization becomes difficult. More preferably, it is 0 to 1 Torr.

The polyesteramide of the present invention 2 is at least one selected from dicarboxylic acids represented by the following general formula (1) and at least one selected from diols represented by the following general formula (2). And 2,2-dimethyl-
A polyester amide comprising a polyester component comprising 1,3-propanediol and a polyamide component having a reduced viscosity (1 g / dL 98% sulfuric acid solution, 20 ° C.) of 0.5 to 7.0, wherein the polyamide component Has an intrinsic viscosity of 3 to 30% by weight (Ubbelohde viscous tube, orthochlorophenol solution, 30 ° C) of 0.1 to 0.5.
It is something that is.

HOOC-R ¹ -COOH (1) (In the formula, R ¹ represents an alkylene group having 2 to 8 carbon atoms.) HO-R ² -OH (2) (In the formula, R ² is 2 carbon atoms. Represents an unbranched alkylene group of ~ 5.)

The diol represented by the above general formula (2) is not particularly limited, and preferably ethylene glycol, 1,2-propanediol, 1,4-butanediol and the like, since they have a high polymerization reaction rate. To be

When 2,2-dimethyl-1,3-propanediol is used as the diol represented by the above general formula (2), the melting point of the polyamide crystal is high and the amide obtained from the polyesteramide of the present invention 2 is used. The obtained molded article has excellent high temperature physical properties.

In the present invention 2, for example, a branching agent such as a polyol, a polycarboxylic acid or an oxy acid is added to the above polyester component to increase the molecular weight of the polyester amide of the present invention 2, increase the viscosity, and increase the polymerization time. It may be shortened.

As the above-mentioned polyol, in addition to the polyol used in the present invention 1, for example, 1,2,6-hexanetriol, sorbitol, 1,1,4,4-tetrakishydroxymethylcyclohexane, tris (2-
Hydroxyethyl) isocyanurate, dipentaerythritol and the like can be mentioned.

The polyesteramide of the second aspect of the present invention contains the polyamide component in an amount of 3 to 30% by weight. If it is less than 3% by weight, the mechanical strength of the molded product obtained from the above polyesteramide will be insufficient, and if it exceeds 30% by weight, the hard segment content will increase and become hard, so it is limited to the above range. More preferably, 5 to 1
8% by weight.

The method for producing the polyesteramide of the present invention 3 is selected from at least one dicarboxylic acid represented by the general formula (1) and diol represented by the general formula (2). It is composed of at least one kind and 2,2-dimethyl-1,3-propanediol, and the molar ratio of dicarboxylic acid and diol is 1.0: 1.0 to 1.
100 parts by weight of the polyester component of 0: 3.5 has a reduced viscosity of 0.5 (1 g / dL 98% sulfuric acid solution, 20 ° C.).
After dissolving 1 to 250 parts by weight of the polyamide component which is ˜7.0, the polyester component is added at 150 to 230 ° C.
The esterification reaction is then carried out, and then the obtained transparent homogeneous solution is polymerized with the above polyamide component at 200 to 260 ° C. under reduced pressure.

In the present invention 3, the molar ratio of dicarboxylic acid to diol in the polyester component is 1.0:
It is 1.0 to 1.0: 3.5. The dicarboxylic acid 1.
When the amount of the diol is less than 1.0 mol per 0 mol, the esterification reaction does not proceed efficiently, and when the amount of the diol exceeds 3.5 mol per 1.0 mol of the dicarboxylic acid, an excess amount is obtained. The diol component easily causes a cleavage reaction of the polyamide, the polyester amide of the present invention has a reduced block property, is inferior in heat resistance, and is also disadvantageous in terms of cost, and therefore is limited to the above range. It is preferably 1: 1.2 to 1: 3.

The amount of the polyamide component added is 1 to 250 parts by weight based on 100 parts by weight of the polyester component. If the amount is less than 1 part by weight, mechanical strength is insufficient when the polyesteramide of the present invention 2 is further polymerized to obtain a molded product, and if it exceeds 250 parts by weight, it becomes difficult to dissolve the polyester component. However, since the above polyesteramide cannot be quantitatively obtained, it is limited to the above range. It is preferably 3 to 18 parts by weight.

In the present invention 3, since the reaction proceeds efficiently, the above polyamide component may be dissolved in the above polyester component at 150 to 230 ° C. to obtain a transparent homogeneous solution, and then the above esterification reaction may be carried out. preferable.

The reaction temperature of the above ester reaction is 150 to
It is 230 ° C. When the temperature is lower than 150 ° C, it becomes difficult to dissolve the polyamide component, and when the temperature is higher than 230 ° C, thermal deterioration such as coloring is affected, so the content is limited to the above range. Since there are applications in which coloring is avoided, it is preferable to reduce coloring as much as possible.

In the third aspect of the present invention, after the ester reaction proceeds and the reaction solution becomes a transparent homogeneous solution, the transparent homogeneous solution is polymerized under reduced pressure at 200 to 260 ° C. with the polyamide component. If the temperature is lower than 200 ° C, the reaction rate is low and the polymerization viscosity becomes high to make efficient polymerization difficult. If the temperature is higher than 260 ° C, thermal deterioration such as coloring is affected. . The polymerization reaction is 0
It is preferably performed at ˜5 mmHg.

The polyesteramide of the present invention can be molded into a molded product after being made to have a high molecular weight, and then molded by, for example, press molding, extrusion molding, injection molding, blow molding, injection compression molding or the like.

Examples of the above-mentioned molded products include automobile parts, electric / electronic parts, industrial parts, sports goods, medical goods and the like. The above-mentioned automobile parts are not particularly limited, and examples thereof include boots such as constant velocity joint boots and rack and opinion boots; ball joint seals, safety belt parts, bumper facias, emblems, moldings and the like. The electric / electronic component is not particularly limited, and examples thereof include wire coating materials, gears, rubber switches, membrane switches, tact switches, O-
Examples include rings.

The industrial parts are not particularly limited, and examples thereof include hydraulic hoses, coil tubes, sealing materials, packings, V-belts, rolls, vibration-damping and damping materials, shock absorbers, couplings, diaphragms and the like.
The sports equipment is not particularly limited, and examples thereof include shoe soles and balls for ball games. The medical supplies are not particularly limited, and examples thereof include medical tubes, infusion bags, catheters and the like. In addition to the above, it is suitable for elastic fibers; elastic sheets; composite sheets; hot melt adhesives; materials for alloy components such as other resins and rubber components.

[0058]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Examples 1 to 8 and Comparative Examples 1 to 11 Various physical properties were measured by the following methods. Polyamide amide content of polyester amide Calculated from the weight of the polyamide amide at the time of charging relative to the weight of the produced polyester amide. Intrinsic viscosity [η] It was measured at 30 ° C. in an o-chlorophenol solvent using an Ubbelohde viscosity tube. The molecular weight of the obtained products was compared using these measured values. Measurement of Melting Point and Glass Transition Point Measurement was performed at a temperature rising rate of 10 ° C./min using a differential scanning calorimeter (hereinafter referred to as “DSC”). The melting point was obtained from the peak derived from the polyamide component.

Example 1 190 parts by weight of adipic acid, 97 parts by weight of ethylene glycol, 119 parts by weight of 1,2-propanediol (the adipic acid component / diol component charging ratio was 1/2.
4), Toyobo Co., Ltd. 6-nylon (T850, 98% sulfuric acid, reduced viscosity at 20 ° C., 3.5) 26 parts by weight (6.4 parts by weight based on 100 parts by weight of polyester component charged), catalyst As a stabilizer, 0.40 part by weight of titanium tetrabutoxy and 1,3,5-trimethyl-2,4,6 as a stabilizer.
0.4 parts by weight of tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (2,4-di-
0.4 part by weight of t-butylphenyl) phosphite was added, and the reaction system was heated to 200 ° C. under nitrogen 10 minutes later, nylon was dissolved and a transparent solution was obtained. The mixture was kept at this temperature for 1 hour to carry out an esterification reaction. The progress of the esterification reaction was confirmed by measuring the amount of distilled water. After the esterification reaction proceeded, 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 conducting polycondensation reaction for 30 minutes in this state, the transparent resin 2
59 parts by weight were obtained. The results of each measurement are shown in Table 1.

Example 2 97 parts by weight of ethylene glycol and 2, 2 were used as the diol component.
162 parts by weight of 2-dimethyl-1,3-propanediol (adipic acid component / diol component is charged at a molar ratio of 1).
/2.4), 28 parts by weight of 6-nylon (5.4 parts by weight per 100 parts by weight of the polyester component charged),
Polymerization was conducted in the same manner as in Example 1 except that 0.80 part by weight of tetrabutoxytitanium as a catalyst was used to obtain 279 parts by weight of a resin. The results of each measurement are shown in Table 1.

Example 3 176 parts by weight of 1,4-butanediol as a diol component,
203 parts by weight of 2,2-dimethyl-1,3-butanediol (addition ratio of adipic acid component / diol component is 1/3 in molar ratio), and 8.3 parts by weight of 6-nylon (preparation amount of polyester component 100) 1.4 parts by weight with respect to parts by weight),
Polymerization was carried out in the same manner as in Example 1 except that 0.40 part by weight of a catalyst, tetrabutoxytitanium, and the polycondensation reaction under reduced pressure were carried out for 1 hour, to obtain 277 parts by weight of a resin.
The results of each measurement are shown in Table 1.

Example 4 59 parts by weight of 1,2-propanediol and 81 parts by weight of 2,2-dimethyl-1,3-propanediol were used as the diol component (the adipic acid component / diol component charging ratio was 1 / molar). 1.2) and 6-nylon was 660 parts by weight (200 parts by weight per 100 parts by weight of the polyester component charged), polymerization was carried out in the same manner as in Example 2 to obtain 920 parts by weight of the resin. Obtained. The results of each measurement are shown in Table 1.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that the esterification reaction temperature was 140 ° C. and the polycondensation reaction under reduced pressure was 180 ° C. The reaction did not proceed.

Comparative Example 2 A reddish brown resin was obtained by the same polymerization procedure as in Example 2 except that the esterification reaction temperature was 240 ° C. and the polycondensation reaction under reduced pressure was 260 ° C. Was given.
The results of each measurement are shown in Table 1.

Comparative Example 3 The same polymerization operation as in Example 3 was carried out except that 6-nylon was 2.8 parts by weight (0.5 parts by weight based on 100 parts by weight of the polyester component charged). In the DSC measurement, a crystal melting peak derived from the ester component was confirmed, and no crystal melting peak derived from the amide component was observed. The results of each measurement are shown in Table 1.

Comparative Example 4 A polymerization operation was performed in the same manner as in Example 4 except that the amount of 6-nylon was 990 parts by weight (300 parts by weight based on 100 parts by weight of the polyester component charged), but the polyamide was dissolved. No, the polymerization reaction did not proceed.

Comparative Example 5 97 parts by weight of ethylene glycol was used as the diol component and 1,4
-Butanediol 141 parts by weight (adipic acid component / diol component charge ratio of 1 / 2.4) and 27 parts by weight of 6-nylon (6.3 parts by weight per 100 parts by weight charge of polyester component). Polymerization operation was performed in the same manner as in Example 1 except that the amount of the resin was 269 parts by weight.
In the DSC measurement, a crystal melting peak derived from the polyester component was confirmed. The results of each measurement are shown in Table 1.

Example 5 190 parts by weight of adipic acid, 1,2-propanediol 1
19 parts by weight, 162 parts by weight of 2,2-dimethyl-1,3-propanediol (mixing ratio of adipic acid component / diol component is 1 / 2.4), Toyobo Co., Ltd. 6-nylon (T850, Reduced viscosity at 20 ° C. in 98% sulfuric acid 3.
5) 14 parts by weight, tetrabutoxy titanium as a catalyst 0.
05 parts by weight and 1,3,5-trimethyl- as a stabilizer
0.4 parts by weight of 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (2,4-di-t-butylphenyl) phosphite.
After adding 4 parts by weight and heating the reaction system to 200 ° C. under nitrogen, 10 minutes later, nylon was dissolved and a transparent solution was obtained.
The mixture was kept at this temperature for 1 hour to carry out an esterification reaction.
The progress of the esterification reaction was confirmed by measuring the amount of distilled water. After the progress of the esterification reaction, the temperature was raised to 240 ° C. in 20 minutes, and the pressure was reduced. Polymerization system is 1
In 0 minutes, the degree of pressure reduction reached 1 mmHg or less. 3 in this state
A polycondensation reaction was performed for 0 minutes to obtain a resin. The results of each measurement are shown in Table 2.

Example 6 141 parts by weight of 1,4-butanediol was added as a diol component,
2,2-dimethyl-1,3-propanediol was used in an amount of 162 parts by weight (the adipic acid component / diol component charge ratio was 1 / 2.4 in a molar ratio), and 6-nylon was 81 parts by weight. Polymerization was carried out in the same manner as in Example 5 to obtain a resin. The results of each measurement are shown in Table 2.

Example 7 121 parts by weight of ethylene glycol and 203 parts by weight of 2,2-dimethyl-1,3-propanediol were used as the diol component (the adipic acid component / diol component charging ratio was 1/3 by mole), Polymerization was performed in the same manner as in Example 5 except that 28 parts by weight of 6-nylon was used to obtain a resin. The results of each measurement are shown in Table 2.

Example 8 70 parts by weight of 1,4-butanediol was added as a diol component,
Except that the amount of 2,2-dimethyl-1,3-propanediol was 81 parts by weight (the adipic acid component / diol component charging ratio was a molar ratio of 1 / 1.2) and 6-nylon was 30 parts by weight. Polymerization was carried out in the same manner as in Example 5 to obtain a resin. The results of each measurement are shown in Table 2.

Comparative Example 6 The same polymerization operation as in Example 5 was carried out except that the amount of 6-nylon charged was 2.4 parts by weight (0.5 parts by weight based on 100 parts by weight of polyester component). To obtain a resin. In the DSC measurement, a crystal melting peak derived from the polyester component was confirmed, and a crystal melting peak derived from the amide component was unclear. The results of each measurement are shown in Table 2.

Comparative Example 7 A polymerization operation was performed in the same manner as in Example 6 except that the amount of 6-nylon charged was 1300 parts by weight (264 parts by weight based on 100 parts by weight of polyester component). Was not dissolved, and the polymerization reaction did not proceed.

Comparative Example 8 A diol component was added with 161 parts by weight of ethylene glycol, 2,
271 parts by weight of 2-dimethyl-1,3-propanediol (the adipic acid component / diol component charging ratio is 1 in molar ratio).
A resin was obtained by carrying out the same polymerization operation as in Example 7 except that the procedure was changed to / 4). In the DSC measurement, a crystal melting peak derived from the ester component was confirmed, and no crystal melting peak derived from the amide component was observed. The results of each measurement are shown in Table 2.

Comparative Example 9 47 parts by weight of 1,4-butanediol was added as a diol component,
The same polymerization operation as in Example 8 was carried out except that the amount of 2,2-dimethyl-1,3-propanediol was 81 parts by weight (the molar ratio of the adipic acid component / diol component was 1 / 0.5). However, the polymerization reaction did not proceed.

Comparative Example 10 97 parts by weight of ethylene glycol was used as the diol component, and 1,2
A resin was obtained by performing the same polymerization operation as in Example 5 except that the amount of propanediol was 119 parts by weight and the amount of 6-nylon charged was 12 parts by weight. The melting point of the obtained resin was low and the heat resistance was lowered. The results of each measurement are shown in Table 2.

Comparative Example 11 97 parts by weight of ethylene glycol was used as the diol component, and 1,4
A resin was obtained by performing the same polymerization operation as in Example 5 except that 141 parts by weight of butanediol and 13 parts by weight of 6-nylon were charged. In the DSC measurement, a crystal melting peak derived from the polyester component was confirmed. The results of each measurement are shown in Table 2.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

EFFECT OF THE INVENTION Since the polyesteramide of the present invention has the above-mentioned constitution, it is excellent in flexibility, mechanical properties, chemical resistance and the like, and is suitable for electric equipment field, automobile field, industrial field and the like.

Claims (3)

[Claims] 1. At least one selected from dicarboxylic acids represented by the following general formula (1) and the following general formula (2):
And at least one selected from the diols represented by the following general formula (3), and the molar ratio of the dicarboxylic acid and the diol is 1.0: 1. 100 parts by weight of a polyester component of 0 to 1.0: 3.5 has a reduced viscosity (1 g / dL98
% Sulfuric acid solution, 20 ° C.) 1 to 250 parts by weight of a polyamide component having a concentration of 0.5 to 7.0 are dissolved, and then the polyester component is subjected to an esterification reaction at 150 to 220 ° C.,
Then, the obtained transparent homogeneous solution was subjected to 170 to 2 under reduced pressure.
A polyesteramide having an intrinsic viscosity (Ubbelohde viscous tube, orthochlorophenol solution, 30 ° C.) of 0.1 to 0.5 obtained by polymerization with the polyamide component at 20 ° C. ^{HOOC-R 1 -COOH (1)} ( wherein R ¹ is,. Represents an alkylene group having 2 to 8 carbon ^{atoms) HO-R 2 -OH (2} ) ( wherein R ² is 2 to 5 carbon atoms represents an unbranched alkylene ^{group.) HO-R 3 -OH (} 3) ( wherein R ³ represents an alkylene group having 3 to 8 carbon atoms and having at least one alkyl group as a branch.) 2. At least one selected from dicarboxylic acids represented by the following general formula (1) and the following general formula (2):
A polyester component composed of at least one selected from diols represented by and 2,2-dimethyl-1,3-propanediol, and a reduced viscosity (1 g / dL 98% sulfuric acid solution, 20 ° C.) of 0.5 to A polyesteramide comprising a polyamide component of 7.0, wherein the content of the polyamide component is 3 to 30% by weight (Ubbelohde viscous tube, orthochlorophenol solution, 30
C.) is 0.1 to 0.5, a polyesteramide. ^{HOOC-R 1 -COOH (1)} ( wherein R ¹ is,. Represents an alkylene group having 2 to 8 carbon ^{atoms) HO-R 2 -OH (2} ) ( wherein R ² is 2 to 5 carbon atoms Represents an unbranched alkylene group.) 3. At least one selected from dicarboxylic acids represented by the following general formula (1) and the following general formula (2):
Of at least one selected from the diols represented by the formula 2, and 2,2-dimethyl-1,3-propanediol, and the molar ratio of the dicarboxylic acid to the diol is 1.0: 1.
Reduced viscosity (1 g / dL 98% sulfuric acid solution, 20 ° C.) in 100 parts by weight of a polyester component of 0 to 1.0: 3.5
After dissolving 1 to 250 parts by weight of the polyamide component having 0.5 to 7.0, the polyester component is added to 150 to
The method for producing a polyesteramide according to claim 2, wherein an esterification reaction is performed at 230 ° C., and then the obtained transparent homogeneous solution is polymerized with the polyamide component at 200 to 260 ° C. under reduced pressure. ^{HOOC-R 1 -COOH (1)} ( wherein R ¹ is,. Represents an alkylene group having 2 to 8 carbon ^{atoms) HO-R 2 -OH (2} ) ( wherein R ² is 2 to 5 carbon atoms Represents an unbranched alkylene group.)