JP3448398B2 - Polyesteramide and method for producing the same - Google Patents

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 Nylon materials such as polyether amide and polyester amide are recyclable and have excellent flexibility, so they can be used as alternative materials to vulcanized rubber in the fields of electrical equipment and automobile industry. Is expected. At present, vulcanized rubber and plasticized nylon are used for these applications, but it is difficult to recycle and the vulcanized rubber, which has a long manufacturing and processing process and may cause environmental pollution, is replaced with a thermoplastic elastomer. The needs to try are high.

Japanese Patent 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. However, with this technique, although the effect of suppressing the extraction of the plasticizer in the oil can be seen due to the addition of 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 this plasticized nylon has a high glass transition temperature, it has an inherent problem that it is inferior in low temperature properties such as low temperature impact resistance and elongation.

Japanese Unexamined Patent Publication No. 61-247732 discloses a technique relating to polyetheramide, which is a flexible nylon material that overcomes the above-mentioned problems. This technique synthesizes a polyetheramide by polymerizing caprolactam in the presence of a polyether segment having a molecular weight of 800 to 5000. The polyetheramide thus obtained has a considerable proportion of polyether segments. Since the chemical resistance inherent in nylon is lowered, it cannot be used in applications requiring chemical resistance. In addition, the heat deterioration resistance is low, and for example, it cannot withstand continuous use at 150 ° C.

Polyesteramides have the property of being more resistant to chemicals than polyetheramides and more flexible than plasticized nylon. Japanese Patent Publication No. 61-36858 discloses a method for producing a polyesteramide. However, this technique has drawbacks such as the need to use a saturated dimer fatty acid and a long reaction time, and is not practical as a method for industrially obtaining a polyesteramide.

Japanese Patent Publication No. 46-2268 discloses a method for producing a copolymer of polyamide and polyester. However, in this technique, it takes a long time to polymerize, and since polyesteramide is produced with sebacic acid as a main component, it easily swells in a solvent such as oil or gasoline, which causes problems such as deterioration in chemical resistance. Have

Further, the nylon used in this production method is a low molecular weight substance, and when a polyesteramide is produced using the low molecular weight nylon, the high temperature characteristics are insufficient and the mechanical strength is particularly high. Can't get enough.

[0008]

In view of the above, it is an object of the present invention to provide a polyester amide excellent in flexibility, mechanical strength, chemical resistance and heat deterioration resistance during polymerization, and a method for producing the same. And

[0009]

Means for Solving the Problems The gist of the present invention is to use polyesteramide as at least one dicarboxylic acid represented by the general formula (1), ethylene glycol and 1,2.
A polyester component consisting of a diol used in combination with propanediol, and a reduced viscosity (1 g / d
L98% sulfuric acid solution, 20 ° C.) consisting of a polyamide component of 0.5 to 7, and the content of the polyamide component is 3 to
It is 30% by weight, and the composition has an intrinsic viscosity (Ubbelohde viscous tube, orthochlorophenol solution, 30 ° C.) of 0.1 to 0.5. ^{HOOC-R 1 -COOH (1)} ( wherein, R ¹ represents an alkylene group having 2 to 8 carbon atoms.)

The dicarboxylic acid used in the present invention is not particularly limited, and examples thereof include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. . Preferred is adipic acid, which is highly reactive and inexpensive.

[0011] The onset Oite to Ming, ethylene glycol and 1,2-propanediol are used as the diol. This combination is more reactive and has a higher polymerization rate than the combination of other diols, so the molecular weight increases most under the same conditions, and thermal deterioration can be prevented.

A branching agent such as a polyol, a polycarboxylic acid or an oxyacid may be added to the polyester component of the present invention for the purpose of increasing the molecular weight of the polyesteramide, increasing the viscosity and shortening the polymerization time. The polyol is not particularly limited, and examples thereof include trimethylolethane, trimethylolpropane, and pentaerythritol. The polycarboxylic acid is not particularly limited, for example, hemimellitic acid, trimellitic acid, trimesic acid,
Examples include pyromellitic acid and 1,1,2,2-ethanetetracarboxylic acid. These may be used alone,
You may use 2 or more types together.

The above 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 above branching agent is preferably used in an amount of 0.1 to 2.5 mol per 100 mol of the dicarboxylic acid used in the present invention. 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.

The polyamide used in the present invention has a reduced viscosity (1 g / dL 98% sulfuric acid solution, 20 ° C.) of 0.5 to
7 If it is less than 0.5, the mechanical strength of the obtained resin at high temperature will be insufficient, and if it exceeds 7, the solubility of the polyamide in the polyester component will decrease and synthesis will be difficult. To be done.

The above-mentioned polyamide is preferably one having an amide bond in the polymer main chain, capable of being melted by heating, and to a mixed solvent having a weight ratio of (toluene) / (isooctane) = 1/1. As for the degree of swelling, the weight change rate is 0 to 5.0%. The molecular weight is preferably 10,000 to 60,000, more preferably 20,000 to 50,000.

The polyamide is not particularly limited,
For example, 4-nylon, 6-nylon, 6,6-nylon, 11-nylon, 12-nylon, 6,10-nylon, 6,12-nylon and other aliphatic nylons; isophthalic acid, terephthalic acid, metaxylylene diene Amine, 2,
2-bis (paraaminocyclohexyl) propane, 4,
4'-diaminodicyclohexylmethane, 2,2,4-
Examples thereof include polyamides obtained by polycondensing aromatic amines such as trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine, aliphatic amines, and amine compounds such as side chain-substituted aliphatic amines.

In the present invention, the content of the polyamide component in the obtained polyesteramide is 3 to 30% by weight. If it is less than 3% by weight, the mechanical strength of the molded product obtained by further polymerizing the produced polyesteramide will be insufficient, and if it exceeds 30% by weight, the hard segment content will increase and the polyesteramide will be hard. However, since it is not possible to obtain an elastomer having good rubber elasticity, it is limited to the above range.

The intrinsic viscosity of the polyesteramide of the present invention (Ubbelohde viscosity tube, orthochlorophenol solution, 3
0 ° C.) is 0.1 to 1.0. When it is less than 0.1, the molded product obtained by further polymerizing the polyesteramide is inferior in high temperature physical properties, and when it exceeds 1.0,
Since the reactivity of the chain extension reaction with the isocyanate compound or polycarbodiimide compound described below decreases, it is limited to the above range. It is preferably 0.1 to 0.5.

The present invention 2 includes at least one dicarboxylic acid represented by the general formula (1), ethylene glycol and
And 1,2-propanediol in combination
100 parts by weight of a polyester component consisting of all and having a molar ratio of dicarboxylic acid to diol of 1.0: 1.1 to 1.0: 3.5 has a reduced viscosity (1 g / dL 98% sulfuric acid solution, 20 ° C.). Polyamide components 1-2 which are 1.8-7
A method for producing a polyesteramide in which 50 parts by weight is dissolved and an esterification reaction of the polyester component is performed at 150 to 230 ° C., and then the obtained transparent homogeneous solution is polymerized at 200 to 260 ° C. under reduced pressure to the polyamide component. Is. ^{HOOC-R 1 -COOH (1)} ( wherein, R ¹ represents an alkylene group having 2 to 8 carbon atoms.)

The molar ratio of the above-mentioned dicarboxylic acid used in the present invention 2 and the above-mentioned diol at the time of charging is (dicarboxylic acid component) :( diol component) = 1: 1.1 to 1: 3.5. If the amount of the diol is less than 1.1 mol with respect to 1 mol of the dicarboxylic acid, the esterification reaction does not proceed efficiently, and if it exceeds 3.5 mol, an excessive amount of the diol component is used, which is costly. It is disadvantageous, and the cleavage reaction of the polyamide is apt to occur due to the excess diol, so that the block property of the obtained polyester is lowered, the heat resistance is lowered, and it is also disadvantageous in terms of cost. It

The amount of the polyamide component used in the present invention 2 is 1 to 100 parts by weight of the polyester component.
It is 250 parts by weight. If it is less than 1 part by weight, the mechanical strength of the molded product obtained by further polymerizing the produced polyesteramide will be insufficient, and if it exceeds 250 parts by weight, it will be difficult to dissolve the polyamide and good rubber elasticity will be obtained. Since it is not possible to obtain an elastomer having the above, the above range is limited. It is preferably 3 to 18 parts by weight.

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

The above polycondensation reaction is carried out under reduced pressure, preferably at 0
˜5 mmHg, 180-260 ° C. If it is lower than 180 ° C, the reaction rate is low and the polymerization viscosity is high, so that efficient polymerization becomes difficult. When it exceeds 260 ° C,
Since a decomposition reaction and coloring occur, it is limited to the above range.

In the present invention, when carrying out the above-mentioned polymerization,
The catalysts commonly used in the production of polyesters may be used. 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, cerium, boron. Metals such as elemental, cadmium, manganese, and zirconium; organic metal compounds thereof; organic acid salts thereof; metal alkoxides thereof; metal oxides thereof.
These may be used alone or in combination of two or more.

Particularly preferred catalysts are tetrabutoxy titanium, calcium acetate, diacyl primary tin, tetraacyl secondary tin, dibutyltin oxide, dibutyltin laurate, dimethyltinmalate, tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyl. Examples thereof include titanate, tetrapropoxy titanate, 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, when carrying out the above-mentioned polymerization,
Stabilizers may be used. The stabilizer is not particularly limited, and 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} -2,
Hindered phenolic antioxidants such as 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, pentaerythritol tetrakis (3-laurylthiopropionate), and ditridecyl-3,3′-thiodipropionate.

The polyester amide obtained by the production method of the present invention 2 is capable of increasing the molecular weight by carrying out a chain extension reaction using a bifunctional or higher functional isocyanate compound or polycarbodiimide compound, and has mechanical strength, heat resistance, etc. Can be further improved. The chain extension reaction using the isocyanate compound or the polycarbodiimide compound is carried out by polymerizing the transparent homogeneous solution obtained in the process for producing the polyesteramide under reduced pressure at 200 to 260 ° C. to obtain the isocyanate compound or the polycarbodiimide compound. By reacting.

The isocyanate compound is not particularly limited as long as it has two or more isocyanate groups in the same molecule. Diisocyanate is preferable in order to avoid gelation of the polyesteramide and efficiently perform chain extension.

The amount of the above-mentioned isocyanate compound added varies depending on the required degree of polymerization of the obtained polyesteramide, but is 0.1 to 30 parts by weight based on 100 parts by weight of the polyesteramide having the above-mentioned intrinsic viscosity. preferable. 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 mechanical strength of the molded product obtained by further polymerizing the polyesteramide is insufficient.

The amount of the polycarbodiimide compound added is such that the polyesteramide 10 having the above-mentioned intrinsic viscosity is used.
0.1 to 20 parts by weight is preferable with respect to 0 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 20 parts by weight, the mechanical strength of the molded product obtained by further polymerizing the polyesteramide is insufficient.

The polyesteramide obtained by the method for producing a polyesteramide of the present invention 2 can increase the molecular weight by solid-state polymerization, and can further improve the mechanical strength, heat resistance and the like.

In the above solid-phase polymerization, the polymerization temperature is preferably 30 ° C. lower than the melting point of the polyesteramide to be polymerized to the melting point of the polyesteramide to be polymerized, and the polymerization pressure is preferably 0 to 5 Torr. The polymerization temperature is 3 or higher than the melting point of the polyesteramide used for the polymerization.
When the temperature is lower than 0 ° C. lower, the polymerization rate is slow and the progress of the polymerization becomes difficult, and when the temperature exceeds the melting point of the polyesteramide to be polymerized, melting of the sample occurs. More preferably, it is 1 from the melting point of the polyesteramide used for the above polymerization.
The temperature is 5 ° C. lower to 5 ° C. lower than the melting point of the polyesteramide used for the above polymerization. The polymerization pressure is 5 Tor
At a pressure higher than r, the progress of polymerization becomes difficult, so
It is preferably performed under reduced pressure of 5 Torr or less. More preferably, it is 0 to 1 Torr.

The polyesteramide obtained by the method for producing a polyesteramide of the present invention 2 has a molecular weight increased by the above-mentioned method, and then, for example, a molding method such as press molding, extrusion molding, injection molding, blow molding or injection compression molding. Therefore, it is suitably used for automobile parts, electric / electronic parts, industrial parts, sports goods, medical goods and the like.

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

The industrial parts are not particularly limited, and examples thereof include hydraulic hoses, coil tubes, sealing materials, packings, V-belts, rolls, vibration-damping / 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 can be suitably used as a material for alloying with elastic fibers; elastic sheets; composite sheets; hot melt adhesives; other resins, rubber components and the like.

The present invention 3 is a polyester component comprising at least one dicarboxylic acid represented by the general formula (1) and at least two diols represented by the general formula (3), and a reduced viscosity ( 1 g / dL 98% sulfuric acid solution, 20 ° C.) is composed of a polyamide component of 0.5 to 7, the content of the polyamide component is 3 to 30% by weight, and the intrinsic viscosity (Ubbelohde viscous tube, orthochlorophenol solution, It is a polyesteramide having a temperature of 30 ° C.) of 0.1 to 0.5. ^{HOOC-R 1 -COOH (1)} ( In the formula, R ^1,. Represents an alkylene group having 2 to 8 carbon ^{atoms) HO-R 3 -OH (3} ) ( wherein, R ³ is at least 1 as a branch Represents an alkylene group having 3 to 5 carbon atoms having 3 alkyl groups.)

The present invention 4 comprises at least one dicarboxylic acid represented by the general formula (1) and at least two diols represented by the general formula (3). Is 1.0: 1.1 to 1.0:
100 parts by weight of a polyester component of 3.5 has a reduced viscosity (1 g / dL 98% sulfuric acid solution, 20 ° C.) of 1.8 to 7
After dissolving 1 to 250 parts by weight of the polyamide component which is, and carrying out the esterification reaction of the polyester component at 150 to 230 ° C., the obtained transparent homogeneous solution is subjected to 200 to 2 under reduced pressure.
It is a method for producing a polyesteramide by polymerizing the polyamide component at 60 ° C. ^{HOOC-R 1 -COOH (1)} ( In the formula, R ^1,. Represents an alkylene group having 2 to 8 carbon ^{atoms) HO-R 3 -OH (3} ) ( wherein, R ³ is at least 1 as a branch Represents an alkylene group having 3 to 5 carbon atoms having 3 alkyl groups.)

In the present invention, the polyester component is
Since it contains at least one branched diol,
Crystallization of the polyesteramide is suppressed by the presence of the branch, and the flexibility of the obtained polyesteramide is improved. When only a diol having no branching is used,
The resulting polyesteramide has high crystallinity, resulting in high hardness, resulting in poor elastomeric properties.

The general formula (3) used in the present inventions 3 and 4
Examples of the diol represented by
Diol, 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-ethanedio
Branched diols such as le and neopentyl glycol
Etc.

[0041]

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

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), 6-nylon (manufactured by Toyobo Co., Ltd., trade name "T85"
0 ", reduced viscosity at 20 ° C in 98% sulfuric acid 3.5) 26
Parts by weight (6.4 parts by weight per 100 parts by weight of the polyester component charged), 0.025 parts by weight of tetrabutoxytitanium as a catalyst, and 1,3,5-trimethyl-2,4,6-tris as a stabilizer. (3,5-di-t-butyl-
0.4 parts by weight of 4-hydroxybenzyl) benzene and 0.4 parts by weight 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. Became a transparent solution as nylon was dissolved. The temperature was kept at this temperature for 1 hour to carry out the esterification reaction. 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. Polymerization system is 1
The degree of reduced pressure of 1 mmHg or less was reached in 0 minutes. 3 in this state
As a result of performing a polycondensation reaction for 0 minutes, 259 parts by weight of a transparent resin was obtained.

Example 2 119 parts by weight of 1,2-propanediol and 2,2-dimethyl-1,3-propanediol 16 were used as the diol component.
2 parts by weight (molar ratio of adipic acid component / diol component: 1 / 2.4), 6-nylon to 46 parts by weight , tetrabutoxytitanium as a catalyst to 0.0
Polymerization was performed in the same manner as in Example 1 except that 5 parts by weight was used to obtain 306 parts by weight of resin.

Example 3 A diol component was added with 48 parts by weight of ethylene glycol and 1,2.
-Propanediol 59 parts by weight (adipic acid component / diol component charging ratio is 1 / 1.2 in molar ratio), catalyst was germanium dioxide 0.25 part by weight, 6-nylon 99 parts by weight (polyester component charging Polymerization was performed in the same manner as in Example 1 except that the amount was 33 parts by weight with respect to 100 parts by weight to obtain 331 parts by weight of a resin.

Comparative Example 1 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 charging ratio is 1 / 2.4 in molar ratio), and 6-
27 parts by weight of nylon (10 parts of polyester component charged)
Polymerization was performed in the same manner as in Example 1 except that the amount was changed to 6.3 parts by weight based on 0 parts by weight) to obtain 269 parts by weight of 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 polyamide component was unclear.

Comparative Example 2 198 parts by weight of 1,2-propanediol and 2,2-dimethyl-1,3-butanediol 271 were used as the diol component.
Polymerization was carried out in the same manner as in Example 2 except that the weight ratio (adipic acid component / diol component charging ratio was 1/4 in terms of molar ratio). In the DSC measurement, a crystal melting peak derived from the polyester component was confirmed, and no crystal melting peak derived from the polyamide component was observed.

Comparative Example 3 176 parts by weight of 1,4-butanediol was added as a diol component,
2,2-Dimethyl-1,3-butanediol 203 weight
Parts (adipic acid component / diol component charge ratio is molar ratio
1/3), 6-nylon was added to 2.7 parts by weight (0.5 parts by weight per 100 parts by weight of the polyester component charged , and tetrabutoxytitanium as a catalyst was added to 0.03 parts by weight).
Polymerization was performed in the same manner as in Example 1 except that 5 parts by weight was used . 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.

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. Measurement of melting point and glass transition point: differential scanning calorimeter (DS
Using C), the measurement was performed at a temperature rising rate of 10 ° C./min. The results are shown in Table 1.

[0049]

[Table 1]

Example 4 190 parts by weight of adipic acid, 97 parts by weight of ethylene glycol, 119 parts by weight of 1,2-propanediol (adipic acid component / diol component was charged at a molar ratio of 1/2.
4), 6-nylon (manufactured by Toyobo Co., Ltd., trade name "T85"
0 ", reduced viscosity at 20 ° C in 98% sulfuric acid 3.5) 26
Parts by weight, 0.05 parts by weight of tetrabutoxytitanium as a catalyst, and 1,3,5-trimethyl-2,4, as a stabilizer.
0.4 parts by weight of 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and 0.4 parts by weight of tris (2,4-di-t-butylphenyl) phosphite were added and reacted. After heating the system to 200 ° C. under nitrogen for 10 minutes, nylon was dissolved to form a transparent solution. The temperature was kept at this temperature for 1 hour to carry out the esterification reaction. 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. Polymerization system is 1mmHg in 10 minutes
The following degree of vacuum was reached. As a result of polycondensation reaction for 15 minutes in this state, 259 parts by weight of a transparent resin was obtained.

Example 5 Polymerization was carried out in the same manner as in Example 4 except that 0.025 parts by weight of tetrabutoxytitanium as a catalyst and 41 parts by weight of 6-nylon were used and the polycondensation reaction time was 30 minutes. Then, 274 parts by weight of resin was obtained.

Example 6 121 parts by weight of ethylene glycol and 148 parts by weight of 1,2-propanediol were used as the diol component (the adipic acid component / diol component charging ratio was 1/3 in molar ratio).
Example 5 except that the amount of 6-nylon was changed to 26 parts by weight.
Polymerization was performed in the same manner as in, to obtain 259 parts by weight of a resin.

Example 7 A diol component was added with 48 parts by weight of ethylene glycol and 1,
59 parts by weight of 2-propanediol (the adipic acid component / diol component charging ratio is 1 / 1.2 in a molar ratio), and 6
Polymerization was carried out in the same manner as in Example 5 except that nylon was changed to 26 parts by weight to obtain 259 parts by weight of resin.

EXAMPLE 8 Example 6 except that 6-nylon was used in 8.5 parts by weight.
Polymerization was performed in the same manner as in 5 to obtain 242 parts by weight of a resin.

Example 9 Example 9 -Except that 100 parts by weight of 6-nylon was used.
Polymerization was performed in the same manner as in 5 to obtain 333 parts by weight of resin.

Example 10 48 parts by weight of ethylene glycol and 1,2 were used as the diol component.
-Propanediol 59 parts by weight (the adipic acid component / diol component charging ratio is 1 / 1.2 in a molar ratio), the catalyst was germanium dioxide 0.25 parts by weight, and 6-nylon was 99 parts by weight. Was polymerized in the same manner as in Example 4 to obtain 331 parts by weight of a resin.

Comparative Example 4 97 parts by weight of a diol component was added to ethylene glycol in an amount of 1,4.
-Butanediol 141 parts by weight (adipic acid component / diol component charging ratio is 1 / 2.4 in molar ratio), and 6-
Polymerization was performed in the same manner as in Example 4 except that nylon was changed to 27 parts by weight to obtain 269 parts by weight of resin. DSC
In the measurement, a crystal melting peak derived from the polyester component was confirmed, and a crystal peak derived from the polyamide component was unclear.

Comparative Example 5 198 parts by weight of 1,2-propanediol and 2,2-dimethyl-1,3-butanediol 271 were used as the diol component.
Polymerization was carried out in the same manner as in Example 6 except that the weight ratio (adipic acid component / diol component charging ratio was 1/4 in terms of molar ratio) was obtained, and 306 parts by weight of resin was obtained. In the DSC measurement, a crystal melting peak derived from the polyester component was confirmed, and no crystal melting peak derived from the polyamide component was observed.

Comparative Example 6 Example 6 except that 6 -nylon was added to 2.7 parts by weight.
Polymerization was performed in the same manner as in 7 to obtain 272 parts by weight of resin.
In the DSC measurement, a crystal melting peak derived from the polyester component was confirmed, and no crystal melting peak derived from the polyamide component was observed.

Comparative Example 7 Example 6 except that 155 parts by weight of 6-nylon was used.
Polymerization was performed in the same manner as in 10 to obtain 387 parts by weight of a resin.

Comparative Example 8 97 parts by weight of a diol component was added to 2,2
162 parts by weight of dimethyl-1,3-butanediol (the addition ratio of adipic acid component / diol component is 1 / molar ratio)
Polymerization was carried out in the same manner as in Example 4 except that the amount of 6-nylon was changed to 2.4) and the amount of 6-nylon was changed to 27 parts by weight, whereby a viscous product was obtained.

Various physical properties were measured by the following methods.
Polyamide amide polyamide component content: Calculated from the weight of the polyamide component at the time of charging relative to the weight of the produced polyester amide. Intrinsic viscosity [η]: Measured in an o-chlorophenol solvent at 30 ° C. using an Ubbelohde viscosity tube and used for comparison of the molecular weights of the obtained products. Measurement of melting point and glass transition point: differential scanning calorimeter (DS
Using C), the measurement was performed at a temperature rising rate of 10 ° C./min. The results are shown in Table 2.

[0063]

[Table 2]

[0064]

Since the method for producing a polyesteramide of the present invention has the above-mentioned constitution, it is possible to easily obtain a polyesteramide excellent in flexibility, mechanical strength, chemical resistance and heat deterioration resistance during polymerization. it can.

─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-9-31191 (JP, A) JP-A-7-62090 (JP, A) JP-B-46-2268 (JP, B1) (58) Field (Int.Cl. ⁷ , DB name) C08G 69/44

Claims (4)

(57) [Claims] 1. At least one dicarboxylic acid represented by the general formula (1), ethylene glycol and 1,2-
Polyester component consisting of diol used in combination with propanediol , and reduced viscosity (1 g / dL
98% sulfuric acid solution, 20 ° C.) consisting of a polyamide component of 0.5 to 7, and the content of the polyamide component is 3 to 3
0% by weight, and the intrinsic viscosity (Ubbelohde viscous tube, orthochlorophenol solution, 30 ° C.) is 0.1 to 0.5, a polyesteramide. ^{HOOC-R 1 -COOH (1)} ( wherein, R ¹ represents an alkylene group having 2 to 8 carbon atoms.) 2. At least one dicarboxylic acid represented by the general formula (1), ethylene glycol and 1,2-
It is composed of a diol used in combination with propanediol, and the molar ratio of dicarboxylic acid to diol is 1.0: 1.
Reduced viscosity (1 g / dL 98% sulfuric acid solution, 20 ° C.) in 100 parts by weight of the polyester component of 1 to 1.0: 3.5
1 to 250 parts by weight of the polyamide component having a ratio of 1.8 to 7 is dissolved, and the esterification reaction of the polyester component is 150 to
A method for producing a polyesteramide, which comprises performing the above-mentioned polyamide component at 200 to 260 ° C. under reduced pressure after carrying out at 230 ° C. ^{HOOC-R 1 -COOH (1)} ( wherein, R ¹ represents an alkylene group having 2 to 8 carbon atoms.) 3. A polyester component comprising at least one dicarboxylic acid represented by the general formula (1) and at least two diols represented by the general formula (3), and a reduced viscosity (1 g / dL98). % Sulfuric acid solution, 20 ° C)
Is 0.5 to 7, and the content of the polyamide component is 3 to 30% by weight, and the intrinsic viscosity (Ubbelohde viscous tube, orthochlorophenol solution, 3
(0 degreeC) is 0.1-0.5, The polyester amide characterized by the above-mentioned. ^{HOOC-R 1 -COOH (1)} ( In the formula, R ^1,. Represents an alkylene group having 2 to 8 carbon ^{atoms) HO-R 3 -OH (3} ) ( wherein, R ³ is at least 1 as a branch Represents an alkylene group having 3 to 5 carbon atoms having 3 alkyl groups.) 4. A dicarboxylic acid represented by the general formula (1) and at least two diols represented by the general formula (3), wherein the molar ratio of the dicarboxylic acid to the diol is 1. 100 parts by weight of a polyester component of 0: 1.1 to 1.0: 3.5 has a reduced viscosity (1 g / d
L98% sulfuric acid solution, 20 ° C.) 1 to 250 parts by weight of a polyamide component having a pH of 7 to 7 is dissolved and the esterification reaction of the polyester component is performed at 150 to 230 ° C. A method for producing a polyesteramide, which comprises polymerizing the polyamide component at 200 to 260 ° C. under reduced pressure. ^{HOOC-R 1 -COOH (1)} ( In the formula, R ^1,. Represents an alkylene group having 2 to 8 carbon ^{atoms) HO-R 3 -OH (3} ) ( wherein, R ³ is at least 1 as a branch Represents an alkylene group having 3 to 5 carbon atoms having 3 alkyl groups.)