JPS6236459A - Polyamide composition and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled compsn. having excellent aging resistance, moldability, etc. by polycondensing an arom. dicarboxylic acid and an aliph. alkylene-diamine in th presence of a primary or secondary amine and a phosphate or phosphite ester. CONSTITUTION:An arom. dicarboxylic acid component (A) composed of 60-100mol% of terephthalic acid and 40-0mol% of other arom. dicarboxylic acid and a 6-18C aliph. alkylenediamine (B) (e.g. 1,6-diaminohexane) are polycondensed in the presence of 0.01-5mol% (based on the quantity of component B) of a monocarboxylic acid (e.g. acetic acid) or a primary or secondary amine and optionally, 0.01-5mol% (based on the quantity of component B) of a phosphate or phosphite ester (e.g. trimethyl phosphate). Alternatively, their nylon salts or oligomers are polycondensed.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyamide composition and a method for producing the same.
The present invention relates to a polyamide composition that provides molded products with excellent mechanical properties, chemical and physical properties, and also has excellent moldability, that is, fluidity, and a method for producing the same.

(Prior art) In general, thermoplastic resins such as polyolefin, polyester, and polyamide have poor moldability, so compression molding,
Although melt molding such as injection molding or extrusion molding can be easily performed, it is still not satisfactory as an engineering plastic in terms of heat resistance, mechanical properties, and chemical properties. They are used in various general-purpose molding fields by taking advantage of their characteristics.

On the other hand, as engineering plastics with superior heat resistance, mechanical properties, and chemical and physical properties,
polytetrafluoroethylene known as Teflon®, polyparaphenylene terephthalamide known as Kevlar®, and 4,4”-diaminodiphenyl ether and pyromellitic anhydride known as Kapton®. Polyimides consisting of condensates, polyhexamethylene adipamide known as 6,6-nylon, poly (2,2,4-)limethylhexamethylene terephthalamide known as Trogamide T (registered trademark), polyphenylene sulfide , polyacetal, etc. are used for various purposes.

However, among these, polytetrafluoroethylene,
Although polyparaphenylene terephthalamide and the above-mentioned polyimides have excellent heat resistance, mechanical properties, and chemical and physical properties, they cannot be melt-molded, so their fields of use are severely limited. For these,
Polyphenylene sulfide, polyhexamethylene adipamide, 2.2.4-trimethylhexamethylene terephthalamide, polyacetal, etc. all have the advantage of being able to be melt-molded, but on the other hand, polyphenylene sulfide has a low melting point, It has poor heat resistance properties such as transition point and heat distortion temperature, and mechanical properties such as impact strength and abrasion resistance.
On the other hand, polyhexamethylene adipamide, 2,4.4-
) Polyamides such as trimethylhexamethylene terephthalamide have various properties such as glass transition point, heat resistance properties such as heat distortion temperature, mechanical properties such as tensile strength, bending strength, limit pv value, and abrasion resistance, as well as chemical resistance and resistance. Poor chemical properties such as boiling water and saturated water absorption. Furthermore, polyacetal is inferior in heat resistance properties such as melting point and heat distortion temperature, and mechanical strength such as bending strength, impact strength, and abrasion resistance.

In order to solve the problems with conventional engineering plastics as described above, the present inventors have already
A polyamide consisting of an aromatic dicarboxylic acid component unit whose main component is a terephthalic acid component unit and an aliphatic alkylene diamine component unit has excellent heat resistance properties, mechanical strength, chemical and physical properties, and molding properties, and in particular, It has been discovered that the sliding properties are excellent (Patent application 1986-120)
No. 40). However, as a result of extensive research into this polyamide in order to improve its heat aging resistance, the present inventors have found that by adding a specified monocarboxylic acid or monoamine, molded products with excellent heat aging resistance can be produced. In particular, by adding a monocarboxylic acid or a monoamine at any stage of polycondensation of polyamide raw materials to produce polyamide, it has been found that it is possible to obtain a polyamide composition as a molding material that provides extremely excellent fluidity. It has been found that a polyamide composition having excellent moldability can be obtained, and furthermore, this polyamide composition can give a molded article having excellent heat aging resistance,
This led to the present invention.

(Structure of the Invention) The polyamide composition according to the present invention has (A)fa) terephthalic acid component units in a range of 60 to 100 mol%, and aromatic dicarboxylic acid component units other than terephthalic acid component units in a range of 0 to 40%. an aromatic dicarboxylic acid component unit in the range of mol %, and (b) a carbon number of 6 to 18
(B) a primary amine or a secondary amine which is a monocarboxylic acid or a monoamine in an amount of 0.01 to 5 mol% based on the aliphatic alkylene diamine component constituting the polyamide; The polyamide composition according to the invention, in particular characterized in that it contains an amine, preferably comprises:
Together with the monocarboxylic acid or monoamine, it contains 0.01 to 5 mol% of phosphoric acid ester or phosphite based on the aliphatic alkylene diamine component constituting the polyamide.

Further, the method for producing a polyamide composition according to the present invention includes: (a) 60 to 100 mol% of terephthalic acid component units;
and (b) an aliphatic alkylene diamine component having 6 to 18 carbon atoms. (c) 0.01 to 5 mol % of a primary amine or a secondary amine that is a monocarboxylic acid or a monoamine based on the aliphatic alkylene diamine component constituting the polyamide.
In the presence of an amine, and preferably in the presence of 0.01 to 5 mol % of a phosphate or phosphite based on the aliphatic alkylene diamine component together with the monocarboxylic acid or monoamine, It is characterized by polycondensing an aromatic dicarboxylic acid component and the aliphatic alkylene diamine component, or polycondensing their nylon salts or oligomers.

In the polyamide composition according to the present invention, polyamide (
A) is (a) an aromatic dicarboxylic acid component having terephthalic acid component units in the range of 60 to 100 mol% and aromatic dicarboxylic acid component units other than terephthalic acid component units in the range of 0 to 40 mol%. and (b) an aliphatic alkylene diamine component unit having 6 to 18 carbon atoms.

The composition of the aromatic dicarboxylic acid component unit (a) may be a single terephthalic acid component unit, but may be a mixture of a terephthalic acid component unit and an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit. There may be. Specific examples of the aromatic dicarboxylic acid component units other than the terephthalic acid component units include isophthalic acid, phthalic acid, 2-methylterephthalic acid, naphthalene dicarboxylic acid, and the like. Among these, isophthalic acid component units or naphthalene dicarboxylic acid component units, particularly isophthalic acid component units, are preferably used.

In the present invention, the aromatic dicarboxylic acid component unit (
Of a), terephthalic acid accounts for 60 to 100 mol%, and aromatic dicarboxylic acids other than terephthalic acid component units account for 0.
It is required that the content be in the range of 40 mol %. When the amount of terephthalic acid in the aromatic dicarboxylic acid component units (a) is less than 60 mol% and the amount of aromatic dicarboxylic acid component units other than the terephthalic acid component units is more than 40 mol%, such a polyamide is used. Molded products obtained from the composition containing the compositions have excellent heat resistance properties including heat aging resistance and heat distortion temperature, mechanical properties such as tensile strength, bending strength, and abrasion resistance, and chemical and physical properties such as chemical resistance and water resistance. Inferior.

However, in the present invention, the above aromatic dicarboxylic acid component unit (al is a terephthalic acid component unit and an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit), as well as a small amount, for example, about 10 mol% of adipic acid. , sebacic acid, trimellitic acid, pyromellitic acid, and other polyhydric carboxylic acid component units.

In the polyamide composition according to the present invention, the aliphatic alkylene diamine component unit (b) is a linear or branched alkylene diamine component unit having 6 to 18 carbon atoms. Specific examples of the alkylene diamine at position 1 include, for example, 1,4-diamino-1,1-dimethylbutane, 1.4
-diamino-1-ethylbutane, 1,4-diamino-1
,2-dimethylbutane, 1,4-diamino-1,3-dimethylbutane, 1,4-diamino-1,4-dimethylbutane, 1,4-diamino-2,3-dimethylbutane, 1
, 2-diamino-1-butylethane, 1,6-diaminohexane, 1,7-diaminohebutane, 1,8-diaminooctane, 1,6-diamino-2,5-dimethylhexane, 1,6-diamino-2 ,4-dimethylhexane,
1,6-Diami2-3,3-dimethylhexane, 1.6
-Diamitwo 2,2-dimethylhexane, 1,9-diaminonane, 1,6-diamitwo 2.2.4-trimethylhexane, 1,6-diamitwo 2.4.4-trimethylhexane, 1,7-diamitwo 2. 3-dimethyl hebutane, 1,7-cyami2゜4-dimethyl hebutane,
1,7-Diami2-2,5-dimethylhebutane, 1.7
~Diamino-2,2-dimethylhebutane, 1,10-diaminodecane, 1,8-diamino-1,3-dimethyloctane, 1,8-diamino-1,4-dimethyloctane, 1,8-diamino- 2,4-dimethyloctane, 1.
8-Diamino-3,4-dimethyloctane, 1,8-diamino-4,5-dimethyloctane, 1.8-diamino-2°2-dimethyloctane, ■, 8-diamino-3.
3-dimethyloctane, 1.8-diamino-4,4-dimethyloctane, 1.6-diamino-2.4-diethylhexane, 1.9-diamino-5-methylnonane, 1.
Examples include component units such as 11-diaminoundecane and 1,12-diaminododecane.

Among these, in particular, 1,6-cyamitsuhexane,
Component units such as 1.8-diaminooctane, 1.10-diaminodecane, and 1.12-diaminododecane, or mixed component units thereof are preferably used.

In the polyamide composition according to the present invention, the composition of the aromatic dicarboxylic acid component unit (a) described above is preferably selected depending on the number of carbon atoms of the aliphatic alkylene diamine. In this way, when selecting the composition of the aromatic dicarboxylic acid component unit (a) according to the number of carbon atoms in the aliphatic alkylene diamine, it is particularly important that the resulting polyamide composition has excellent moldability, heat aging resistance and This is because it provides a molded product with excellent heat resistance properties such as heat distortion temperature, and mechanical properties such as bending strength and abrasion resistance.

That is, when the number of carbon atoms in the aliphatic alkylene diamine is, for example, 6, the aromatic dicarboxylic acid component unit +8)
The composition preferably has 60 to 8 terephthalic acid component units.
The amount of aromatic dicarboxylic acid component units other than terephthalic acid component units is in the range of 15 to 40 mol%. When the number of carbon atoms in the aliphatic alkylene diamine is, for example, 8, the composition of the aromatic dicarboxylic acid component unit (a) is preferably in the range of 65 to 100 mol% of terephthalic acid component units, and other than terephthalic acid component units. The amount of aromatic dicarboxylic acid component units is in the range of 0 to 35 mol%. Further, when the aliphatic alkylene diamine component unit (b) has, for example, 10 to 18 carbon atoms, the composition of the aromatic dicarboxylic acid component unit (a) preferably has 75 to 100 terephthalic acid component units. mole% range, and aromatic dicarboxylic acid component units other than terephthalic acid component units are 0 to 0.
It is in the range of 25 mol%.

Further, in the polyamide composition according to the present invention, the polyamide described above is soluble in concentrated sulfuric acid at a temperature of 50°C, and has an intrinsic viscosity [η] of 0.5 dl when measured in concentrated sulfuric acid at a temperature of 30°C. /g or more is preferable. Preferably, [η] is 0.6 dl/g or more, particularly preferably in the range of 0.7 to 3.0 dl/g.

Such a concentrated sulfuric acid-soluble polyamide can be obtained by a conventionally known method. For example, P
olymer Reviews+10+ Conden
sationPolymers by Interfa
ctal and 5solution Methods
(P.W. Morgan, Interscience
ce Publishers (1965)) and Mak
romol, Chem, 47.93-113 (19
As described in 61)), it can be obtained by polycondensing the diacid halide of an aromatic dicarboxylic acid, which is a constituent unit of the polyamide described above, and an aliphatic alkylene diamine using a solution method.

It can also be obtained by interfacial polymerization.

Alternatively, it can also be obtained by polycondensing the aromatic dicarboxylic acid and alkylene diamine or its nylon salt by a melt method in the presence or absence of a solvent such as water. Furthermore, it can also be obtained by polycondensing the polyamide oligomer obtained by the former method using a solid phase polymerization method.

Furthermore, in the polyamide composition according to the present invention, the polyamide contains not only the above-mentioned concentrated sulfuric acid soluble polyamide, but also a polyamide having a composition in the same range as this concentrated sulfuric acid soluble polyamide, but which is insoluble in 50'c concentrated sulfuric acid. You can leave it there. Here, polyamide that is insoluble in concentrated sulfuric acid at 50°C refers to pulverized polyamide, heated and stirred 1% by weight concentrated sulfuric acid solution of polyamide that has passed through 32 meshes at 50°C for 10 hours, and then heated and stirred at 50°C. This refers to polyamide that has been filtered through a 2G glass filter to remove the soluble portion. Such concentrated sulfuric acid-insoluble polyamide is not particularly limited, but can be used at 360'C and a load of 2.16kg.
The melt viscosity (MFR) in is usually 20 g/10 min or less, preferably 5 g/lO min or less, particularly preferably 0-1 gz'IO min or less.

Such concentrated sulfuric acid-insoluble polyamide can be produced as a by-product during the production of the concentrated sulfuric acid-soluble polyamide. Furthermore, by selecting the reaction conditions, the amount produced can be intentionally increased. Therefore, in such a case, a mixture of a polyamide soluble in concentrated sulfuric acid and a polyamide insoluble in concentrated sulfuric acid can be obtained. Furthermore, if necessary, the polyamide soluble in concentrated sulfuric acid or the mixture thereof with the polyamide insoluble in concentrated sulfuric acid can be further crosslinked to have a high molecular weight, thereby making it entirely insoluble in concentrated sulfuric acid.

Therefore, although not limited in any way, as a method for producing concentrated sulfuric acid-insoluble polyamide or a mixture of concentrated sulfuric acid-soluble polyamide and concentrated sulfuric acid-insoluble polyamide, for example,
A method of further solid-phase polymerizing the concentrated sulfuric acid-soluble polyamide,
When producing concentrated sulfuric acid-soluble polyamide by melt polycondensation, the polycondensation temperature is set to a higher temperature, e.g.
℃ or above, a method of polycondensing alkylene diamine and aromatic dicarboxylic acid with a charging molar ratio of 1603 or more, and a method of using trifunctional or higher polyamine or polycarboxylic acid together with alkylene diamine and aromatic dicarboxylic acid. A method of polycondensing this can be exemplified.

In the polyamide composition according to the present invention, the concentrated sulfuric acid-insoluble polyamide is preferably contained in an amount of 1000 parts by weight or less per 100 parts by weight of the concentrated sulfuric acid-soluble polyamide. In particular, according to the invention, concentrated sulfuric acid soluble polyamide 100! When the concentrated sulfuric acid-insoluble polyamide is contained in an amount of 2 to 1.00 parts by weight, preferably 3 to 600 parts by weight, particularly preferably 5 to 400 parts by weight, the polyamide composition obtained from such a polyamide composition The molded product has excellent mechanical strength such as bending strength.

Here, the ratio of the polyamide soluble in concentrated sulfuric acid and the polyamide insoluble in concentrated sulfuric acid in the polyamide is determined by the following method. That is, a 1% by weight concentrated sulfuric acid solution of the polyamide mixture ground through 32 meshes was heated with stirring at a temperature of 50°C for 10 hours, cooled to room temperature, and filtered through a 2G glass filter to obtain the polyamide as a precipitate. and polyamide, which is obtained by precipitating the polyamide contained in the filtrate with water, are collected, dried, and their weights are measured.

The polyamide composition according to the present invention has a monocarboxylic acid or
contains a primary amine or a secondary amine which is a monoamine. Here, as the monocarboxylic acid, aliphatic, alicyclic and aromatic carboxylic acids can be used, and preferred monocarboxylic acids include aliphatic monocarboxylic acids having 2 to 30 carbon atoms, and those having an alkyl substituent. Examples thereof include benzenecarboxylic acid and naphthalenecarboxylic acid which may have an alkyl substituent, and cyclohexane monocarboxylic acid which may have an alkyl substituent. More specifically, for example, aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, valmitic acid, stearic acid, oleic acid, and linoleic acid. Examples of the alicyclic monocarboxylic acid include cyclohexanecarboxylic acid, and examples of the aromatic monocarboxylic acid include benzoic acid, toluic acid, naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.

Monoamines also include aliphatic, cycloaliphatic and aromatic primary
Amines and secondary amines can be used. Preferred specific examples include methylamine, ethylamine,
Aliphatic primary and secondary amines such as propylamine, butylamine, hexylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, alicyclic primary and secondary amines such as cyclohexylamine, dicyclohexylamine, etc. Mention may be made of aromatic primary and secondary amines such as diamine, aniline, toluidine, diphenylamine, naphthylamine.

In the polyamide composition according to the present invention, these monocarboxylic acids or amines are contained in an amount of 0.01 to 5 mol%, preferably 0.02 to 2 mol%, based on the aliphatic alkylene diamine component constituting the polyamide. It is blended in a range, particularly preferably in a range of 0.05 to 1 mol%. When the blending amount of the monocarboxylic acid or monoamine is less than 0.01 mol % based on the aliphatic alkylene diamine component, the heat aging resistance of the molded product obtained from such a polyamide composition is not sufficiently improved; When blending in a large amount exceeding 5 mol %, mechanical strength such as tensile strength and bending strength decreases. In particular, as described below,
When producing a polyamide composition by polycondensing polyamide raw materials in the presence of a monocarboxylic acid or monoamine, the molecular weight of the resulting polyamide is not large enough.
Tensile strength and bending strength begin to decrease.

Furthermore, the polyamide composition according to the invention preferably contains a phosphoric acid ester or a phosphorous acid ester, in particular a phosphoric acid triester or a phosphorous acid triester, together with the above-mentioned monocarboxylic acids or monoamines as additives. Specific examples of such phosphate triesters include trimethyl phosphate, triethyl phosphate, triisopropyl phosphate, tributyl phosphate, trihexyl phosphate, triisodecyl phosphate, triotadecyl phosphate, tridecyl phosphate, tristearyl phosphate, and phosphoric acid. Acid triphenyl etc. can be mentioned. In addition, specific examples of phosphite triesters include trimethyl phosphite, triethyl phosphite,
Examples include triisopropyl phosphite, tributyl phosphite, trihexyl phosphite, triisodecyl phosphite, triotadecyl phosphite, tridecyl phosphite, tristearyl phosphite, and triphenyl phosphite.

In the polyamide composition according to the present invention, these phosphoric acid esters or phosphite esters also have a content of 0.0% relative to the aliphatic alkylene diamine component constituting the polyamide.
It is blended in a range of 1 to 5 mol%, preferably in a range of 0.02 to 2 mol%, particularly preferably in a range of 0.05 to 1 mol%. When the phosphoric acid ester or phosphite ester is used in combination with the monocarboxylic acid or monoamine described above,
The fluidity of the resulting polyamide composition is further improved, and the heat aging resistance of molded products obtained from this polyamide composition is further improved. However, when blending in a large amount exceeding 5 mol %, the mechanical strength such as tensile strength and bending strength of the molded product from the resulting polyamide composition is reduced for the same reason as explained for monocarboxylic acids or monoamines. This is not preferable because it lowers the temperature.

As described above, polyamide can be obtained by any method such as a melt method, a solid phase method, or a combination thereof, but the polyamide composition according to the present invention can be obtained by any method for producing polyamide in these methods. It can be obtained by adding the monocarboxylic acid or monoamine in a step, preferably adding the phosphoric acid ester or phosphite together with the monocarboxylic acid or monoamine. However, the timing of addition of these additives does not have to be the same. It can also be obtained by adding a monocarboxylic acid or a monoamine to a polyamide obtained by any method, preferably by adding and mixing a sulfite ester or a phosphite ester together.

However, in the present invention, the monocarboxylic acid or monoamine is added at the stage of polycondensing the dicarboxylic acid component and the aliphatic alkylene diamine component, or their nylon salts or oligomers, and preferably a phosphoric acid ester or monoamine is added together with these. By adding a phosphite in combination, it is possible to obtain a polyamide composition with particularly excellent fluidity, and furthermore, such a polyamide composition provides a molded article with particularly excellent heat aging resistance.

In the polyamide composition according to the present invention, in addition to the above-mentioned monocarboxylic acid or monoamine, phosphate ester or phosphite ester, conventionally known polymers, stabilizers, plasticizers, It may contain a molding agent, a lubricant, a filler, etc. Examples of the polymer include polyamides such as nylon 66 and nylon 6.

As fillers, conventionally known powder-like, plate-like,
Organic or inorganic substances having various forms such as fibrous or cross-like forms can be used.

Examples of inorganic fillers include silica, alumina, silica alumina, talc, diatomaceous earth, clay, kaolin, quartz, glass, mica, graphite, molybdenum disulfide, gypsum, red iron oxide, titanium dioxide, zinc oxide, aluminum, and copper. , powdered or plate-like materials such as stainless steel, fibrous materials such as glass fiber, carbon fiber, boron fiber, ceramic fiber, asbestos fiber, stainless steel fiber, or cross-like materials as secondary processed products of these. can be mentioned.

In addition, examples of the organic filler include polyparaphenylene terephthalamide, polymetaphenylene terephthalamide, polyparaphenylene isophthalamide, polymetaphenylene isophthalamide, a condensate of diaminodiphenyl ether and terephthalic acid and/or isophthalic acid, Fully aromatic polyamides such as condensates of para- or meta-aminobenzoic acid, fully aromatic polyamideimides such as condensates of diaminodiphenyl ether and trimellitic anhydride and/or pyromellitic acid, fully aromatic polyimides, polybenz Examples include heterocycle-containing polymers such as imidazole and polyimidazophenanthroline, powders such as polytetrafluoroethylene, plate-like products, fibrous products, and cross-like products as secondary products thereof.

The fillers described above may be blended alone or as a mixture, but if necessary, these fillers may be treated with a silane coupling agent, a titanium coupling agent, or the like.

Among the fillers described above, silica, silica-alumina, alumina, titanium dioxide, graphite, molybdenum disulfide, polytetrafluoroethylene, etc. are preferably used as powdered materials, but in particular, graphite, molybdenum disulfide, and polytetrafluoroethylene are preferably used. Fluoroethylene is preferably used because it improves the wear resistance of the molded product obtained from the composition, such as the coefficient of dynamic friction, Taber, -wear, and limit PV value.

Such fillers usually have an average particle size of 0.1 mμ to 2
It is preferable that the particle diameter is in the range of .degree.O.mu., particularly in the range of 1 m.mu.

The blending amount of the powdery filler as described above is 200 parts by weight or less per 100 parts by weight of the polyamide composition, preferably,
The amount is 100 parts by weight or less, particularly preferably in the range of 0.5 to 50 parts by weight.

Furthermore, when the fibers made of the wholly aromatic polyamide are used as the filler, the mechanical properties such as tensile strength and Izot impact strength, and the heat resistance properties such as heat distortion temperature of the molded product obtained from the composition are further improved.

In addition, when glass fiber, carbon fiber or boron fiber is used as the fibrous inorganic filler, the mechanical properties such as tensile strength, bending strength, bending modulus, etc. of the molded product obtained from the composition, heat distortion temperature, etc. Chemical and physical properties such as heat resistance and water resistance are further improved.

These fibrous fillers are usually 061-20m, especially,
Preferably, it has an average length in the range 1 to 10 m. The blending amount is usually about 100 parts by weight of polyamide.
The amount is preferably 5 to 180 parts by weight, particularly preferably 5 to 150 parts by weight.

The polyamide composition according to the invention can be molded by conventional melt molding, such as compression molding, injection molding or extrusion molding.

(Effects of the Invention) As described above, the polyamide composition of the present invention contains a polyamide having a predetermined composition, a monocarboxylic acid or a monoamine, and preferably further contains a phosphoric acid ester or a phosphorous acid ester. Molded articles obtained from such polyamide compositions have particularly improved heat aging resistance. Of course, heat resistance properties such as melting point, glass transition point and heat distortion temperature, mechanical properties such as tensile strength, bending strength, impact properties, dynamic friction coefficient, taper wear, chemical resistance, boiling water resistance, saturated water absorption, etc. It also has excellent molding properties such as physical properties, fluidity of the melt composition, melt compression moldability, melt injection moldability, and melt extrusion moldability.

In particular, high temperature conditions are required when producing a polyamide having the component unit composition specified in the present invention and having a high molecular weight, for example, by melt polymerization or solid phase polymerization. By polycondensing the polyamide raw material in the presence of phosphoric acid ester or phosphite ester, thermal deterioration of the polymer is prevented even during polycondensation, and furthermore, a polyamide with excellent fluidity can be obtained. A composition can be obtained. Moreover, this composition provides molded articles with excellent heat aging resistance.

(Examples) The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples in any way. still,
In the table below, abbreviations indicate the following compounds, respectively.

TA: Terephthalic acid IA: Isophthalic acid C, D^: 1,6-hexamethylenediamine C+0D
A: The method for preparing the 1.10-decamethylenediamine test piece and the evaluation method for each performance are as follows.

(Preparation of test piece of polyamide composition molded product and evaluation of physical properties) The polyamide composition was crushed in a crusher (passed through 32 meshes),
Dry for an hour. This polyamide composition was molded using a press molding machine in a nitrogen atmosphere at a weight of 100 kg/co! After hot pressing at a temperature 20° C. higher than the melting point of polyamide under a pressure of

These molded plates were cut into test pieces having the dimensions listed in Table 1, and then left in an atmosphere at a temperature of 23°C and a relative humidity of 65% for 96 hours, and then subjected to each test. The heat aging resistance was evaluated by the bending strength after storing the bending test piece in an air oven at 250° C. for 2 days and its retention rate with respect to the initial value.

In addition, the glass fiber compound molded product is made of 60 parts by weight of a predetermined pulverized and dried polyamide and glass fibers (average length 5 + n,
Nitto Boseki Chopped Strand CS 6PE-23
1) Add 40 parts by weight and a specified stabilizer to a single screw extruder (L/
D = 28.20 m diameter) and mixed to obtain about 6 fl of a strand-shaped polyamide composition, which was then press-molded in the same manner as in the case where no glass fiber was blended to form a test piece. Manufactured.

Example 1 Terephthalic acid 123.6g (0,744 mol), isophthalic acid 52.9g (0,318 mol), benzoic acid 1.
22 g (0.01 mol), 123.4 g (1.06 mol) hexamethylene diamine and 33 g ion-exchanged water
was charged into an 11-capacity autoclave, and after thorough nitrogen purging, the temperature was raised to 280° C. over 2 hours while stirring. Furthermore, after allowing the reaction to proceed for 1 hour at 280°C in a sealed state, stirring was stopped and a differential pressure of 10 kg/c++! was applied from the bottom of the autoclave. The reaction mixture was taken out. This was dried overnight at 100° C. and 100 Hg in nitrogen.

This oligomer was extruded using a twin-screw extruder (screw diameter 30 m, L
/D=42, barrel temperature ('C) 30/2/340/3
40/340, the fourth and sixth zones were vented to the atmosphere, the rotation speed was 8 Orpm, the oligomer supply IL was 2 kg/hour, and the exhaust was purged with nitrogen) to advance polycondensation and increase the molecular weight to obtain a polyamide composition. Table 2 shows the properties of the polyamide composition thus obtained and the physical properties of molded test pieces obtained from this composition.

Example 2 In Example 1, except that 0.93 g (0.01 mol) of aniline was used instead of 1.22 g of benzoic acid.
A polyamide composition was produced in the same manner as in Example 1. Table 2 shows the properties of the polyamide thus obtained and the physical properties of molded test pieces obtained from this composition.

(Manufacture of concentrated sulfuric acid-insoluble polyamide) Example 3 The polyamide composition obtained in Example 1 was heated at 280°C for 1
Solid-phase polymerization was carried out under stirring for 4 hours under mmHH conditions to increase the molecular weight to obtain a concentrated sulfuric acid-insoluble polyamide composition. Table 2 shows the properties of the polyamide thus obtained and the physical properties of molded test pieces obtained from this composition.

Example 4 In Example 1, hexamethylene diamine 129.6
An oligomer was obtained in the same manner as in Example 1, except that g (1.12 mol) was used, and the oligomer was made to have a high molecular weight in the same manner as in Example 3 to obtain a concentrated sulfuric acid-insoluble polyamide composition. Table 2 shows the properties of the polyamide thus obtained and the physical properties of molded test pieces obtained from this composition.

Example 5 In Example 2, 114.7 g of terephthalic acid (0.7
An oligomer was obtained in the same manner as in Example 2, except that 61.7 g (0.37 mol) of isophthalic acid, and 0.666 g (1°06 mmol) of tridecyl phosphite were used. The molecular weight of perilla was increased in the same manner as in Example 3 to obtain a concentrated sulfuric acid-insoluble polyamide composition. Table 2 shows the properties of the polyamide thus obtained and the physical properties of molded test pieces obtained from this composition.

Example 6 232 g (1,40 mol) of terephthalic acid, 1.10-
241 g (1.4 mol) of diaminodecane and 10 J of ion-exchanged water were added to a 10-liter tube equipped with a stirring bar, a thermometer, and a reflux condenser.
Charged into a reactor with a capacity of 2, and heated under a nitrogen atmosphere at 95 to 10
The reaction was carried out for 1 hour at a temperature of 0°C.

After the reaction was completed, the transparent solution was air-cooled, and the precipitated nylon salt was collected by suction filtration and dried at 100°C and 100 Hg to obtain 450 g of nylon salt of terephthalic acid-1,10-diaminodecane. Ta.

450 g (1,33 moles) of this nylon salt and 1.23 g (0,013 moles) of aniline were charged into an 11-capacity reactor, and after purging the inside of the reactor with nitrogen, the temperature was gradually raised in a nitrogen stream. When 300°C was reached, 2.27 g (2.66 mmol) of tristearyl phosphate was added,
The reaction was carried out at the same temperature for 1.5 hours, and the produced water was extracted from the system to obtain 390 g of an oligomer consisting of terephthalic acid-1,10-diaminodecane. [η] measured in concentrated sulfuric acid at 30°C was 0.45 dl/g.

This polyamide was crushed in a crusher (passed through 32 meshes), dried for 12 hours at 80°C and 50 mm 11 g, and then dried at 300°C and 0.7 dragon Hg for 10
Solid phase polymerization was carried out for a period of time to obtain a polyamide consisting of terephthalic acid-1,10-diaminodecane.

Table 2 shows the properties of the polyamide thus obtained and the physical properties of molded test pieces obtained from this composition.

Example 7 A composition was prepared in which 40 parts by weight of glass fiber (average length 6 dragons, chopped strand C56PE-231 manufactured by Nitto Boseki 0 Kiku) was blended with 60 parts by weight of the polyamide synthesized by the method of Example 2. Physical properties were evaluated. The results are shown in Table 2.

Comparative Examples 1 to 3 Polyamides were produced by the method described in Example 1, except that instead of using 1.22 g of benzoic acid in Example 1, benzoic acid or aniline was used in the amounts listed in Table 2. did. The results are shown in Table 2.

Comparative Example 4 In Example 1, instead of using 1.22 g of benzoic acid, 1.22 g of benzoic acid and 40 g of tridecyl phosphite were used.
Polyamide was synthesized by the method described in Example 1, except that g was used. The results are shown in Table 2.

Claims (4)

[Claims] (1) (A) (a) Terephthalic acid component unit is 60 to 10
aromatic dicarboxylic acid component units in the range of 0 mol % and aromatic dicarboxylic acid component units other than terephthalic acid component units in the range of 0 to 40 mol %, and (b) carbon number 6
A polyamide consisting of ~18 aliphatic alkylene diamine component units, and (B) a primary amine or monocarboxylic acid or monoamine in an amount of 0.01 to 5 mol% based on the aliphatic alkylene diamine component constituting the polyamide. A polyamide composition containing a secondary amine. (2) (A) (a) Terephthalic acid component unit is 60 to 10
aromatic dicarboxylic acid component units in the range of 0 mol % and aromatic dicarboxylic acid component units other than terephthalic acid component units in the range of 0 to 40 mol %, and (b) carbon number 6
A polyamide consisting of ~18 aliphatic alkylene diamine component units, and (B) a primary amine or monocarboxylic acid or monoamine in an amount of 0.01 to 5 mol% based on the aliphatic alkylene diamine component constituting the polyamide. A polyamide composition containing a secondary amine and 0.01 to 5 mol% of a phosphoric acid ester or a phosphorous acid ester. (3) (a) Aromatic dicarboxylic acid component units in which the terephthalic acid component units are in the range of 60 to 100 mol% and the aromatic dicarboxylic acid component units other than the terephthalic acid component units are in the range of 0 to 40 mol%. (b) When producing a polyamide consisting of aliphatic alkylene diamine component units having 6 to 18 carbon atoms, (c) 0.01 to 5 mol % based on the aliphatic alkylene diamine component constituting the polyamide. Polycondensing the aromatic dicarboxylic acid component and the aliphatic alkylene diamine component, or polycondensing their nylon salts or oligomers in the presence of a primary amine or secondary amine that is a monocarboxylic acid or monoamine. A method for producing a polyamide composition characterized by: (4) (a) Aromatic dicarboxylic acid component units in which the terephthalic acid component units are in the range of 60 to 100 mol%, and the aromatic dicarboxylic acid component units other than the terephthalic acid component units are in the range of 0 to 40 mol% (b) When producing a polyamide consisting of aliphatic alkylene diamine component units having 6 to 18 carbon atoms, (c) 0.01 to 5 mol % based on the aliphatic alkylene diamine component constituting the polyamide. The above aromatic dicarboxylic acid component and the above aliphatic alkylene diamine in the presence of a primary amine or secondary amine that is a monocarboxylic acid or monoamine, and 0.01 to 5 mol% of a phosphoric acid ester or a phosphorous acid ester. 1. A method for producing a polyamide composition, which comprises polycondensing the components, or polycondensing their nylon salts or oligomers.