JPS61285252A - Polyamide composition - Google Patents

Abstract

PURPOSE:A composition, obtained by adding a copper compound and preferably further an alkali metal halide to a polyamide consisting of an aromatic dicarboxylic acid consisting essentially of terephthalic acid and aliphatic alkylenediamine and having improved heat aging resistance. CONSTITUTION:A polyamide composition obtained by adding (B) a copper compound, preferably a copper halide, e.g. cupric chloride, and copper phosphate, e.g. cupric pyrophosphate, in an amount of 1-1,000ppm range based on a component (A) expressed in terms of copper metal and preferably further (C) an alkali metal halide, preferably potassium iodide in an amount of 1-10,000ppm range based on the component (A) to (A) a polyamide consisting of (i) aromatic dicarboxylic acid component units containing 60-100mol% terephthalic acid component units and (ii) 6-18C aliphatic alkylenediamine component units, preferably component units, e.g. 1,6-diaminohexane or 1,8-diaminooctane, or mixed component units thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyamide composition, and more particularly, it has excellent heat aging resistance, and has excellent heat resistance, mechanical properties, and chemical and physical properties. The present invention relates to a polyamide composition which not only provides excellent molded products but also has good moldability.

(Prior art) In general, thermoplastic resins such as polyolefins, polyesters, and polyamides have excellent 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 (registered trademark), polyparaphenylene terephthalamide known as Kevlar (registered trademark), and 4,4'-diaminodiphenyl ether and pyromellitic anhydride known as Kapton (registered trademark). Polyimides consisting of condensates, polyhexamethylene adipamide known as 6,6-nylon, poly(2,2,4-trimethylhexamethylene terephthalamide) known as Trogamide T (registered trademark), polyphenylene sulfide, Polyacetal and the like are used for various purposes.

However, among these, polytetrafluoroethylene,
Although polyvalent phenylene terephthalamide and the above-mentioned polyimides have excellent heat resistance, mechanical properties, and chemical and physical properties, their fields of use are severely limited because they cannot be melt-molded. For these,
Polyphenylene sulfide, polyhexamethylene adipamide, 2.2.4-)limethylhexamethylene terephthalamide, polyacetal, etc. all have the advantage of being melt moldable, but on the other hand, polyphenylene sulfide has a low melting point, It has poor heat resistance properties such as glass 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 all have heat resistance properties such as glass transition point and heat distortion temperature, mechanical properties such as tensile strength, bending strength, limit pv value, abrasion resistance, chemical resistance, and boiling water resistance. Chemical properties such as water absorption and saturated water absorption are inferior. Moreover, 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 discovered that a predetermined copper compound, preferably a predetermined copper compound and a predetermined alkali metal halide are added to this polyamide. The inventors have discovered that, by doing so, it is possible to obtain a polyamide composition as a molding material that provides molded products with excellent heat aging resistance, and has thus arrived at the present invention.

(Structure of the Invention) The first polyamide composition according to the present invention is (A) fa)
An aromatic dicarboxylic acid component unit in which the terephthalic acid component unit is in the range of 60 to 100 mol%, and the aromatic dicarboxylic acid component unit other than the terephthalic acid component unit is in the range of 0 to 40 mol%, and fb) carbon A polyamide consisting of 6 to 18 aliphatic alkylene diamine component units, and (
B) 1 to 1100 as copper metal to the above polyamide
It is characterized by containing a copper compound in the range of 0 pp.

Moreover, the second polyamide composition according to the present invention is the above-mentioned (
In addition to A) and (B), CC") 1 to 110,000 pp to the above polyamide
It is characterized by containing an alkali metal halide within the range of .

In the polyamide composition according to the present invention, polyamide (
A) is an aromatic dicarboxylic acid component unit in which the fat terephthalic acid component unit is in the range of 60 to 100 mol%, and the aromatic dicarboxylic acid component unit other than the terephthalic acid component unit is 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. Specific examples of aromatic/group dicarboxylic acid component units other than terephthalic acid component units include component units such as isophthalic acid, phthalic acid, 2-methylterephthalic acid, and naphthalene dicarboxylic acid. I can give an example. 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 al, 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 such alkylene diamine component units 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-diaminohexane 2.4-dimethylhexane, 1.6-diami23.3-dimethylhexane, 1,
6-diamino-2,2-dimethylhexane, 1.9-diaminononane, 1.6-diamino-2.2.4-trimethylhexane, 1.6-diamino-2.4.4-)
Dimethylhexane, 1,7-diamy2-2,3-dimethylhebutane, 1,7-cyami2-2-4-dimethylhebutane, 1,7-diami2-2,5-dimethylhebutane,
1,7-Diami2-2,2-dimethylhebutane, ■, 1
0-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, 1,8-diamino-3,3-dimethyloctane, 1,8-diamino-4,
Examples of component units include 4-dimethyloctane, 1,6-diamino-2,4-diethylhexane, 1.9=diamino-5-methylnonane, 1,11-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 (al) described above is preferably selected depending on the number of carbon atoms in the aliphatic alkylene diamine. When selecting the composition of aromatic dicarboxylic acid component units (al), it is important to ensure that the resulting polyamide composition has excellent moldability, as well as heat resistance properties such as heat aging resistance and heat distortion temperature, and bending strength. This is because it provides a molded product with excellent mechanical properties such as wear resistance.

That is, when the aliphatic alkylene diamine has, for example, 6 carbon atoms, aromatic dicarboxylic acid forming units (al
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) is preferably 75 to 100 mol% of the terephthalic acid component unit. range, and aromatic dicarboxylic acid component units other than terephthalic acid component units are 0 to 25
in the range of 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 Inter
facial and 5solution Me
thods (by P. W. Morgan, Inter
science Publishers (1965))
Makromol, Chem, 47.93-1
13 (1961)), it can be obtained by polycondensing a 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 concentrated sulfuric acid at 50°C. It's okay. Here, polyamide that is insoluble in concentrated sulfuric acid at 50°C means pulverizing the polyamide, adding a 1% by weight concentrated sulfuric acid solution of the polyamide that has passed through 32 meshes at 50°C for 10 hours, and then stirring at 50°C. This refers to polyamide that has been filtered through a 2G glass filter at a temperature of Although such concentrated sulfuric acid-insoluble polyamide is not particularly limited, the melt viscosity (MFR) at 360° C. and a load of 2.16 kg is usually 20 g/10 minutes or less, preferably 5 g/10 minutes or less, Particularly preferably, 0
．． It is 1g/10 minutes 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.
°C or above, a method of polycondensing alkylene diamine and aromatic dicarboxylic acid at a charging molar ratio of 1.03 or more, and a method of polycondensing alkylene diamine and aromatic dicarboxylic acid together with trifunctional or higher polyamine Examples include a method of polycondensing polycarboxylic acids together with polycarboxylic acids.

In addition, when producing the concentrated sulfuric acid soluble polyamide or the concentrated sulfuric acid insoluble polyamide, catalysts and stabilizers such as phosphoric acid, hypophosphite, octyl phosphate, tristridecyl phosphite, etc. may be used.

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, the concentrated sulfuric acid-insoluble polyamide is contained in an amount of 2 to 1000 parts by weight, preferably 3 to 600 parts by weight, particularly preferably 5 to 400 parts by weight, based on 100 parts by weight of the concentrated sulfuric acid soluble polyamide. In this case, the molded product obtained from such a polyamide composition 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 invention contains a copper compound. As such copper compounds, copper halides and copper phosphates are particularly preferred. Examples of copper halides include cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, etc., and examples of copper phosphate include cupric phosphate. Examples include copper, cupric pyrophosphate, and the like. In addition, organic copper compounds such as copper acetate, salicyl weights, and benign weights, as well as copper oxide, copper sulfide, copper nitrate, copper sulfate, and sulfamine weights can also be used. In the polyamide composition according to the present invention, these copper compounds are contained in an amount of 1 to 100 Qppm as copper metal, preferably 1
It is blended in a range of 0 to 1100 pp. When the content of the copper compound is less than 1 ppm as copper metal based on the polyamide, the heat aging resistance of the molded product obtained from the polyamide composition is not sufficiently improved; If the amount is exceeded, mechanical strength such as tensile strength and bending strength will decrease.

In particular, according to the present invention, when the above-mentioned copper compound is used in combination with an alkali metal halide and is blended into the polyamide, the molded product obtained from the polyamide becomes significantly superior in heat aging resistance.

Examples of the alkali metal halides include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, etc. Among them, potassium iodide is particularly effective and is therefore preferably used.

The amount of alkali metal halide blended is 1 to 110,000 pp, preferably 10 to 5,000 pp to the polyamide.
It is blended within the pm range. As in the case of the copper compound, when the amount of the alkali metal halide is less than 1 ppm based on the polyamide, the effect of improving the heat aging resistance of the molded product due to the addition of the alkali metal halide is still insufficient; , 110,000 pp or more, the mechanical strength at room temperature, such as tensile strength and bending strength, decreases. Further, in the present invention, a polyamide composition can also be obtained by adding a copper compound and an alkali metal halide compound to raw materials and performing polycondensation.

In addition to the above-described copper compound and alkali metal halide, the polyamide composition according to the present invention may optionally contain conventionally known polymers, stabilizers, plasticizers, mold release agents, lubricants, fillers, etc. may contain. 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 improves the dynamic friction coefficient, taper wear, and limit P of molded products obtained from the composition.
It is preferably used because it improves wear resistance such as V 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 00μ, particularly in the range of 1 mμ to 100μ, because the wear resistance of the resulting molded product is significantly improved.

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 fibers made of the wholly aromatic polyamide are used as fillers, 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 usually preferably have an average length in the range of 0.1 to 201 m, particularly 1 to Low.

The amount incorporated is usually 200 parts by weight or less, preferably 5 to 180 parts by weight, particularly preferably 5 to 150 parts by weight, per 100 parts by weight of the polyamide.

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 according to the present invention comprises a polyamide having a predetermined composition and a predetermined metal copperide, or a polyamide having a predetermined composition, a predetermined copper compound, and a predetermined alkali metal halide. A molded article obtained from such a polyamide composition has 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.

(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 TA: Isophthalic acid C, DA: 1,6-hexamethylene diamine C1
゜mouth A: 1. The method for preparing the to-decamethylene diamine test piece and the method for evaluating each performance are as follows.

(Preparation of polyamide composition, test piece and evaluation of physical properties) Polyamide was crushed in a crusher (passed through 32 meshes), dried for 12 hours at 100°C and 1 g Hg,
Predetermined amounts of a copper compound and an alkali metal halide were triblended in nitrogen to form a polyamide composition.

Next, such a polyamide composition is hot pressed in a nitrogen atmosphere under a pressure of 100 kg/cut at a temperature 20° C. higher than the melting point of the polyamide using a press molding machine, and then cold pressed at a temperature of 20° C. A compression molded plate having a thickness of 2 to 4 fl was produced. These molded plates were cut into test pieces having the dimensions listed in Table 1, and then heated at a temperature of 23°C.
After being left in an atmosphere with a relative humidity of 65% for 96 hours, it was 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 compounded molded product was made of 60 parts by weight of a predetermined polyamide that had been crushed and dried and glass fiber (average length 6 fl, chopped strand C36PU-231 manufactured by Nitto Boseki Co., Ltd.).
40 parts by weight and a prescribed stabilizer were added to a single screw extruder (L/D=
28.20 m diameter) and mixed to obtain a polyamide composition in the form of approximately 6 strands, which was then press-molded in the same manner as in the case without the glass fiber blended above to produce a test piece. did.

Reference Example 1 123.6 g (0,744 mol) of terephthalic acid, 52.9 g (0,318 mol) of isophthalic acid, 123.4 g (1,0'6 mol) of hexamethylene diamine and 33 g of ion-exchanged water were mixed into 11 Place in a capacity autoclave,
After sufficient nitrogen substitution, the temperature was raised to 280° C. over 2 hours while stirring. Furthermore, keep it sealed at 280℃.
After the reaction proceeded for 1 hour, stirring was stopped and the reaction mixture was taken out from the bottom of the autoclave at a differential pressure of 10 kg/cal. This was dried overnight at 100° C. and 100 Hg in nitrogen.

This oligomer was extruded using a twin-screw extruder (screw diameter 30 days, L
/D=42, Barrel temperature (℃) 30/2/340/34
0/340, the 4th and 6th zones were vented to the atmosphere, the rotation speed was 8 Qrpm, the oligomer supply rate was 2 kg/hour, and the exhaust gas was purged with nitrogen) to advance polycondensation and increase the molecular weight. The results are shown in Table 2.

Reference Example 2 Polyamide was prepared in the same manner as in Reference Example 1, except that 97.0 g (0.58 mol) of terephthalic acid and 79.4 g (0.48 mol) of isophthalic acid were used in Reference Example 1. Manufactured. The results are shown in Table 2.

(Manufacture of sulfuric acid-insoluble polyamide) Reference Example 3 The polymer obtained in Reference Example 1 was subjected to solid phase polymerization at 280° C. and 1 mg for 4 hours with stirring to increase its molecular weight. The results are shown in Table 2.

Reference Example 4 In Reference Example 1, hexamethylenediamine 129.6
An oligomer was obtained in the same manner as in Reference 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 Reference Example 3. The results are shown in Table 2.

Reference Example 5 In Reference Example 1, 114.7 g (o,
An oligomer was obtained in the same manner as in Reference Example 1, except that 7 o mol) and 61.7 g (0.37 mol) of isophthalic acid were used, and this was made to have a high molecular weight in the same manner as in Reference Example 3. The results are shown in Table 2.

Reference example 6 232 g (1,40 mol) of terephthalic acid, 1.10-
241 g (1.4 mol) of diaminodecane and 10 I of ion-exchanged water! 1 equipped with a stirring bar, thermometer and reflux condenser
0! Pour into a reactor with a capacity of 95 to 1 V under nitrogen atmosphere
The reaction was carried out at a temperature of 00°C for 1 hour.

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

450 g (1.33 mol) of this nylon salt was charged into a 1i capacity reactor, the pressure was reduced to 1 Tsuru Hg, the inside of the reaction vessel was replaced with nitrogen, and the reaction was carried out at 300°C for 1.5 hours in a nitrogen stream to produce The water is extracted from the system and terephthalic acid-1
, 10-diaminodecane was obtained. [η] measured in concentrated sulfuric acid at 30°C is 0.45
It was dl/g.

This polyamide was crushed in a crusher (passed through 32 meshes), dried for 12 hours at 80°C and 5 (lnflg), and then subjected to solid phase polymerization at 300°C and 0.7 mmHg for 10 hours. A polyamide consisting of terephthalic acid-1,10-diaminodecane was obtained.

The results are shown in Table 2.

Example 1 30 ppm each of cupric chloride and potassium iodide (as Cu) was added to the polyamide described in Reference Example 1.
and 1400 ppm were triblended in nitrogen to prepare a polyamide composition. Table 3 shows the physical properties of test pieces prepared using this composition.

Examples 2 to 7 and Comparative Examples 1 to 5 Polyamides were prepared in the same manner as in Example 1, except that the polyamides listed in Table 3 and the stabilizers listed in Table 3 were used in the amounts listed in Table 3. A composition was prepared. Table 3 shows the physical properties of test pieces prepared using these compositions.

Claims (1)

[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) a fat having 6 to 18 carbon atoms. 1. A polyamide composition comprising a polyamide comprising a group alkylene diamine component unit, and (B) a copper compound in an amount of 1 to 1000 ppm as copper metal based on the polyamide. (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) a fat having 6 to 18 carbon atoms. (B) a copper compound having an amount of copper metal in the range of 1 to 1000 ppm based on the polyamide; and (C) an alkali halide having an amount of 1 to 10000 ppm based on the polyamide. A polyamide composition containing a metal.