JPS63196625A - Polyamide composition and its production - Google Patents

Abstract

PURPOSE:To produce the title composition excellent in thermal aging resistance and moldability, by polycondensing an aromatic dicarboxylic acid with an aliphatic alkylene-diamine in the presence of a specified prim. or sec. amine and a hypophosphite. CONSTITUTION:An aromatic dicarboxylic acid component unit (A) comprising 60-100mol.% terephthalic acid component units and 40-0mol.% other aromatic dicarboxylic acid component units (e.g., isophthalic acid) is polycondensed with a 6-18C aliphatic alkylenediamine component units (B) (e.g., 1,4-diamino-1,1- dimethylbutane) in the presence of 0.01-5mol.%, based on component B monocarboxylic acid or prim. or sec. monoamine and 0.01-5mol.% hypophos phite (e.g., calcium hypophosphite) to obtain a polyamide composition of an intrinsic viscosity (as measured in conc. sulfuric acid at 30 deg.C) >= 0.5dl/g.

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 physical properties as well as excellent moldability, that is, fluidity, and a method for producing the same.

[Conventional technology]

-i, thermoplastic resins such as polyolefin, polyester, and polyamide 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, it has better heat resistance, mechanical properties and chemical properties.

Engineering plastics with excellent physical properties include polytetrafluoroethylene known as Teflon (registered trademark), polyparaphenylene terephthalamide known as Kevlar (registered trademark), and Kapton (
Polyimide consisting of a condensate of 4,4''-diaminodiphenyl ether and pyromellitic anhydride known as 6,6-nylon, polyhexamethylene aziboamide known as 6,6-nylon, Trogamide T (registered trademark) Known poly(2,2,4-trimethylhexamethylene terephthalamide), polyphenylene sulfide, boria tar, 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 aziboamide, 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 S impact strength and abrasion resistance.
On the other hand, polyhexamethylene aziboamide, 2,4.4-
) Polyamides such as trimethylhexamethylene terephthalamide have various properties such as glass transition point, heat resistance properties such as heat distortion temperature, tensile strength, bending strength, limit PV (ii), mechanical properties such as abrasion resistance, chemical resistance, etc. Polyacetal has poor chemical properties such as boiling water resistance and saturated water absorption.In addition, polyacetal has poor melting point,
It is inferior in heat resistance properties such as 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
Polyamides consisting of aromatic dicarboxylic acid component units whose main component is terephthalic acid component units and aliphatic alkylene diamine component units have excellent heat resistance properties, mechanical strength, chemical and physical properties, and molding properties, and are particularly , discovered that it has excellent sliding characteristics (Patent application 1986-120)
No. 40).

However, as a result of intensive research into this polyamide in order to improve its heat aging resistance, the present inventors found that
It has been discovered that by adding a predetermined monocarboxylic acid or monoamine and hypophosphite, it is possible to obtain a polyamide composition as a molding material that gives molded products with excellent heat aging resistance. By adding a monocarboxylic acid or a monoamine and a hypophosphite at any stage of polycondensation to produce polyamide, it is possible to obtain a polyamide composition that has excellent fluidity and excellent moldability. Furthermore, it was discovered that this polyamide composition can give molded articles having excellent heat aging resistance, leading to the present invention.

[Structure of the invention]

The polyamide composition according to the present invention comprises: (A) (a) Terephthalic acid component units are in the range of 60 to 100 mol%, and aromatic dicarboxylic acid component units other than terephthalic acid component units are in the range of 0 to 40 mol%. (B) a monocarboxylic acid or monoamine in an amount of 0.01 to 5 mol% based on the aliphatic alkylene diamine component constituting the polyamide; 1 amine or secondary amine, and 0.01 to 5 mol% of hypophosphite. Further, the method for producing a polyamide composition according to the present invention includes: (a) terephthalic acid component units are in the range of 60 to 100 mol%, and aromatic dicarboxylic acid component units other than terephthalic acid component units are in the range of 0 to 40 mol%; (c) a primary 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; or in the presence of a secondary amine and 0.01 to 5 mol% hypophosphite,
It is characterized by polycondensing the 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) 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%. and (b) tL division of labor prime number 6 to 1
Consists of 8 aliphatic alkylene diamine component units.

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 dicarboxylic acid component units other than terephthalic acid component units that may be present include component units such as isophthalic acid, phthalic acid, 2-methylterephthalic acid, and naphthalene dicarboxylic acid. can do. 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 %. Among the aromatic dicarboxylic acid component units fa), when terephthalic acid is less than 60 mol% and aromatic dicarboxylic acid component units other than terephthalic acid component units are more than 40 mol%, such a polyamide is included. The molded product obtained from the composition is inferior in 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. .

However, in the present invention, the aromatic dicarboxylic acid component unit (a), together with the terephthalic acid component unit and the aromatic dicarboxylic acid component unit other than the terephthalic acid component unit, contains a small amount, for example, about 10 mol% of adipine. There is no problem in including a polyhydric carboxylic acid component such as acid, sebacic acid, trimellitic acid, and pyromellitic acid.

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-Diami2,5-dimethylhexane, 1,6-Diami2,4-dimethylhexane, 1,6-Diami2,3,3-dimethylhexane, 1
．． 6-Diami2,2-dimethylhexane, 15.9
-diaminononane, 1.6-diamitsu2.2.4-
) dimethylhexane, 1,6-diami2,4,4-
Trimethylhexane, 1,7-diamy22,3-dimethylhebutane, 1,7-diamy22゜4, dimethylhebutane, 1,7-diamy22,5-dimethylhebutane, 1,7-diamy22.2 -dimethyl hebutane, 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, 1,8-diamino-3,3-dimethyloctane, 1,8-diamino-
4,4-dimethyloctane, 1,6-diami2,4
Examples include component units such as -diethylhexane, 1,9-diamino-5-methylnonane, 1,11-diaminoundecane, and 1,12-diaminododecane.

Among these, in particular, 1,6-diethylhexane,
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 fa) according to the number of carbon atoms in the aliphatic alkylene diamine, it is particularly important to ensure that the resulting polyamide composition has excellent moldability, heat aging resistance and heat aging resistance. This is because it provides a molded product with excellent heat resistance properties such as deformation temperature, and mechanical properties such as bending strength and abrasion resistance.

That is, when the aliphatic alkylene diamine has, for example, 6 carbon atoms, the aromatic dicarboxylic acid component unit (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) preferably includes 75 to 100 moles of terephthalic acid component unit. % range, and aromatic dicarboxylic acid component units other than terephthalic acid component units are 0 to 2
It is in the range of 5 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, preferably [η] is 0.6 dl/.

Above, the range is particularly preferably from 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
sationPoly+aers by Interf
acial and 5solution Method
s(P, W0 Morgan, Interscience
e Publishers (1965)) and Makr.
omol, Chem, 47.93-113 (196
As described in 1)), it can be obtained by fU polycondensation of the diacid halide of an aromatic dicarboxylic acid and an aliphatic alkylene diamine, which are the polyamide constituent units described above, by a solution method.

It can also be obtained by interfacial polymerization.

Alternatively, it can be obtained by polycondensing the aromatic dicarboxylic acid and alkylene diamine or its nylon salt in the presence or absence of a solvent such as water by a solution MA method. Furthermore, it can also be obtained by subjecting the polyamide oligomer obtained by the former method to 11 polymerization 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 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. refers to polyamide that has been filtered through a 2G glass filter to remove the soluble portion.
Such concentrated sulfuric acid-insoluble polyamides are not particularly limited, but the melt viscosity (MFR) at 360°C and a load of 2.16 kg is usually 20 g/l 0 min or less, preferably 5 g/10 min. Below, particularly preferably,
It is 0.1 g/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 t;g acid-soluble polyamides by melt polycondensation, the polycondensation temperature is increased to a higher temperature, e.g.
0°C or higher, a method of polycondensing alkylene diamine and aromatic dicarboxylic acid with 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 functional polyamine or polycarboxylic acid. Examples include a method in which an acid is used in combination to cause polycondensation.

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. 2 to 1000 parts by weight, preferably 3 to 600 parts by weight, particularly preferably 5 to 400 parts by weight of the concentrated sulfuric acid-insoluble polyamide per 100 parts by weight! When the polyamide composition is contained in an amount of i parts, the molded product obtained from the 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 primary or secondary amine that is a monocarboxylic acid or 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, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid as aliphatic monocarboxylic acids. 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 amines, aniline, toluidine, diphenylamine, naphthylamine and the like.

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 o, oi 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 a large amount exceeding 5 mol % is blended, 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 hypophosphite, in particular an alkali metal hypophosphite salt, together with the above-mentioned monocarboxylic acid or monoamine as an additive. Specifically, such hypophosphites include potassium hypophosphite, sodium hypophosphite, calcium hypophosphite, barium hypophosphite, magnesium hypophosphite, manganese hypophosphite, and hypophosphite. Examples include nickel and cobalt hypophosphite.

In the polyamide composition according to the present invention, these hypophosphite salts are also contained in a range of 0.01 to 5 mol%, based on the aliphatic alkylene diamine component constituting the polyamide.
It is preferably blended in a range of 0.02 to 2 mol%, particularly preferably in a range of 0.05 to 1 mol%. When adding a large amount of hypophosphite exceeding 5 mol %, for the same reason as explained for monocarboxylic acids or monoamines, the tensile strength, bending strength, etc. of molded products from the resulting polyamide composition may be This is not preferable because it reduces mechanical strength.

As mentioned above, polyamide can be obtained by any method such as a melt method, an in-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 the step, preferably adding the hypophosphite 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 and mixing a monocarboxylic acid or a monoamine and a hypophosphite together to a polyamide obtained by any method.

However, in the present invention, the monocarboxylic acid or monoamine and hypophosphite are added in combination at the stage of polycondensing the dicarboxylic acid component and the aliphatic alkylene diamine component, or their nylon salts or oligomers. By doing so, it is possible to obtain a polyamide composition having particularly excellent fluidity, and furthermore, such a polyamide composition can provide a molded article having particularly excellent heat aging resistance.

In the polyamide composition according to the present invention, in addition to the monocarboxylic acid or monoamine and hypophosphite described above, conventionally known polymers, stabilizers, plasticizers, mold release agents, and lubricants may be used as necessary. , fillers, etc. may be contained.

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 transitional or cross-like 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.

Examples of organic fillers include polyparaphenylene terephthalamide, polymetaphenylene terephthalamide, polyparaphenylene isophthalamide, polymetaphenylene isophthalamide, condensates 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 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 usually preferably have an average length in the range of 0.1 to 2011 m, particularly 1 to 10 m.

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 of the present invention contains a polyamide having a predetermined composition, a monocarboxylic acid or a monoamine, and a hypophosphite, and can be obtained from such a polyamide composition. In particular, the heat aging resistance of the molded product is significantly improved. 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 polyamide raw materials in the presence of and hypophosphite, thermal deterioration of the polymer is prevented during polycondensation.
Furthermore, a polyamide composition with excellent fluidity can be obtained. Moreover, this composition provides molded articles with excellent heat aging resistance.

〔Example〕

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

TA: Terephthalic acid IA: Isophthalic acid C, DA: 1,6-hexamethylenediamine CI
t+DA: The method for preparing the 1,10-decamethylenediamine test piece and the method for evaluating each performance are as follows.

[Preparation of test pieces of polyamide composition molded products and evaluation of physical properties]

The polyamide composition was crushed in a crusher (passed through 32 meshes) and dried under conditions of 100° C. and lmHg for 12 hours. This polyamide composition was molded using a press molding machine in a nitrogen atmosphere at 100 kg/an! After hot pressing at a temperature 20°C higher than the melting point of the polyamide under a pressure of
Cold pressing was performed at a temperature of 20° C. to produce a compression molded plate having a thickness of 2 to 4 mm.

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 open air 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 61 m, chopped strand C36PE-231 manufactured by Nitto Boseki Co., Ltd.).
40 parts by weight and a prescribed stabilizer were uniaxially extruded (L/D
= 28.20 m diameter) and mixed to obtain a strand-shaped polyamide composition of approximately 6B, which was then press-molded in the same manner as in the case where no glass fiber was blended, and a test piece was performed. Example 1 Terephthalic acid 123.6 g (0,744 mol), isophthalic acid 52.9 g (0,318 mol), benzoic acid 1.22 g (0,01 mol), hexamethylenediamine 123.4 g (1, 0.06 mol), 0.2254 g (0.00212 mol) of sodium hypophosphite hydrate, and 33 g of ion-exchanged water. ! The mixture was charged into a volumetric autoclave, and after sufficient 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°C was applied from the bottom of the autoclave.
The reaction mixture was removed at kg/cd. This was dried in nitrogen at 100° C. and 100 mmHg overnight.

This oligomer was extruded using a twin-screw extruder (screw diameter 30 mm,
L/D-42, barrel temperature ("C) 30/2
60/4th and 6th zones are vented to atmosphere, rotation speed 8O
Polycondensation was carried out at an rpm oligomer supply rate of 2 kg/hour and the exhaust gas was purged with nitrogen, and the molecular weight was increased 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 (Q, 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 mdg 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,
An oligomer was obtained in the same manner as in Example 2, except that 61.7 g (0.37 mol) of isophthalic acid was used, and the oligomer was made to have a high molecular weight in the same manner as in Example 3.
A hydrochloric acid-insoluble polyamide composition was obtained. Table 2 shows the properties of the polyamide thus obtained and the physical properties of molded test pieces obtained from this composition.

Example 6 Terephthalic acid 232 g (1.40 mol), 1.1
241 g (1.4 mol) of 0-diaminodecane, 0.297 g (0,0028 mol) of sodium hypophosphite monohydrate, and 10 j2 of ion-exchanged water were mixed into a 102-liter tube equipped with a stirring bar, a thermometer, and a reflux condenser. The mixture was charged into a large capacity reactor and reacted for 1 hour at a temperature of 95 to 100°C under a nitrogen atmosphere.

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 a+laHg to obtain 450 g of nylon salt of terephthalic acid-1,10-diaminodecane.

450 g (1.33 mol) of this nylon salt was
After filling a large capacity reactor and purging the inside of the reaction vessel with nitrogen,
Gradually raise the temperature in a nitrogen stream, and after reaching 300℃,
．． The reaction was allowed to proceed for 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. Measured in concentrated sulfuric acid at 30°C [η]
is 0.4! It was M7/g.

This polyamide was crushed in a crusher (passed through 32 meshes), dried at 80°C and 50 mmHg for 12 hours, and then subjected to solid phase polymerization at 300°C and 0.7++a+Hg for 10 hours to produce terephthalic acid- A polyamide consisting of 1,10-diaminodecane was obtained. 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 611II11, chopped strand C56PE-231 manufactured by Nittobo Co., Ltd.) was blended with 60 parts by weight of the polyamide synthesized by the method of Example 2, and its physical properties were evaluated. did. 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 6.0 g of sodium hypophosphite monohydrate were used.
A polyamide was produced as described in Example 1, except that 74 g was used. The results are shown in Table 2.

Claims (1)

[Claims] [1] (A) (a) Terephthalic acid component units are 60 to 10
(b) aliphatic alkylene having 6 to 18 carbon atoms; and (b) an aliphatic alkylene having 6 to 18 carbon atoms. a polyamide consisting of a diamine component unit, and (B) a primary amine or a secondary amine that 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; A polyamide composition comprising 0.01 to 5 mol% of hypophosphite. [2] (a) 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%. , (b) aliphatic alkylene diamine component unit 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 compound dicarboxylic acid and the above aliphatic alkylene diamine component in the coexistence of a primary amine or a secondary amine which is a monocarboxylic acid or a monoamine, and 0.01 to 5 mol% of hypophosphite. A method for producing a polyamide composition, which comprises polycondensing or polycondensing their nylon salts or oligomers.