JPH06322111A - Aromatic polyamide resin and resin composition containing the same - Google Patents

Abstract

PURPOSE:To provide a polyamide resin having a combination of inherent heat resistance with excellent processability and low water absorptivity and good in mechanical properties and dimensional stability, containing a specific bis[(aminophenoxy)benzoyl]diphenyl ether. CONSTITUTION:The objective aromatic polyamide of formula I (X is <=20C condensed polycyclic aromatic group or of formula II; Y is direct bond, O, S, etc.; R is 1-4C alkyl, halogen, etc.; a is 0-2; b is 0-4; n is 1-1000). This polyamide can be obtained by polycondensation between (A) 3,3-bis[4-(4aminophenoxy) benzoyl]diphenyl ether of formula III and (B) an aromatic dicarboxylic dihalide in the presence of a dehydrohalogenating agent and a monocarboxylic acid in an organic solvent at <=60 deg.C or by polycondensation between the compound of the formula III and an aromatic dicarboxylic acid in the presence of a condensation agent in an organic solvent at 10-15 deg.C. This polyamide has the basic skeleton of the formula I with the molar ratio of the aromatic carboxylic acid constituent to the aromatic diamine constituent being 0.7-1.0.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel heat-resistant melt-moldable aromatic polyamide. Further, the present invention relates to a novel aromatic polyamide resin composition which is excellent in dimensional stability and mechanical properties and is excellent in processability.

[0002]

2. Description of the Related Art Aromatic polyamides obtained by reacting aromatic diamines or aromatic diisocyanates with aromatic dicarboxylic acids or their derivatives have hitherto been known for their various excellent physical properties and good heat resistance. It is expected that it will be widely used in the fields where heat resistance is required in the future.
However, although many aromatic polyamides that have been conventionally developed have excellent mechanical properties and heat resistance, they all have the drawbacks of poor moldability and high water absorption. For example, the following formula [Chemical formula 5]

[0003]

[Chemical 5] The aromatic polyamide having a basic skeleton represented by (Dupont's product: Trademark Nomex) has excellent properties such as flame retardancy and high heat resistance. However, this aromatic polyamide does not have a clear glass transition temperature and has a thermal decomposition temperature of 4
Since it is about 00 ° C and the processing temperature and the thermal decomposition temperature are close to each other, there is a drawback that processing is difficult to use as a molding material. Therefore, it is only used in the field of fibers, films, pulp, etc. by the wet spinning method (for example, Japanese Patent Publication No. 48-17551). Further, the water absorption rate is as high as 5.5%, and it is obvious that it has a bad influence on dimensional stability, insulation, solder heat resistance, etc. when used as a base material for electric / electronic parts.

[0004]

An object of the present invention is to provide an aromatic polyamide which has excellent processability and low water absorption in addition to the excellent heat resistance inherent in the aromatic polyamide, and a method for producing the same. . Further, it is to provide a novel resin composition which has improved mechanical strength and dimensional stability of the aromatic polyamide and has excellent processability.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies to achieve the above-mentioned objects, and as a result, found a novel aromatic polyamide having a desired performance and a resin composition thereof, and completed the present invention. Came to. That is, the present invention provides (1) Formula (I) [Chemical Formula 6]

[0006]

[Chemical 6] (In the formula, X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound of the formula [Chem. 7]

[0007]

[Chemical 7] R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a halogen group, a phenyl group, a is 0, 1 or 2, and b is 0.
Alternatively, it represents an integer of 1 to 4. Moreover, n represents the integer of 1-1000. (2) Formula (II) [Chemical formula 8]

[0008]

[Chemical 8] Which is obtained by polycondensing 3,3′-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether represented by and an aromatic dicarboxylic acid in an organic solvent, (1 (3) A method for producing an aromatic polyamide, (3) a polymer having a repeating unit represented by the formula (I) as a basic skeleton and using a monovalent amine or a monovalent carboxylic acid or a carboxylic acid derivative. Aromatic polyamide with molecular ends blocked and good thermal stability, and method for producing the same, (4) 100 parts by weight of the aromatic polyamide according to (1) or (3), and fibrous reinforcing materials 5 to 1
The aromatic polyamide resin composition comprises 100 parts by weight.

The aromatic polyamide of the present invention comprises a diamine represented by the formula (II) as a diamine component, that is, 3,3'-
It is obtained by polymerizing bis [4- (4-aminophenoxy) benzoyl] diphenyl ether with an aromatic dicarboxylic acid or its derivative. Furthermore, the aromatic polyamide resin composition of the present invention can be obtained by adding a fibrous reinforcing material to the aromatic polyamide of the present invention. That is, the aromatic polyamide and the resin composition thereof of the present invention are characterized by using 3,3′-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether as a diamine component, and the aromatic polyamide originally has A thermoplastic aromatic polyamide and a resin composition thereof, which have excellent processability in addition to heat resistance. Since the aromatic polyamide and the resin composition have excellent heat resistance and thermoplasticity, they can be extrusion-molded and injection-molded. Further, as a base material for space / aircraft, a base material for electric / electronic parts, Further, it can be expected to be used for various purposes as a raw material of high-strength, high-heat-resistant fiber by the melt spinning method, and is extremely useful. The aromatic polyamide of the present invention is an aromatic polyamide using the above-mentioned diamine as a raw material, but other diamines can be mixed and used as long as the good physical properties of the aromatic polyamide are not impaired.

Examples of diamines that can be mixed and used include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 2-chloro-1,4-.
Phenylenediamine, 4-chloro-1,2-phenylenediamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 2 -Methoxy-1,4-phenylenediamine, 4-methoxy-1,
2-phenylenediamine, 4-methoxy-1,3-phenylenediamine, benzidine, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,
4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfoxide, 3,
4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,
3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone,
3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] Methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4
-(3-Aminophenoxy) phenyl] ethane, 1,2
-Bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane , 2,2-bis [4- (3
-Aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane,
2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl]- 1,1,1,3,3,3-hexafluoropropane, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3 -Aminophenoxy) phenyl]
Ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3 -Aminophenoxy) phenyl] sulfoxide, bis [4- (4-
Aminophenoxy) phenyl] sulfoxide, bis [4
-(3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone,
Bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy)
Benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-Aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4
-Aminophenoxy) phenoxy} phenyl] ketone,
Bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4 -(4-aminophenoxy)-
α, α-Dimethylbenzyl] benzene and the like can be used, and these can be used alone or in admixture of two or more.

The method for producing the aromatic polyamide of the present invention is not particularly limited, and conventionally known methods can be adopted. For example, (a) a method of polycondensing an aromatic diamine and an aromatic dicarboxylic acid in the presence of a condensing agent in an organic solvent at a reaction temperature of 10 to 150 ° C., (a) an aromatic diamine and an aromatic dicarboxylic acid A method of polycondensing a dihalide with an organic solvent at a reaction temperature of 60 ° C. or lower in the presence of a dehydrohalogenating agent, and (c) an aromatic diamine and an aromatic dicarboxylic acid dialkylate and / or an aromatic dicarboxylic acid diallylate. Is polycondensed in an organic solvent at a reaction temperature of 100 to 300 ° C.

The aromatic diamine used in this method is
It is 3,3'-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether. As the aromatic dicarboxylic acid used, an aromatic dicarboxylic acid is used in the method (a). For example, when a in the above formula is 0, phthalic acid, methylphthalic acid, ethylphthalic acid, methoxyphthalic acid, ethoxyphthalic acid, chlorophthalic acid, bromophthalic acid, isophthalic acid, methylisophthalic acid, ethylisophthalic acid, methoxyisophthalic acid, Examples thereof include ethoxyisophthalic acid, chloroisophthalic acid, bromoisophthalic acid, terephthalic acid, methylterephthalic acid, ethylterephthalic acid, methoxyterephthalic acid, ethoxyterephthalic acid, chloroterephthalic acid and bromoterephthalic acid. When a is 1 or 2, 2,2′-biphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,
4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfide dicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) -1,
Examples include 1,1,3,3,3-hexafluoropropane. When X in the above formula is a condensed polycyclic aromatic group, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and the like can be mentioned. These aromatic dicarboxylic acids are
They may be used alone or in combination of two or more.

In the method (a), aromatic dicarboxylic acid dihalide is used. For example, the above-mentioned aromatic dicarboxylic acid dihalide, that is, aromatic dicarboxylic acid dichloride, aromatic dicarboxylic acid dibromide and the like can be mentioned. These aromatic dicarboxylic acid dihalides may be used alone or in admixture of two or more. Further, in the method (c), an aromatic dicarboxylic acid dialkyl ester and / or an aromatic dicarboxylic acid diallyl ester is used. For example, each of the above aromatic dicarboxylic acids, a dialkyl ester having 1 to 10 carbon atoms, a diphenyl ester, a di (fluorophenyl) ester,
Di (chlorophenyl) ester, di (bromophenyl)
Ester, di (methylphenyl) ester, di (ethylphenyl) ester, di (propylphenyl) ester, di (isopropylphenyl) ester, di (butylphenyl) ester, di (isobutylphenyl) ester, di (t-butylphenyl) ) Ester, di (methoxyphenyl) ester, di (ethoxyphenyl) ester, di (nitrophenyl) ester, di (phenylphenyl) ester, dinaphthyl ester and the like. These aromatic dicarboxylic acid diesters may be used alone or in combination of two or more.

The diamine component and the aromatic dicarboxylic acid or its derivative are polymerized in a solvent. Examples of the solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3- Dimethyl
2-imidazolidinone, N-methylcaprolactam, dimethyl sulfoxide, dimethyl sulfone, sulfolane,
Tetramethylurea, hexamethylphosphoramide, pyridine, α-picoline, β-picoline, γ-picoline,
2,4-lutidine, 2,6-lutidine, quinoline, isoquinoline, triethylamine, tripropylamine, tributylamine, tripentylamine, N, N-dimethylaniline, N, N-diethylaniline, dichloromethane, chloroform, carbon tetrachloride , 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, 1,1,2,2-tetrachloroethane, tetrachloroethylene, n-hexane, cyclohexane, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, Acetonitrile, propionitrile, acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, isopropyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxy 1,1,4-dioxane, anisole, phenetole, benzyl ether, phenyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, benzene, toluene , O-xylene, m-
Xylene, p-xylene, diphenyl, terphenyl,
Benzyl chloride, nitrobenzene, 2-nitrotoluene,
3-nitrotoluene, 4-nitrotoluene, chlorobenzene, 2-chlorotoluene, 3-chlorotoluene, 4-
Chlorotoluene, o-dichlorobenzene, p-dichlorobenzene, bromobenzene, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2, 6-xylenol, 3,4-xylenol,
3,5-xylenol, o-chlorophenol, p-chlorophenol, methanol, ethanol, propanol, isopropanol, butanol, isobutanol,
Examples thereof include t-butanol, cyclohexanol, benzyl alcohol, water and the like. In addition, these solvents may be used alone or as a mixture of two or more, depending on the type of reaction raw material monomer and the polymerization technique.

When an aromatic dicarboxylic acid dihalide is used as the monomer of the reaction raw material, a dehydrohalogenating agent is usually used together. Examples of the dehydrohalogenating agent used include trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine,
N, N-dimethylbenzylamine, N, N-diethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-
Dimethylaniline, N, N-diethylaniline, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-methylmorpholine, N-ethylmorpholine, pyridine, α-picoline,
β-picoline, γ-picoline, 2,4-lutidine, 2,
6-lutidine, quinoline, isoquinoline, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate,
Calcium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium oxide, lithium oxide, sodium acetate,
Examples thereof include potassium acetate, ethylene oxide, propylene oxide and the like.

When an aromatic dicarboxylic acid is used as the reaction raw material monomer, a condensing agent is usually used.
As the condensing agent used, sulfuric anhydride, thionyl chloride,
Sulfite, picryl chloride, phosphorus pentoxide, phosphorus oxychloride, phosphite-pyridine-based condensing agent, triphenylphosphine-hexachloroethane-based condensing agent, propylphosphoric anhydride-N-methyl-2-pyrrolidone-based condensing agent Etc. The reaction temperature is usually 300 ° C. or lower, though it varies depending on the polymerization method and the type of solvent. The reaction pressure is not particularly limited and can be carried out at normal pressure. The reaction time is
Although it varies depending on the type of reaction raw material monomer, the polymerization method, the type of solvent, the type of dehydrohalogenating agent, the type of condensing agent, and the reaction temperature, the formation of the aromatic polyamide represented by the formula (I) is usually completed. Allow sufficient time for reaction. Normal,
10 minutes to 24 hours is sufficient. By such a reaction, the compound represented by the formula (I)

[0017]

[Chemical 9] (In the formula, X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound of the formula

[0018]

[Chemical 10] R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a halogen group, a phenyl group, a is 0, 1 or 2, and b is 0.
Alternatively, it represents an integer of 1 to 4. Moreover, n represents the integer of 1-1000. An aromatic polyamide having a repeating unit represented by That is, the aromatic polyamide of the present invention can be obtained by any method such as a low-temperature solution polycondensation method and a direct polycondensation method which are conventionally known as polyamide synthesis methods.

The aromatic polyamide of the present invention contains 3,3'-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether as a reaction raw material monomer and an aromatic dicarboxylic acid or an aromatic dicarboxylic acid dihalide. It is characterized by using a dicarboxylic acid derivative. However, in order to improve the thermal stability and moldability of the aromatic polyamide, it does not matter even if the end of the polymer molecule is capped with a monovalent carboxylic acid or a carboxylic acid derivative or a monovalent amine. Absent. Such an aromatic polyamide has the above formula (I
I) an aromatic diamine containing 3,3'-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether as a main component and an aromatic dicarboxylic acid or an aromatic dicarboxylic acid derivative as a monovalent carboxylic acid or carboxylic acid It can be obtained by reacting in the presence of a derivative or a monovalent amine. That is, a part of the aromatic dicarboxylic acid or the aromatic dicarboxylic acid derivative is a monocarboxylic acid derivative such as an aromatic and / or aliphatic and alicyclic monocarboxylic acid or a monocarboxylic acid halide, and a diamine component It is produced by substituting a part of the aromatic and / or aliphatic and / or alicyclic monoamine.

The monocarboxylic acids used in these methods include benzoic acid, chlorobenzoic acids, bromobenzoic acids, methylbenzoic acids, ethylbenzoic acids, methoxybenzoic acids, ethoxybenzoic acids, nitrobenzoic acids,
Acetylbenzoic acid, acetoxybenzoic acid, hydroxybenzoic acid, biphenylcarboxylic acid, benzophenonecarboxylic acid, diphenylethercarboxylic acid, diphenylsulfidecarboxylic acid, diphenylsulfonecarboxylic acid, 2,2-diphenylpropanecarboxylic acid, 2,2-diphenyl-1 , 1,1,3,3,3-hexafluoropropanecarboxylic acid, naphthalenecarboxylic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, nitroacetic acid, propionic acid, butyric acid, Examples include valeric acid, caproic acid, cyclohexanecarboxylic acid and the like. These monocarboxylic acids may be used alone or in admixture of two or more.

As the monocarboxylic acid halide,
Examples thereof include acid chlorides and acid bromides of the above monocarboxylic acids. These monocarboxylic acid halides may be used alone or in admixture of two or more. Examples of the monocarboxylic acid ester include alkyl esters of the above monocarboxylic acids having 1 to 10 carbon atoms, phenyl ester, fluorophenyl ester, chlorophenyl ester, bromophenyl ester, methylphenyl ester, ethylphenyl ester, propylphenyl ester. Examples thereof include ester, isopropylphenyl ester, butylphenyl ester, isobutylphenyl ester, t-butylphenyl ester, methoxyphenyl ester, ethoxyphenyl ester, nitrophenyl ester, phenylphenyl ester and naphthyl ester. These monocarboxylic acid esters may be used alone or
Used as a mixture of two or more species. The amount of the monocarboxylic acid used is 0.001 to 1.
It is 0 mol. If it is less than 0.001 mol, the viscosity is increased during high temperature molding, which causes deterioration of molding processability. Further, if it exceeds 1.0 mol, the mechanical properties are deteriorated. The preferable amount used is 0.01 to 0.5 mol.

When a monovalent amine is used, for example, aniline, o-toluidine, m-toluidine, p
-Toluidine, 2,3-xylidine, 2,4-xylidine, 2,5-xylidine, 2,6-xylidine, 3,4
-Xylidine, 3,5-xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p -Nitroaniline, o-anisidine, m-anisidine, p-
Anisidine, o-phenetidine, m-phenetidine, p
-Phenetidine, o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile , 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-
Aminophenyl phenyl ether, 4-aminophenyl phenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-
Aminophenyl phenyl sulfide, 3-aminophenyl phenyl sulfide, 4-aminophenyl phenyl sulfide, 2-aminophenyl phenyl sulfone, 3-
Aminophenylphenyl sulfone, 4-aminophenylphenyl sulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 2-amino-1
-Naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 5-amino-2-naphthol, 7
-Amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, methylamine, dimethylamine, ethylamine, diethylamine, propylamine , Dipropylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, isobutylamine, diisobutylamine, pentylamine, dipentylamine, benzylamine, cyclopropylamine, cyclobutylamine,
Examples thereof include cyclopentylamine and cyclohexylamine. These monoamines may be used alone or in combination of two or more.

The amount of monoamine used is 0.001 to 1.0 mol per mol of the aromatic dicarboxylic acid.
If it is less than 0.001 mol, the viscosity is increased during high temperature molding, which causes deterioration of molding processability. Further, if it exceeds 1.0 mol, the mechanical properties are deteriorated. The preferred usage is
It is a ratio of 0.01 to 0.5 mol. The aromatic polyamide and its resin composition of the present invention can be subjected to melt molding. In this case, another thermoplastic resin may be blended in an appropriate amount depending on the purpose within a range not impairing the purpose of the present invention. As the thermoplastic resin that can be blended, polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polyimide, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyphenylene sulfide, polyamide imide, polyether imide, modified Examples thereof include polyphenylene oxide. It is also possible to add a thermosetting resin or a filler to an extent that the object of the invention is not impaired. As a thermosetting resin,
Examples include phenolic resins and epoxy resins. As the filler, graphite, carborundum, silica stone powder,
Wear resistance improving materials such as molybdenum disulfide and fluororesin, glass fibers, carbon fibers, boron fibers, silicon carbide fibers, carbon whiskers, asbestos, metal fibers, reinforcing materials such as ceramic fibers, antimony trioxide, magnesium carbonate, carbonic acid Flame retardant improver such as calcium, electrical property improver such as clay and mica, tracking resistance improver such as asbestos, silica and graphite, acid resistance improver such as barium sulfate, silica and calcium metasilicate,
Examples include thermal conductivity improvers such as iron powder, zinc powder, aluminum powder, and copper powder, as well as glass beads, talc, diatomaceous earth, alumina, silasbaln, hydrated alumina, metal oxides, and colorants.

As the fibrous reinforcing material used in the present invention, various ones are used, such as glass fiber, carbon fiber,
Potassium titanate fibers, aromatic polyamide fibers, silicon carbide fibers, alumina fibers, boron fibers, ceramic fibers and the like can be mentioned, but particularly preferably used are glass fibers, carbon fibers, potassium titanate fibers, aromatic polyamide fibers. Is.

The glass fiber used in the present invention is a glass fiber having a predetermined diameter, which is obtained by rapidly cooling molten glass while stretching it by various methods. A strand obtained by bundling single fibers together with a sizing agent, It means a roving or the like in which strands are evenly aligned and bundled, and any of them can be used in the present invention. The glass fiber is a silane coupling agent such as aminosilane and epoxysilane, chromic chloride, in order to have an affinity with the base resin of the present invention.
Other surface treatment agents can be used depending on the purpose. The length of the glass fiber in the present invention greatly affects the physical properties of the obtained molded product and the workability at the time of manufacturing the molded product. Generally, as the glass fiber length increases, the physical properties of the molded product improve, but conversely, the workability during manufacturing of the molded product deteriorates. Therefore, the length of the glass fiber is 0.1 to 6 in the present invention.
mm, preferably in the range of 0.3-4 mm,
It is preferable because the physical properties and workability of the molded product are well balanced.

The carbon fiber used in the present invention is a high elasticity and high strength fiber obtained by carbonizing polyacrylonitrile, petroleum pitch, etc. as a main raw material. In the present invention, both polyacrylonitrile type and petroleum pitch type can be used. As the carbon fiber, one having an appropriate diameter and an appropriate aspect ratio (ratio of length / diameter) is used depending on the reinforcing effect and the mixing property. The diameter of carbon fiber is usually 5 to 20 μm,
In particular, a thickness of about 8 to 15 μm is preferable. In addition, the aspect ratio is 1 to 600, and particularly 1 due to the reinforcing effect and the mixing property.
It is preferably about 00 to 350. When the aspect ratio is small, there is no reinforcing effect, and when the aspect ratio is large, the mixing properties are poor and good molded products cannot be obtained. Further, the surface of the carbon fiber may be treated with various kinds of treatment agents such as epoxy resin, polyamide resin, polycarbonate resin, polyacetal resin, or the like, and other known surface treatment agents may be used according to the purpose.

The potassium titanate fiber used in the present invention is a kind of high-strength fiber (whisker), and its chemical composition is K ₂ O.6TiO ₂ , K ₂ O .6TiO ₂ .1 / 2 H ₂ O. It is a basic needle crystal and has a typical melting point of 1300 to 135.
It is 0 ° C. The average fiber length is 5 to 50 μm and the average fiber diameter is 0.05 to 1.0 μm, but the average fiber length is 20 to 30 μm and the average fiber diameter is 0.1 to 0.3 μm.
Are preferred. The potassium titanate fiber can be usually used without any treatment, but in order to have an affinity with the base resin of the present invention, a silane coupling agent such as aminosilane or epoxysilane, a chromic chloride, or a surface treatment according to other purposes. Agents can be used.

The aromatic polyamide fiber used in the present invention is a relatively new heat-resistant organic fiber,
It is expected to develop into each field by taking advantage of many unique characteristics. For example, as a representative example, a compound represented by the following structural formula [Chemical Formula 11] is mentioned, and at least one kind or a mixture of two or more kinds thereof is used.

[0029]

[Chemical 11] In addition, there are aromatic polyamide fibers having various skeletons due to structural isomers in the ortho, meta, and para positions. Among them, the one having a para position-para position bond of (1) has a high softening point and melting point and is used as a heat resistant organic fiber in the present invention. Most preferred. When the amount of glass fiber and carbon fiber is 5 parts by weight or less, the reinforcing effect peculiar to the glass fiber or carbon fiber, which is a feature of the present invention, cannot be obtained. On the contrary, if it is used in an amount of 100 parts by weight or more, the fluidity of the composition at the time of molding becomes poor, and it becomes difficult to obtain a satisfactory molded product. When the content of the potassium titanate fiber is 5 parts by mass or less, the improvement in mechanical properties at high temperature, which is a feature of the present invention, is insufficient. On the contrary, if the amount is too large, the dispersion in the melt mixing becomes insufficient, the fluidity becomes low, and the molding under normal conditions becomes difficult, which is not preferable. The preferred amount used is 10 to 100 parts by weight. When the amount of aromatic polyamide fiber is 5 parts by weight or less, the composition excellent in moldability and mechanical strength, which is a feature of the present invention, cannot be obtained. Further, if it is used in an amount of 100 parts by weight or more, the fluidity of the composition at the time of molding becomes poor, and it becomes difficult to obtain a satisfactory molded product. The preferred amount used is 10 to 50 parts by weight.

The resin composition using the aromatic polyamide of the present invention can be produced by a generally known method, but the following method is particularly preferable. (1) Aromatic polyamide powder and fibrous reinforcing material are premixed by using a mortar, Henshall mixer, drum blender, tumbler blender, ball mill, ribbon blender, and the like, and then by a commonly known melt mixer, hot roll, etc. After kneading, pelletize or powder. (2) Aromatic polyamide powder is previously dissolved or suspended in an organic solvent, the fibrous reinforcing material is immersed in this solution or suspension, and then the solvent is removed in a hot air oven,
Pellet or powder. In this case, as the solvent, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N,
N-dimethylmethoxyacetamide, N-methyl-2-
Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-
Bis (2-methoxyethoxy) ethane, bis [2- (2
-Methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide and the like. These organic solvents may be used alone or in combination of two or more. The aromatic polyamide resin composition of the present invention has an injection molding method,
It is molded by a known molding method such as an extrusion molding method, a compression molding method, and a rotational molding method, and put into practical use.

[0031]

EXAMPLES Hereinafter, production examples of the aromatic polyamide of the present invention and physical properties and performances of the obtained aromatic polyamides will be described in detail with reference to Examples and Comparative Examples. In the examples, various physical properties were measured by the following methods. Logarithmic viscosity: 0.50 g of polyamide powder was dissolved in 100 ml of hexamethylphosphoric triamide and then measured at 35 ° C. Glass transition temperature (Tg): DSC (Shimadzu DT-40 series, DSC-41
Measured by M). 5% weight loss temperature: Measured in air with DTA-TG (Shimadzu DT-40 series, DTG-40M). Melt viscosity: Measured with a Shimadzu Koka type flow tester CFT500A under a load of 100 kg. Example 1 59.27 g (0.10 mol) of 3,3′-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether and N-methyl-2-pyrrolidone were placed under a nitrogen atmosphere in a container equipped with a stirrer and a nitrogen introducing tube. After charging and dissolving 650 g, 24.29 g (0.24 mol) of triethylamine was added and cooled to 5 ° C. After that, stir to increase the strength of terephthalic acid chloride 20.30g
(0.10 mol) was charged and stirring was continued at room temperature for 3 hours. The viscous polymer solution thus obtained was discharged into methanol under vigorous stirring to precipitate a white powder. The white powder is filtered off, washed with methanol and dried at 180 ° C for 12
After drying under reduced pressure for 70 hours, 70.76 g (yield 98%) of polyamide powder was obtained. The logarithmic viscosity of this polyamide powder is 0.74dl /
g, glass transition temperature is 191 ° C, 5% weight loss temperature is 485
It was ℃. The results of elemental analysis of the obtained polyamide powder are as follows. The infrared absorption spectrum of the obtained polyamide powder is shown in FIG. This spectrum diagram, in the vicinity of 1650 cm ^-1 and near 1500 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed. Further, the obtained polyamide powder was dissolved in N-methyl-2-pyrrolidone, cast on a glass plate, and heated at 150 ° C for 1 hour and 250 ° C for 2 hours to obtain a colorless and transparent polyamide film. The tensile strength of this polyamide film was 1300 kg / cm ² , and the tensile elongation was 20%. Both measurement methods are based on ASTM D-882. The water absorption of this film was 0.60%. The measuring method is based on ASTM D-750-63.

Example 2 70.18 g (yield 97%) of polyamide powder having an inherent viscosity of 0.66 dl / g was obtained in the same manner as in Example 1 except that terephthalic acid chloride in Example 1 was replaced with isophthalic acid chloride. . The glass transition temperature of this polyamide powder is 188 ℃, 5%
The weight loss temperature was 479 ° C. The results of elemental analysis of the obtained polyamide powder are as follows. The infrared absorption spectrum of the obtained polyamide powder is shown in FIG. This spectrum diagram, in the vicinity of 1650 cm ^-1 and near 1500 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed. Further, using the obtained polyamide powder, a colorless transparent polyamide film was obtained in the same manner as in Example 1. The tensile strength of this polyamide film is 1250
kg / cm ² , tensile elongation was 23%, and water absorption was 0.62%.

Example 3 The same as Example 1 except that 20.30 g (0.10 mol) of terephthalic acid chloride in Example 1 was replaced with 10.15 g (0.05 mol) of terephthalic acid chloride and 10.15 g (0.05 mol) of isophthalic acid chloride. This was performed to obtain 70.16 g (yield 97%) of polyamide powder having an inherent viscosity of 0.72 dl / g. This polyamide powder had a glass transition temperature of 188 ° C and a 5% weight loss temperature of 481 ° C. Using the obtained polyamide powder, a colorless and transparent polyamide film was obtained in the same manner as in Example 1. The tensile strength of this polyamide film was 1240 kg / cm ² , the tensile elongation was 20%, and the water absorption was 0.60%.

Example 4 16.62 g (0.10 mol) of terephthalic acid and 2 parts of lithium chloride were placed in a container equipped with a stirrer and a nitrogen introducing tube under a nitrogen atmosphere.
After charging and dissolving 0.0 g, 60.0 g of calcium chloride, 200 g of pyridine, 62.0 g (0.20 mol) of triphenyl phosphite and 950 g of N-methyl-2-pyrrolidone, the temperature was raised to 120 ° C. Then, 59.27 g (0.10 mol) of 3,3′-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether was charged, and the mixture was stirred at 120 ° C. for 2 hours. The viscous polymer solution thus obtained was discharged into methanol with vigorous stirring to precipitate a white powder. The white powder was separated by filtration, washed with methanol, and dried under reduced pressure at 180 ° C. for 12 hours to obtain 70.98 g (yield 98%) of polyamide powder. The polyamide powder had an inherent viscosity of 0.77 dl / g, a glass transition temperature of 190 ° C, and a 5% weight loss temperature of 488 ° C. The results of elemental analysis of the obtained polyamide powder are as follows. The infrared absorption spectrum of the obtained polyamide powder is shown in FIG. The spectrogram is exactly the same as the polyamide powder obtained in Example 1, in the vicinity of 1650 cm ^-1 and near 1500 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed.

Example 5 19.42 g (0.10 mol) of dimethyl terephthalate in a container equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere, 3,3'-
Bis [4- (4-aminophenoxy) benzoyl] diphenyl ether 59.27 g (0.10 mol), diphenyl ether
1000 g was charged and stirred at 250 ° C. for 8 hours. The reaction product thus obtained was discharged into methanol under vigorous stirring to obtain a white powder. The white powder was separated by filtration, washed with methanol, and dried under reduced pressure at 180 ° C. for 12 hours to obtain 68.23 g (yield 94%) of polyamide powder. This polyamide powder has an inherent viscosity of 0.51 dl / g and a glass transition temperature of 187 ° C, 5
The% weight loss temperature was 480 ° C. The results of elemental analysis of the obtained polyamide powder are as follows. The infrared absorption spectrum of the obtained polyamide powder is shown in FIG. The spectrogram is exactly the same as the polyamide powder obtained in Example 1, in the vicinity of 1650 cm ^-1 and near 1500 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed.

Example 6 59.27 g (0.10 mol) of 3,3'-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether and N-methyl were placed in a container equipped with a stirrer and a nitrogen introducing tube under a nitrogen atmosphere.
-2-650 g of pyrrolidone was charged and dissolved, and then 24.29 g (0.24 mol) of triethylamine was added and cooled to 5 ° C. Then, stirring was strengthened and terephthalic acid chloride 19.29 g
(0.095 mol) was charged and stirring was continued for 2 hours at room temperature. Then, 2.11 g (0.015 mol) of benzoyl chloride was charged and stirring was continued at room temperature for 2 hours. The obtained polymer solution was discharged into methanol under vigorous stirring to precipitate a white powder. The white powder was separated by filtration, washed with methanol, and dried under reduced pressure at 180 ° C for 12 hours to obtain 69.78 g (yield:
95%) of polyamide powder was obtained. The polyamide powder had an inherent viscosity of 0.43 dl / g. When the melt viscosity of the obtained polyamide powder was measured, it was 2800 poise at 360 ° C. Moreover, the obtained strand was light yellow transparent, rich in flexibility, and extremely tough. Further, the thermal stability of the polyamide obtained in this example was measured by changing the residence time in the cylinder of the flow tester. Measurement temperature is 3
Performed at 60 ° C. Results are shown in FIG. It can be seen that even if the residence time in the cylinder becomes long, the melt viscosity hardly changes, and the thermal stability is good. The heat distortion temperature of a molded product obtained by compression molding this polyamide powder at 340 ° C and 150 kg / cm ² for 15 minutes was 183 ° C. The measurement method is based on ASTM D-648 and a load of 18.6 kg / cm ² .

Example 7 56.30 g (0.095 mol) of 3,3'-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether and N-methyl-in a nitrogen atmosphere in a container equipped with a stirrer and a nitrogen introducing tube. After charging and dissolving 650 g of 2-pyrrolidone, 24.29 g (0.24 mol) of triethylamine was added and the mixture was cooled to 5 ° C. After that, stirring was strengthened and 20.30 g of terephthalic acid chloride was added.
(0.10 mol) was charged and stirring was continued for 2 hours at room temperature. After that, 1.40 g (0.015 mol) of aniline was charged and the mixture was allowed to stand at room temperature for 2
Stirring was continued for hours. The obtained polymer solution was discharged into methanol under vigorous stirring to precipitate a white powder. The white powder is filtered off and washed with methanol,
After drying under reduced pressure at 80 ° C. for 12 hours, 66.75 g (yield 94%) of polyamide powder was obtained. The logarithmic viscosity of this polyamide powder is 0.4
It was 1 dl / g. When the melt viscosity of the obtained polyamide powder was measured, it was 2100 poise at 360 ° C.
Moreover, the obtained strand was light yellow transparent, rich in flexibility, and extremely tough.

Comparative Example 1 2.16 g (0.020 mol) of p-phenylenediamine and N-methyl were placed under a nitrogen atmosphere in a container equipped with a stirrer and a nitrogen inlet tube.
-2-Pyrrolidone (56.2 g) was charged and dissolved, then 4.86 g (0.048 mol) of triethylamine was added, and the mixture was cooled to 5 ° C. After that, stirring was strengthened and terephthaloyl chloride 3.86g
(0.019 mol) was charged all at once, and stirring was continued at room temperature for 2 hours. After that, 0.443 g (0.003 mol) of benzoyl chloride
Was charged and stirring was continued at room temperature for 2 hours. The obtained polymer solution was discharged into methanol under vigorous stirring to precipitate a white powder. The white powder is filtered off, washed with methanol and dried under vacuum at 180 ° C for 12 hours to give 4.75.
Polyamide powder of g (yield 97.7%) was obtained. When the glass transition temperature of this polyamide powder was measured, no clear value was shown. Moreover, the melt viscosity was measured at 360 ° C. and 400 ° C., but no melt flow was observed at any temperature.

Comparative Example 2 Polyamide powder was synthesized in the same manner as in Example 6, except that benzoyl chloride was not used. The polyamide powder had an inherent viscosity of 0.43 dl / g. The melt viscosity was measured by changing the residence time in the flow tester cylinder in the same manner as in Example 6, and as shown in FIG. 5, the melt viscosity increased as the residence time increased. It was inferior in thermal stability to the obtained polyamide.

Examples 8 and 9 100 polyamides obtained in Examples 1 and 2, respectively
Silane-treated glass fibers having a fiber length of 3 mm and a fiber diameter of 13 μm with respect to parts by weight (trade name: CS-3PE-476S, Nitto Boseki Co., Ltd.)
) Was added in the amount shown in Table-1, mixed with a drum blender mixer (Kawata Manufacturing Co., Ltd.), melt-kneaded at a temperature of 360 ° C. with a single screw extruder having a diameter of 30 mm, and then the strand was air-cooled and cut. To obtain pellets. The obtained pellets are injection-molded (Arburg molding machine, maximum mold clamping force 35 tons, injection pressure 500kg / cm ² , cylinder temperature 360 ℃, mold temperature 150).
Then, various test pieces for measurement were obtained and measured. Measured tensile strength (according to ASTM D-638), bending strength and flexural modulus (ASTM D-790), Izod impact strength (notched) (ASTM D-256), heat distortion temperature (ASTM D-648), molding The results of shrinkage ratio (ASTM D-955) are shown in Table-1.

Comparative Examples 3 and 4 The same glass fiber as in Examples 8 and 9 was added to 100 parts by weight of the polyamides obtained in Examples 1 and 2, respectively.
The results used outside the scope of the present invention are shown in Table-2.

Examples 10 and 11 To 100 parts by weight of each of the polyamides obtained in Examples 1 and 2, carbon fibers having an average diameter of 12 μm, a length of 3 mm and an aspect ratio of 250 (trade name: Torayca) are listed. The amount shown in Table 3 was added, and the results shown in Table 3 were obtained in the same manner as in Examples 8 and 9.

Comparative Examples 5 and 6 To 100 parts by weight of each of the polyamides obtained in Examples 1 and 2, 120 parts by weight of the same carbon fiber as in Examples 10 and 11 was added, and Examples 13 and 14 were added.
An attempt was made to extrude strands in the same manner as in, but none of them could be formed into strands.

Examples 12 and 13 For 100 parts by weight of the polyamides obtained in Examples 1 and 2, respectively, potassium titanate fibers having a cross-sectional diameter of 0.2 μm and an average fiber length of 20 μm (Otsuka Chemical Co., Ltd .: Tismo-
D) was added in the amount shown in Table 4, and the results shown in Table 4 were obtained in the same manner as in Examples 8 and 9.

Examples 14 and 15 For 100 parts by weight of the polyamides obtained in Examples 1 and 2, respectively, the amount of aromatic polyamide fiber having an average fiber length of 3 mm (trade name: Kevlar manufactured by DuPont) is shown in Table-5. The results were shown in Table-5 in the same manner as in Examples-8 and 9.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

[Table 5]

[0051]

INDUSTRIAL APPLICABILITY The present invention provides a completely novel aromatic polyamide having excellent processability or thermal stability in addition to the excellent heat resistance inherent in aromatic polyamide. Furthermore, the aromatic polyamide resin composition of the present invention has excellent dimensional stability and mechanical strength, and has extremely good workability.
It is an extremely useful material used for electrical / electronic parts, automobile parts, precision machine parts, medical equipment parts, base materials for space aircraft, etc. that require these physical properties, and has a very great industrial application effect. .

[Brief description of drawings]

FIG. 1 is a diagram of an infrared absorption spectrum of the polyamide powder obtained in Example 1 according to the present invention.

FIG. 2 is a diagram of the infrared absorption spectrum of the polyamide powder obtained in Example 2 according to the present invention.

FIG. 3 is a diagram of the infrared absorption spectrum of the polyamide powder obtained in Example 4 according to the present invention.

FIG. 4 is an infrared absorption spectrum diagram of the polyamide powder obtained in Example 5 according to the present invention.

[Fig. 5] In order to compare the thermal stability of the respective polyamide powders obtained in Example 6 and Comparative Example 2 according to the present invention, the resin residence time in the cylinder of the flow tester at a measurement temperature of 360 ° C and a load of 100 kg. Is the result of measuring the melt viscosity under different conditions.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masanori Asanuma 1190, Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Akihiro Yamaguchi 1190, Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Within the corporation

Claims (10)

[Claims] 1. The following formula (I) [Chemical formula 1] (In the formula, X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound of the formula [Chemical Formula 2] R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a halogen group, a phenyl group, a is 0, 1 or 2, and b is 0.
Alternatively, it represents an integer of 1 to 4. Moreover, n represents the integer of 1-1000. ) An aromatic polyamide represented by. 2. Formula (II) [Chemical Formula 3] [Chemical Formula 3] In the presence of a dehydrohalogenating agent, 3,3'-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether and a reaction temperature of 60 ° C or less in an organic solvent. The method for producing an aromatic polyamide according to claim 1, which is obtained by polycondensation with. 3. 3,3′-bis [4- (4-
2. Aminophenoxy) benzoyl] diphenyl ether and an aromatic dicarboxylic acid are obtained by polycondensation in the presence of a condensing agent in an organic solvent at a reaction temperature of 10 to 150 ° C. Method for producing aromatic polyamide. 4. 3,3′-bis [4- (4-
Aminophenoxy) benzoyl] diphenyl ether, an aromatic dicarboxylic acid dialkylate and / or an aromatic dicarboxylic acid diarylate, in an organic solvent
The method for producing an aromatic polyamide according to claim 1, which is obtained by polycondensation at a reaction temperature of 00 to 300 ° C. 5. An aromatic polyamide having good thermal stability represented by the formula (I), the molecular end of which is capped with a monovalent carboxylic acid, the carboxylic acid derivative or a monovalent amine. 6. An aromatic polyamide obtained by reacting a diamine with a dicarboxylic acid or a dicarboxylic acid derivative, which has a repeating unit represented by the formula (I) as a basic skeleton, and a polycondensation reaction is a monovalent carboxylic acid. It is carried out in the coexistence of an acid or a carboxylic acid derivative, and the amount of the aromatic dicarboxylic acid or the aromatic dicarboxylic acid derivative is 0.7 to 1.0 mol per 1 mol of the aromatic diamine, and the monovalent carboxylic acid is used. An aromatic polyamide having good thermal stability according to claim 5, which is obtained by reacting an acid or a carboxylic acid derivative in an amount of 0.001 to 1.0 mol with respect to 1 mol of an aromatic diamine. Manufacturing method. 7. An aromatic polyamide obtained by reacting a diamine with a dicarboxylic acid or a dicarboxylic acid derivative, which has a repeating unit represented by the formula (I) as a basic skeleton and whose polycondensation reaction is a monovalent amine. The amount of aromatic diamine is 0.7 to 1.0 mol per 1 mol of aromatic dicarboxylic acid or aromatic dicarboxylic acid derivative, and the amount of monovalent amine is aromatic. The method for producing an aromatic polyamide having good thermal stability according to claim 5, which is obtained by reacting at a ratio of 0.001 to 1.0 mol with respect to 1 mol of a dicarboxylic acid or an aromatic dicarboxylic acid derivative. . 8. 100 parts by weight of the aromatic polyamide according to claim 1 and / or 5 and fibrous reinforcing materials 5 to 10
An aromatic polyamide resin composition comprising 0 part by weight. 9. The fibrous reinforcing material is glass fiber, carbon fiber,
The aromatic polyamide resin composition according to claim 8, which is selected from the group consisting of potassium titanate fibers and aromatic polyamide fibers. 10. The aromatic polyamide fiber is at least one selected from the group consisting of those having a repeating structural unit represented by the following formulas (1), (2) and (3) [Chemical formula 4]. The aromatic polyamide resin composition according to claim 9. [Chemical 4]