JPH05310916A - Aromatic polyamide resin and resin composition thereof - Google Patents

Abstract

(57) [Summary] [Structure] An aromatic polyamide obtained by polycondensing a diamine of the formula 1) and an aromatic dicarboxylic acid in an organic solvent, and a method for producing the same. 2) An aromatic polyamide from a diamine represented by the formula, in which the molecular ends of the polymer are sealed and which has good thermal stability, and a method for producing the same. A resin composition comprising 100 parts by weight of an aromatic polyamide derived from the diamine of the formula 3) and 5 to 100 parts by weight of glass fiber, carbon fiber, potassium titanate fiber or aromatic polyamide fiber. [Effect] A melt-moldable aromatic polyamide having excellent heat resistance and thermal stability was obtained. Moreover, an aromatic polyamide resin composition having excellent dimensional stability, mechanical properties, and processability was obtained.

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 developed so far have excellent mechanical properties and heat resistance, they all have the drawbacks of poor moldability and high water absorption. It was For example, the following formula (Formula 1
3)

[0004]

[Chemical 13] An aromatic polyamide having a basic skeleton as represented by (Dupont's product: trademark Kevlar) has excellent properties such as flame retardancy, heat resistance, high tensile strength and high elastic modulus. However, this aromatic polyamide does not have a clear glass transition temperature, its thermal decomposition temperature is about 430 ° C, and its processing temperature and thermal decomposition temperature are close to each other, so it is difficult to process it as a molding material. There was a flaw. Therefore, it is only used in the field of fibers or pulp by the wet spinning method. Further, it has a high water absorption rate of 4.5%, and it is obvious that it has a bad influence on dimensional stability, insulating property, solder heat resistance and the like when used as a base material for electric / electronic parts.
("Latest heat-resistant polymer": General Technology Center Co., Ltd.)

[0005]

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

[0006]

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 is based on the formula (1) (1)

[0007]

[Chemical 14] (In the formula, X is a condensed polycyclic aromatic group having 20 or less carbon atoms, or

[0008]

[Chemical 15] R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or 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 the formula: (2) Formula (2)

[0009]

[Chemical 16] Bis [4- (4-aminophenoxy) phenyl]
Ketone and / or bis [4- (3-aminophenoxy)
Phenyl] ketone and aromatic dicarboxylic acids are obtained by polycondensation in an organic solvent, a method for producing an aromatic polyamide represented by the following formula (1)

[0010]

[Chemical 17] (In the formula, X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound of the formula

[0011]

[Chemical 18] R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or 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. ) (3) Formula (1) (Formula 19)

[0012]

[Chemical 19] (In the formula, X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound of the formula

[0013]

[Chemical 20] R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or 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. ) Having a repeating unit represented by the formula (1) as a basic skeleton, and using a monovalent amine or a monovalent carboxylic acid or a carboxylic acid derivative to seal the molecular end of the polymer, an aromatic polyamide having good thermal stability and a method thereof Manufacturing method, (4) Formula (1) (Chemical formula 21)

[0014]

[Chemical 21] (In the formula, X is a condensed polycyclic aromatic group having 20 or less carbon atoms, or a compound represented by the formula:

[0015]

[Chemical formula 22] R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or 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 resin composition comprising 100 parts by weight of the aromatic polyamide represented by the formula (4) and 5 to 100 parts by weight of the fibrous reinforcing material. The aromatic polyamide of the present invention has the formula (2) as a diamine component.

[0016]

[Chemical formula 23] Bis [4- (4-aminophenoxy) phenyl]
Ketone and / or bis [4- (3-aminophenoxy)
Phenyl] ketone is used and obtained by polymerizing this 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 of the present invention and the resin composition thereof use bis [4- (4-aminophenoxy) phenyl] ketone and / or bis [4- (3-aminophenoxy) phenyl] ketone as a diamine component. A thermoplastic aromatic polyamide and a resin composition thereof, which are characterized by the above, and which have excellent processability in addition to the heat resistance inherent in the aromatic polyamide.

Since the aromatic polyamide and the resin composition have excellent heat resistance and thermoplasticity, they can be extrusion-molded and injection-molded, and they are substrates for space / aircraft and substrates for electric / electronic parts. As a raw material of high-strength and high-heat-resistant fiber obtained by the melt spinning method, it can be expected to be utilized for various purposes and is extremely useful. The aromatic polyamide of the present invention is an aromatic polyamide which uses 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, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene,
1,4-bis (3-aminophenoxy) benzene, 1,
4-bis (4-aminophenoxy) benzene, 4,4 '
-Bis (3-aminophenoxy) biphenyl, 4,4 '
-Bis (4-aminophenoxy) biphenyl, 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] 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] benzophenone, 4,
4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenyl sulfone, 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, and these may be used alone or in admixture of two or more. It

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 at a reaction temperature of 100 to 300 ° C. in an organic solvent. The aromatic diamine used in this method is bis [4- (4-aminophenoxy) phenyl] ketone and / or bis [4- (3-aminophenoxy) phenyl] ketone. 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 and the like. 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. Moreover, in the method (a), an aromatic dicarboxylic acid dihalide is used. For example, dihalides of the above-mentioned aromatic dicarboxylic acids, 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.

In the method (c), an aromatic dicarboxylic acid dialkyl ester and / or an aromatic dicarboxylic acid diallyl ester is used. For example, a dialkyl ester having 1 to 10 carbon atoms, a diphenyl ester, a di (fluorophenyl) ester, a di (chlorophenyl) ester, each of the above aromatic dicarboxylic acids,
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,
Examples thereof include di (phenylphenyl) ester and dinaphthyl ester. 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 in combination of two or more depending on the type of reaction raw material monomer and the polymerization method. When an aromatic dicarboxylic acid dihalide is used as a monomer of a reaction raw material, a dehydrohalogenating agent is usually used together. The dehydrohalogenating agent used is trimethylamine,
Triethylamine, tripropylamine, tributylamine, tripentylamine, N, N-dimethylbenzylamine, N, N-diethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-dimethyl Aniline, 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, potassium acetate, Examples thereof include ethylene oxide and propylene oxide.

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 varies depending on the polymerization technique and the type of solvent, but is usually 300 ° C. or lower. The reaction pressure is not particularly limited and can be carried out at normal pressure.

The reaction time varies depending on the type of the starting material monomer, the polymerization method, the type of the solvent, the type of the dehydrohalogenating agent, the type of the condensing agent and the reaction temperature.
The reaction is allowed to proceed for a time sufficient to complete the production of the aromatic polyamide represented by 10 minutes to 24 hours is usually sufficient.
By such a reaction, the compound represented by the formula (1)

[0025]

[Chemical formula 24] (In the formula, X is a condensed polycyclic aromatic group having 20 or less carbon atoms, or a compound represented by the formula:

[0026]

[Chemical 25] R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or 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 bis [4- (4-aminophenoxy)] as a reaction raw material monomer.
It is characterized by using phenyl] ketone and / or bis [4- (3-aminophenoxy) phenyl] ketone and an aromatic dicarboxylic acid or an aromatic dicarboxylic acid derivative such as dicarboxylic acid dihalide. 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 contains bis [4- (4-aminophenoxy) phenyl] ketone and / or bis [4- (3-aminophenoxy) phenyl] ketone of the formula (2) as a main component. It is obtained by reacting an aromatic diamine with an aromatic dicarboxylic acid or an aromatic dicarboxylic acid derivative in the presence of a monovalent carboxylic acid, a carboxylic acid 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 / or alicyclic monocarboxylic acid or a monocarboxylic acid halide, and It is produced by replacing a part of the diamine component with an 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 acids, acetoxybenzoic acids, hydroxybenzoic acids, biphenylcarboxylic acids, benzophenonecarboxylic acids, diphenylethercarboxylic acids, diphenylsulfidecarboxylic acids, diphenylsulfonecarboxylic acids, 2,2-diphenylpropanecarboxylic acids, 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.

As the monocarboxylic acid ester,
For example, alkyl ester having 1 to 10 carbon atoms of the above monocarboxylic acid, phenyl ester, fluorophenyl ester, chlorophenyl ester, bromophenyl ester, methylphenyl ester, ethylphenyl ester, propylphenyl ester, isopropylphenyl ester, butylphenyl ester. , Isobutylphenyl ester, t-butylphenyl ester, methoxyphenyl ester, ethoxyphenyl ester, nitrophenyl ester, phenylphenyl ester, naphthyl ester and the like. These monocarboxylic acid esters may be used alone or in combination of two or more.

The amount of monocarboxylic acids used is 0.001 to 1.0 mol per mol of the aromatic diamine.
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.

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 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 according to the purpose within the range not impairing the purpose of the present invention. Thermoplastic resins that can be blended include polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyphenylene sulfide, polyamideimide, polyetherimide, modified polyphenylene oxide. Etc. It is also possible to add a thermosetting resin or a filler to an extent that the object of the invention is not impaired.
Examples of the thermosetting resin include phenol resin and epoxy resin. As the filler, graphite, carborundum, silica powder, molybdenum disulfide, wear resistance improving material such as fluororesin, glass fiber, carbon fiber, boron fiber, silicon carbide fiber, carbon whiskers, asbestos, metal fiber, ceramic fiber Reinforcing material such as antimony trioxide, magnesium carbonate, calcium carbonate, etc. flame retardant improving material, clay, mica, etc. electrical property improving material, asbestos, silica, graphite, etc. tracking improving material, barium sulfate, silica, Acid resistance improving materials such as calcium metasilicate, iron powder, zinc powder, aluminum powder, copper powder and other thermal conductivity improving materials, other glass beads, talc,
Examples include 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 quenching molten glass while drawing it by various methods. It means a roving or the like in which strands are uniformly 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 or epoxysilane, chromic chloride, in order to have an affinity with the base resin of the present invention.
Other surface treatment agents can be used according to 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 the manufacturing of the molded product deteriorates. Therefore, in the present invention, the glass fiber has a length of 0.1 to 6
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 or the like 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,
Particularly, those having a thickness of about 8 to 15 μm are 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, the reinforcing effect is not obtained, and when the aspect ratio is large, the mixing property is deteriorated and a good molded product cannot be obtained. Further, the surface of the carbon fiber may be treated with various kinds of treating agents such as epoxy resin, polyamide resin, polycarbonate resin, polyacetal resin and the like, and other known surface treating agents may be used according to the purpose.

Further, potassium titanate used in the present invention
Fiber is a type of high-strength fiber (whisker) and is a chemical group.
K as a success₂O ・ 6TiO₂, K₂O ・ 6TiO₂・ 1/2
 H₂ It is a needle-like crystal based on O and has a typical melting point of 13
It is 00-1350 degreeC. The average fiber length is 5 to 50 μm,
An average fiber diameter of 0.05 to 1.0 μm is applied.
However, the average fiber length is 20 to 30 μm, and the average fiber diameter is 0.1.
It is preferably about 0.3 μm. The potassium titanate fiber
Although the fibers can be used without any treatment, the base resin of the present invention
Aminosilane and epoxy sila for compatibility
Silane coupling agents such as silane, chromic chloride
It is possible to use surface treatment agents according to the purpose and other purposes.
Wear.

The aromatic polyamide fiber used in the present invention is a relatively newly developed heat resistant organic fiber,
It is expected to develop into various fields by taking advantage of many unique characteristics. For example, typical examples include those having the following structural formulas and the like, and at least one kind or a mixture of two or more kinds thereof is used.

[0042]

[Chemical formula 26] 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 or 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, when the amount is large, the dispersion in the melt mixing becomes insufficient, and further the fluidity becomes low, which makes molding under normal conditions 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 10-5
0 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, etc., 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 is
It is molded by a known molding method such as an injection molding method, an extrusion molding method, a compression molding method, and a rotational molding method, and put into practical use.

[0046]

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 with a load of 100 kg.

Example 1 Bis [4- (4-aminophenoxy) phenyl] ketone was placed in a container equipped with a stirrer and a nitrogen introducing tube under a nitrogen atmosphere.
After 39.65 g (0.10 mol) and N-methyl-2-pyrrolidone (470 g) were charged and dissolved, triethylamine (24.29 g, 0.24 mol) was added, and the mixture was cooled to 5 ° C. Then, stirring was intensified and 20.30 g (0.10 mol) of terephthaloyl chloride 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 was filtered off, washed with methanol and dried under reduced pressure at 180 ° C for 12 hours to give 51.12g.
A polyamide powder (yield 97.1%) was obtained. The polyamide powder has an inherent viscosity of 0.85 dl / g and a glass transition temperature of 25.
The temperature at 7 ° C and the 5% weight loss were 510 ° 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 1660 cm ^-1 and near 1530 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed.

Further, the obtained polyamide powder was treated with N-methyl.
-2- After being dissolved in pyrrolidone, it was 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 10%. Both measurement methods are based on ASTM D-882. The water absorption of this film was 0.98%. The measuring method is ASTM D-750-63
According to.

Example 2 The same procedure as in Example 1 was carried out except that terephthalic acid chloride in Example 1 was replaced by isophthalic acid chloride, and 50.97 g of polyamide powder having a logarithmic viscosity of 0.71 dl / g (yield 96.8).
%) The glass transition temperature of this polyamide powder is 23.
The temperature at 6 ° C and 5% weight loss was 500 ° 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 1660 cm ^-1 and near 1540 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed. 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 is
1210 kg / cm ² , tensile elongation 12%, water absorption 0.94%
Met.

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. Then, 51.28 g (yield 97.4%) of polyamide powder having an inherent viscosity of 0.73 dl / g was obtained. This polyamide powder has a glass transition temperature of 241 ° C and a 5% weight loss temperature of 500.
It was ℃. 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 is 1230 kg / c
m ² , tensile elongation was 12%, and water absorption was 0.95%.

Example 4 Example 4 was repeated except that the bis [4- (4-aminophenoxy) phenyl] ketone in Example 1 was replaced with bis [4- (3-aminophenoxy) phenyl] ketone. 50.96 g of polyamide powder having a logarithmic viscosity of 0.87 dl / g (yield: 96.8
%) The glass transition temperature of this polyamide powder is 21.
The temperature at 2 ℃ and 5% weight loss was 501 ℃. 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 1660 cm ^-1 and near 1540 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed. 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 is
1160 kg / cm ² , tensile elongation 27%, water absorption 0.99%
Met.

Example 5 51.59 g of polyamide powder having a logarithmic viscosity of 0.90 dl / g (yield 98.0%) was obtained in the same manner as in Example 4 except that terephthalic acid chloride in Example 4 was replaced with isophthalic acid chloride.
Got The glass transition temperature of this polyamide powder is 208
℃, 5% weight loss temperature was 500 ℃. 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 1660 cm ^-1 and near 1520 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed. 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 is
1120 kg / cm ² , tensile elongation 18%, water absorption 1.05%
Met.

Example 6 As in Example 4, except that 20.30 g (0.10 mol) of terephthaloyl chloride in Example 4 was replaced with 10.15 g (0.05 mol) of terephthalic acid chloride and 10.15 g (0.05 mol) of isophthalic acid chloride. Then, 51.13 g (yield 97.1%) of polyamide powder having an inherent viscosity of 0.89 dl / g was obtained. This polyamide powder has a glass transition temperature of 209 ° C and a 5% weight loss temperature of 503.
It was ℃. 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 is 1150 kg / c
m ² , the tensile elongation was 20%, and the water absorption was 1.01%.

Example 7 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 700 g of N-methyl-2-pyrrolidone, the temperature was raised to 120 ° C. 39.65 g (0.10 mol) of bis [4- (3-aminophenoxy) phenyl] ketone was charged therein, and the mixture was stirred at 120 ° C. for 2 hours. The viscous polymer solution thus obtained was discharged into vigorously stirred methanol 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 give 52.04 g (yield 98.8 g).
%) Of polyamide powder was obtained. The polyamide powder had an inherent viscosity of 0.92 dl / g, a glass transition temperature of 214 ° C. and a 5% weight loss temperature of 502 ° 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 is exactly the same as that of the polyamide powder obtained in Example 4, and remarkable absorption was observed in the characteristic absorption bands of amide near 1650 cm ^-1 and 1530 cm ^-1 .

Example 8 19.42 g (0.10 mol) of dimethyl terephthalate and 39.65 g of bis [4- (3-aminophenoxy) phenyl] ketone in a nitrogen atmosphere in a container equipped with a stirrer and a nitrogen introducing tube.
(0.10 mol) and 1000 g of diphenyl ether were charged,
The mixture was stirred at 250 ° C for 8 hours. The reaction product thus obtained was discharged into vigorously stirred methanol to obtain a white powder. The white powder is filtered off and washed with methanol,
After vacuum drying at 12 ° C. for 12 hours, 49.66 g (yield 94.3%) of polyamide powder was obtained. The logarithmic viscosity of this polyamide powder is 0.
The glass transition temperature was 73 dl / g, the glass transition temperature was 211 ° C, and the 5% weight loss temperature was 501 ° C. The results of elemental analysis of the obtained polyad powder are as follows. The infrared absorption spectrum of the obtained polyamide powder is shown in FIG. This spectrum diagram is exactly the same as that of the polyamide powder obtained in Example 4, and remarkable absorption was observed in the characteristic absorption bands of amide near 1650 cm ^-1 and 1530 cm ^-1 .

Example 9 Bis [4- (3-aminophenoxy) phenyl] ketone was placed in a container equipped with a stirrer and a nitrogen introducing tube under a nitrogen atmosphere.
After 39.65 g (0.10 mol) and 470 g of N-methyl-2-pyrrolidone were charged and dissolved, 24.29 g (0.24 mol) of triethylamine was added and the mixture was cooled to 5 ° C. Then, the stirring was intensified and 19.29 g (0.095 mol) of terephthaloyl chloride was charged, and the stirring was continued at room temperature for 2 hours. Then benzoyl chloride
2.11 g (0.015 mol) was charged and stirring was continued at room temperature for 2 hours. The obtained polymer solution was discharged into vigorously stirred methanol 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 50.14 g (yield 95.2%) of polyamide powder. The polyamide powder had an inherent viscosity of 0.51 dl / g. When the melt viscosity of the obtained polyamide powder was measured, it was 8000 poise at 350 ° C. Also,
The obtained strand was light yellow transparent, highly flexible, 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. The measurement temperature was 350 ° C. The results are shown in Fig. 7. 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. In addition, this polyamide powder is
The heat distortion temperature of the molded product obtained by compression molding at 150 Kg / cm ² for 15 minutes was 198 ° C. The measurement method is
According to ASTM D-648, load 18.6 Kg / cm ² .

Example 10 Bis [4- (3-aminophenoxy) phenyl] ketone was placed under a nitrogen atmosphere in a container equipped with a stirrer and a nitrogen introducing tube.
37.66 g (0.095 mol) and N-methyl-2-pyrrolidone 470 g
After charging and dissolving, 24.29 g (0.24 g) of triethylamine
Mol) was added and cooled to 5 ° C. Then, stirring was intensified, 20.30 g (0.10 mol) of terephthaloyl chloride was charged, and stirring was continued for 2 hours at room temperature. After that, 1.40 g of aniline (0.0
(15 mol) and charged with stirring at room temperature for 2 hours. The obtained polymer solution was discharged into vigorously stirred methanol 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 49.96 g (yield 94.9%) of polyamide powder. The polyamide powder had an inherent viscosity of 0.49 dl / g.
When the melt viscosity of the obtained polyamide powder was measured,
It was 7700 poise at 350 ° C. Further, 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 in a container equipped with a stirrer and a nitrogen introducing tube under a nitrogen atmosphere.
-2-Pyrrolidone (56.2 g) was charged and dissolved, and triethylamine (4.86 g, 0.048 mol) 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. Then 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 vigorously stirred methanol 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.
g (yield 97.7%) of polyamide powder was obtained. When the glass transition temperature of this polyamide powder was measured, no clear value was shown. Further, the melt viscosity was measured at 350 ° C. and 400 ° C., but melt flow did not occur at any temperature.

Comparative Example 2 Polyamide powder was synthesized in exactly the same manner as in Example 9, but without using benzoyl chloride. The polyamide powder had an inherent viscosity of 0.50 dl / gl / g. Example 9
The melt viscosity was measured by changing the residence time in the flow tester cylinder by the same method as in Example 1. As shown in FIG. 7, the melt viscosity increased as the residence time increased, and the melt viscosity was obtained in Example 9. It was inferior in thermal stability to polyamide.

Examples 11 and 12 10 polyamides obtained in Examples 4 and 5, respectively.
Silane-treated glass fiber having a fiber length of 3 mm and a fiber diameter of 13 μm with respect to 0 part by weight (trademark: Nitto Boseki Co., Ltd .: CS-
3PE-476S) in an amount shown in Table 1 and mixed in a drum blender mixer (Kawata Manufacturing Co., Ltd.), and then melt-kneaded at a temperature of 350 ° C. by a single-screw extruder having a diameter of 30 mm, and then the strand is air-cooled. , And cut to obtain pellets.

The obtained pellets were injection molded (Arburg molding machine, maximum mold clamping force 35 tons, injection pressure 500 kg /
cm ² , cylinder temperature 350 ° C, mold temperature 150 ° C)
Then, various test pieces for measurement were obtained and measured. Measured tensile strength (according to ASTM D-638), flexural strength and flexural modulus (ASTM D-790), Izod impact strength (notched) (ASTM D-256), heat distortion temperature (ASTM D-648), molding Shrinkage rate (AST
The results of MD-955) are shown in Table 1.

[0062]

[Table 1] Comparative Examples-3 and 4 Polyamides 10 obtained in Examples-4 and 5, respectively
Table 2 shows the results of using the same glass fibers as those in Examples-11 and 12 in an amount other than the range of the present invention with respect to 0 part by weight.

[0063]

[Table 2] Examples-13 and 14 Polyamides 10 obtained in Examples-4 and 5, respectively.
Carbon fibers having an average diameter of 12 μm, a length of 3 mm, and an aspect ratio of 250 (trade name: Torayca, Inc.) were added to 0 parts by weight in the amounts shown in Table-3, and in the same manner as in Examples-11 and 12, The results shown in Table 3 were obtained.

[0064]

[Table 3] Comparative Examples-5 and 6 Polyamides 10 obtained in Examples-4 and 5, respectively
120 parts by weight of the same carbon fibers as those in Examples-13 and 14 were added to 0 parts by weight, and an extrusion strand formation was tried in the same manner as in Examples-13 and 14, but it was impossible to form a strand. It was

Examples-15 and 16 Polyamides 10 obtained in Examples-4 and 5, respectively.
Cross-sectional diameter 0.2 μm, average fiber length 2 with respect to 0 parts by weight
0 μm potassium titanate fiber (Otsuka Chemical Co., Ltd .: Tismo-D) was added in the amount shown in Table 4, and Example-11 was added.
The results shown in Table 4 were obtained in the same manner as in Nos. 12 and 12.

[0066]

[Table 4] Examples-17 and 18 Polyamides obtained in Examples-4 and 5 10 respectively
To 0 parts by weight, an aromatic polyamide fiber having an average fiber length of 3 mm (trade name: Kevlar, manufactured by DuPont) was added in the amount shown in Table-5, and in the same manner as in Examples-11 and 12, shown in Table-5. I got the result.

[0067]

[Table 5]

[0068]

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 is excellent in 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 a polyamide powder obtained in Example 1 according to the present invention.

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

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

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

FIG. 5: Infrared absorption spectrum of polyamide powder obtained according to Example 7 of the present invention

FIG. 6 is an infrared absorption spectrum chart of the polyamide powder obtained in Example 8 according to the present invention.

FIG. 7: To compare the thermal stability of the respective polyamide powders obtained in Example 9 and Comparative Example 2 according to the present invention, the resin residence time in the cylinder of the flow tester was measured at a measurement temperature of 350 ° C. and a load of 100 kg. The results are obtained by changing the melt viscosity.

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

Claims (10)

6 [Claims] 1. The following formula (1) (formula 1) (In the formula, X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound represented by the following formula: R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or 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 (2) (Formula 3) [Formula 3] Bis [4- (4-aminophenoxy) phenyl]
Ketone and / or bis [4- (3-aminophenoxy)
The aromatic compound according to claim 1, which is obtained by polycondensing a phenyl] ketone and an aromatic dicarboxylic acid dihalide in the presence of a dehydrohalogenating agent in an organic solvent at a reaction temperature of 60 ° C or lower. For the production of aromatic polyamide. 3. Formula (2) (Formula 4) [Formula 4] Bis [4- (4-aminophenoxy) phenyl]
Ketone and / or bis [4- (3-aminophenoxy)
The aromatic polyamide according to claim 1, which is obtained by polycondensing a phenyl] ketone 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. Manufacturing method. 4. Formula (2) (Formula 5) [Formula 5] Bis [4- (4-aminophenoxy) phenyl]
Ketone and / or bis [4- (3-aminophenoxy)
A phenyl] ketone and an aromatic dicarboxylic acid dialkylate and / or an aromatic dicarboxylic acid diarylate are obtained by polycondensation in an organic solvent at a reaction temperature of 100 to 300 ° C. 1. A method for producing an aromatic polyamide. 5. An aromatic compound having good thermal stability represented by the following formula (1) (Chemical Formula 6), the molecular end of which is capped with a monovalent carboxylic acid, the carboxylic acid derivative or a monovalent amine. polyamide. [Chemical 6] (In the formula, X is a condensed polycyclic aromatic group having 20 or less carbon atoms, or a compound represented by the following formula: R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or 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. ) 6. An aromatic polyamide obtained by reacting a diamine with a dicarboxylic acid or a dicarboxylic acid derivative, wherein the following formula (1) (Chemical Formula 8): (In the formula, X is a condensed polycyclic aromatic group having 20 or less carbon atoms, or a compound represented by the formula: R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or 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. ) As a basic skeleton, the polycondensation reaction is carried out in the presence of a monovalent carboxylic acid or carboxylic acid derivative, and the amount of aromatic dicarboxylic acid or aromatic dicarboxylic acid derivative is aromatic diamine. The amount of the monocarboxylic acid or the carboxylic acid derivative is 0.7 to 1.0 mol per mol, and the amount of the monovalent carboxylic acid or the carboxylic acid derivative is 0.001 to 1.0 mol per 1 mol of the aromatic diamine. The method for producing an aromatic polyamide having good thermal stability according to claim 5, which is obtained by 7. An aromatic polyamide obtained by reacting a diamine with a dicarboxylic acid or a dicarboxylic acid derivative, which is represented by the following formula (1) (Chemical Formula 10): (In the formula, X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound represented by the following formula: R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or 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. ) Has a repeating unit represented by the basic skeleton, the polycondensation reaction is carried out in the presence of 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 dicarboxylic acid or aromatic dicarboxylic acid. 0.0 for 1 mole of derivative
The method for producing an aromatic polyamide having good thermal stability according to claim 5, which is obtained by reacting at a ratio of 01 to 1.0 mol. 8. 100 parts by weight of the aromatic polyamide according to claim 1 and / or 5 and the fibrous reinforcing materials 5 to 10
An aromatic polyamide resin composition consisting of 0 parts 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 resin composition according to claim 9, wherein the aromatic polyamide fiber is selected from the group consisting of aromatic polyamides having the structure of the following formula (Formula 12). [Chemical formula 12]