JPH05310919A - Aromatic polyamide resin and resin composition thereof - Google Patents

Abstract

(57) [Summary] (Correction) [Structure] 1) Diamine of the following formula and aromatic dicarboxylic acid are mixed at 60 ° C. in an organic solvent in the presence of a dehydrohalogenating agent.
An aromatic polyamide obtained by polycondensation below and a method for producing the same. 2) An aromatic polyamide from a diamine represented by the following formula, which is obtained by sealing a polymer molecular end and has good thermal stability, and a method for producing the same. 3) A resin composition comprising 100 parts by weight of an aromatic polyamide from a diamine represented by the following formula 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, it has excellent dimensional stability and mechanical properties,
Moreover, the present invention relates to a novel aromatic polyamide resin composition having excellent processability.

[0003]

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 of the 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 5)

[0006]

[Chemical 5] 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.)

[0007]

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.

[0008]

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)

[0009]

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

[0010]

[Chemical 7] 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)

[0011]

[Chemical 8] 1,3-bis (3-aminophenoxy) benzene represented by
At least one selected from the group consisting of 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene and 1,4-bis (4-aminophenoxy) benzene, Aromatic dicarboxylic acids, characterized by being obtained by polycondensation in an organic solvent,
(1) A method for producing an aromatic polyamide according to the item (3), having a repeating unit represented by the formula (1) as a basic skeleton,
Aromatic polyamide having a good thermal stability, in which the molecular ends of the polymer are capped with a monovalent amine or a monovalent carboxylic acid or a carboxylic acid derivative, and a method for producing the same,
(4) An aromatic polyamide resin composition comprising 100 parts by weight of the aromatic polyamide described in (1) and (3) and 5 to 100 parts by weight of the fibrous reinforcing material.

The aromatic polyamide of the present invention has a diamine component of the formula (2)

[0013]

[Chemical 9] Diamines represented by 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene and 1,4- It can be obtained by polymerizing at least one selected from the group consisting of bis (4-aminophenoxy) benzene and 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 include 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, and 1,4-bis (4-aminophenoxy) benzene.
At least one selected from the group consisting of bis (3-aminophenoxy) benzene and 1,4-bis (4-aminophenoxy) benzene is used as a diamine component, and the heat resistance originally possessed by aromatic polyamide In addition to the above, it is a thermoplastic aromatic polyamide having excellent processability and a resin composition thereof.

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, 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] 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
Examples include -bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene and the like, and these may be used alone or in combination 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) aromatic diamine and aromatic dicarboxylic acid in the presence of a condensing agent, in an organic solvent 10 to 1
Polycondensation method at a reaction temperature of 50 ° C., (a) Polycondensation of aromatic diamine and aromatic dicarboxylic acid dihalide in an organic solvent at a reaction temperature of 60 ° C. or lower in the presence of a dehydrohalogenating agent. , (C) aromatic diamine and aromatic dicarboxylic acid dialkylate and / or aromatic dicarboxylic acid diallylate in an organic solvent in an amount of 100 to 30
A method of polycondensation at a reaction temperature of 0 ° C.

The aromatic diamine used in this method is
1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene and 1,4-bis (4-aminophenoxy) It is at least one selected from the group consisting of benzene.

As the aromatic dicarboxylic acid used, an aromatic dicarboxylic acid is used in the above 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,
Ethoxyisophthalic acid, chloroisophthalic acid, bromoisophthalic acid, terephthalic acid, methylterephthalic acid, ethylterephthalic acid, methoxyterephthalic acid,
Examples thereof include ethoxyterephthalic acid, chloroterephthalic acid and bromoterephthalic acid. When a is 1 or 2, 2,2′-biphenyldicarboxylic acid,
4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylsulfidedicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid,
4,4'-diphenylmethanedicarboxylic acid, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3
-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 may be used alone or in admixture of two or more.

In the method (a), 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 above diamine component and 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 method 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 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, but usually the aromatic polyamide of the formula (1) is used. Allow to react for a sufficient time to complete production. Usually 10 minutes ~
24 hours is enough. By such a reaction, the formula (1)
(Chemical formula 10)

[0025]

[Chemical 10] (In the formula, X is a condensed polycyclic aromatic group having 20 or less carbon atoms, or

[0026]

[Chemical 11] 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 1,3-bis (3-aminophenoxy) as a reaction raw material monomer.
Benzene, 1,3-bis (4-aminophenoxy) benzene,
At least one selected from the group consisting of 1,4-bis (3-aminophenoxy) benzene and 1,4-bis (4-aminophenoxy) benzene and an aromatic dicarboxylic acid such as aromatic dicarboxylic acid or dicarboxylic acid dihalide It is characterized by using an 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 is prepared by using 1,3-bis (3-aminophenoxy) benzene of the above formula (2), 1,
3-bis (4-aminophenoxy) benzene, 1,4-bis (3-
An aromatic diamine and an aromatic dicarboxylic acid or an aromatic dicarboxylic acid derivative containing at least one selected from the group consisting of aminophenoxy) benzene and 1,4-bis (4-aminophenoxy) benzene as a main component are monovalent. It can be obtained by reacting in the presence of the carboxylic acid or carboxylic acid derivative or the 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 aromatic and / or aliphatic and / or alicyclic monoamine.

The monocarboxylic acid used in these methods includes 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. Examples of the monocarboxylic acid ester include alkyl esters of the above-mentioned 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 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 the resin composition thereof 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. 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. 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 improver such as calcium metasilicate, heat conductivity improver such as iron powder, zinc powder, aluminum powder, copper powder, other glass beads, talc, diatomaceous earth, alumina, silasbaln, hydrated alumina, metal oxide , Coloring agents and the like.

As the fibrous reinforcing material used in the present invention, various materials 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 thin glass fiber having a predetermined diameter, which is obtained by rapidly cooling molten glass while drawing it by various methods. A strand obtained by bundling single fibers with a sizing agent, 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, 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,
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.

The potassium titanate fiber used in the present invention is a kind of high strength fiber (whisker), and has a chemical composition of K ₂ O.6TiO ₂ and K ₂ O.6TiO ₂ .1 /.
It is a needle-like crystal based on 2H ₂ O and has a typical melting point of 1
It is 300-1350 degreeC. Average fiber length is 5-50μ
The average fiber length is 20 to 30 μm, and the average fiber diameter is preferably 0.1 to 0.3 μm. The potassium titanate fiber can be usually used without any treatment, but in order to have 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 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.

[0040]

[Chemical formula 12] 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 molded for practical use by a known molding method such as an injection molding method, an extrusion molding method, a compression molding method, and a rotational molding method.

[0043]

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 with DTA-TG (Shimadzu DT-40 series, DTG-40M) in air. Melt viscosity: Measured with a Shimadzu Koka type flow tester CFT500A with a load of 100 kg.

Example 1 29.23 g of 1,4-bis (3-aminophenoxy) benzene in a nitrogen atmosphere in a container equipped with a stirrer and a nitrogen introducing tube
(0.10 mol) and 350 g of N-methyl-2-pyrrolidone were charged and dissolved, and then 24.29 g (0.24 mol) of triethylamine 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 separated by filtration, washed with methanol, and dried under reduced pressure at 180 ° C. for 12 hours to give 40.89 g (yield 9
7%) of polyamide powder was obtained. This polyamide powder has an inherent viscosity of 0.61 dl / g, a glass transition temperature of 195 ° C. and 5%.
The weight loss temperature was 505 ° 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 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 polyamide film had a tensile strength of 1000 kg / cm ² and a tensile elongation of 2.1%. Both measurement methods are based on ASTM D-882. The water absorption of this film was 0.74%. The measuring method is ASTM D-750-63
According to.

Example 2 The procedure of Example 1 was repeated except that terephthalic acid chloride in Example 1 was replaced with isophthalic acid chloride, and 41.02 g (yield 97%) of polyamide powder having an inherent viscosity of 0.67 dl / g.
Got The glass transition temperature of this polyamide powder is 192
℃, 5% weight loss temperature was 502 ℃. 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 1530 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
1200 kg / cm ² , tensile elongation 15%, water absorption 0.70%
Met.

Example 3 Similar to 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, 40.89 g (yield 97%) of polyamide powder having an inherent viscosity of 0.63 dl / g was obtained. This polyamide powder has a glass transition temperature of 192 ° C and a 5% weight loss temperature of 503 ° C.
Met. Example 1 was performed using the obtained polyamide powder.
A colorless and transparent polyamide film was obtained in the same manner as in.
The tensile strength of this polyamide film is 1200 Kg / cm
^{2. The} tensile elongation was 11% and the water absorption was 0.71%.

Example 4 Logarithmic viscosity was the same as in Example 1 except that 1,4-bis (3-aminophenoxy) benzene in Example 1 was replaced with 1,3-bis (3-aminophenoxy) benzene. 0.75 dl /
40.72 g of polyamide powder (yield 96%) was obtained. This polyamide powder had a glass transition temperature of 182 ° C and a 5% weight loss temperature of 486 ° 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. 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 0.71%
Met.

Example 5 41.10 g (yield 97%) of polyamide powder having an inherent viscosity of 0.76 dl / g was obtained in the same manner as in Example 4 except that terephthalic acid chloride in Example 4 was replaced with isophthalic acid chloride. .. The glass transition temperature of this polyamide powder is 177 ° C,
The 5% weight loss temperature was 490 ° 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 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
1060Kg / cm ² , tensile elongation 22%, water absorption 0.75%
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, 41.02 g (yield 97%) of polyamide powder having an inherent viscosity of 0.77 dl / g was obtained. This polyamide powder has a glass transition temperature of 179 ° C and a 5% weight loss temperature of 487 ° C.
Met. Example 1 was performed using the obtained polyamide powder.
A colorless and transparent polyamide film was obtained in the same manner as in.
The tensile strength of this polyamide film is 1180 Kg / cm
^{2. The} tensile elongation was 19% and the water absorption was 0.70%.

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 450 g of N-methyl-2-pyrrolidone, the temperature was raised to 120 ° C. There, 1,3-bis (3-aminophenoxy) benzene
29.23 g (0.10 mol) was charged 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 is filtered off and washed with methanol,
After drying under reduced pressure at ℃ for 12 hours, 39.87g (yield 94%) of polyamide powder was obtained. The logarithmic viscosity of this polyamide powder is 0.8
The glass transition temperature was 1 dl / g, the glass transition temperature was 183 ° C, and the 5% weight loss temperature was 490 ° 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 in a container equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere, 1,3-
Charge 29.23 g (0.10 mol) of bis (3-aminophenoxy) benzene and 750 g of diphenyl ether, and add 8 at 250 ° C.
Stir for hours. The reaction product thus obtained was discharged into vigorously stirred methanol 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 39.37 g (yield 93%) of polyamide powder. The logarithmic viscosity of this polyamide powder is 0.63 dl /
g, glass transition temperature 179 ° C, 5% weight loss temperature 484 ° C
Met. 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 4, in the vicinity of 1650 cm ^-1 and near 1520 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed.

Example 9 29.23 g of 1,3-bis (3-aminophenoxy) benzene in a nitrogen atmosphere in a container equipped with a stirrer and a nitrogen introducing tube
(0.10 mol) and 350 g of N-methyl-2-pyrrolidone were charged and dissolved, and then 24.29 g (0.24 mol) of triethylamine was added and cooled to 5 ° C. Then, stirring was intensified and 19.29 g (0.095 mol) of terephthaloyl chloride was charged, and stirring was continued at room temperature for 2 hours. Then 2.11 g of benzoyl chloride
(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 40.17 g (yield 95%) of polyamide powder. The polyamide powder had an inherent viscosity of 0.44 dl / g. When the melt viscosity of the obtained polyamide powder was measured, it was 5200 poise at 330 ° C. Further, the obtained strand was light yellow transparent, rich in flexibility, and extremely tough.

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 330 ° 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. Also, this polyamide powder is used at 310 ° C and 150 K.
The heat distortion temperature of the molded product obtained by compression molding at g / cm ² for 15 minutes was 168 ° C. The measuring method is ASTM D
-648, based on a load of 18.6 Kg / cm ² .

Example 10 29.23 g of 1,3-bis (3-aminophenoxy) benzene in a nitrogen atmosphere in a container equipped with a stirrer and a nitrogen introducing tube
(0.095 mol) and 350 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, stirring was intensified, 20.30 g (0.10 mol) of terephthaloyl chloride was charged, and stirring was continued for 2 hours at room temperature. Then 1.40 g (0.015 mol) of aniline
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 reduced pressure at 180 ° C for 12 hours.
8 g (yield 94%) of polyamide powder was obtained. The logarithmic viscosity of this polyamide powder was 0.42 dl / g. When the melt viscosity of the obtained polyamide powder was measured, it was 4700 poise at 330 ° 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 under a nitrogen atmosphere in a container equipped with a stirrer and a nitrogen introducing tube.
-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 330 ° C. and 400 ° C., but no melt flow was observed 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 0.45 dl / g. When the residence time in the flow tester cylinder was changed and the melt viscosity was measured in the same manner as in Example 9, the melt viscosity increased as the residence time increased, as shown in FIG. 7. It was inferior in thermal stability to the obtained 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 by a drum blender mixer (Kawata Manufacturing Co., Ltd.), and then melt-kneaded at a temperature of 330 ° 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 pellets obtained were injection-molded (Arburg molding machine, maximum mold clamping force 35 tons, injection pressure 500 kg /
cm ² , cylinder temperature 330 ° 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.

[0060]

[Table 1]

Comparative Examples 3 and 4 Polyamides obtained in Examples 4 and 5 10 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.

[0062]

[Table 2]

Examples 13 and 14 10 polyamides 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 Tens of the polyamides 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 obtained in Examples-4 and 5, respectively 10
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.

[0067]

[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.

[0069]

[Table 5]

[0070]

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 330 ° 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)

[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. The following formula (2) (formula 3): 1,3-bis (3-aminophenoxy) benzene represented by
At least one selected from the group consisting of 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene and 1,4-bis (4-aminophenoxy) benzene, A process for producing an aromatic polyamide according to claim 1, which is obtained by polycondensation with 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. .. 3. 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) represented by formula (2) At least one selected from the group consisting of benzene and 1,4-bis (4-aminophenoxy) benzene and an aromatic dicarboxylic acid in the presence of a condensing agent in an organic solvent at 10 to 150 ° C.
The method for producing an aromatic polyamide according to claim 1, which is obtained by polycondensation at the reaction temperature of. 4. A 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) represented by the formula (2). 100 to 300 of at least one selected from the group consisting of benzene and 1,4-bis (4-aminophenoxy) benzene, an aromatic dicarboxylic acid dialkylate and / or an aromatic dicarboxylic acid diallylate 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 ° C. 5. An aromatic polyamide having good thermal stability represented by the formula (1), which has a molecular terminal blocked with a monovalent carboxylic acid, a 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 (1) as a basic skeleton, and a polycondensation reaction is a monovalent carboxylic acid. It is carried out in the presence 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 the acid or carboxylic acid derivative in an amount of 0.001 to 1.0 mol per 1 mol of the 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 (1) 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 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 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 fiber is at least one kind selected from the group consisting of those having repeating structural units represented by the following formulas (1), (2) and (3). Aromatic polyamide resin composition. (Chemical formula 4) [Chemical formula 4]