JP3174387B2 - Aromatic polyamide resin and its resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel heat-meltable aromatic polyamide having high heat resistance.

Furthermore, it has excellent dimensional stability and mechanical properties,
In addition, the present invention relates to a novel aromatic polyamide resin composition having excellent processability.

[0003]

2. Description of the Related Art Conventionally, aromatic polyamides obtained by reacting an aromatic diamine or aromatic diisocyanate with an aromatic dicarboxylic acid or a derivative thereof have been known for their excellent physical properties and good heat resistance. It is expected that it will be widely used in fields requiring heat resistance in the future.

[0004] However, the aromatic polyamides which have been developed in the past have many mechanical properties and heat resistance, but all have the drawback of poor moldability and high water absorption. Was. For example, the following formula (Formula 1)
3)

[0005]

Embedded image An aromatic polyamide having a basic skeleton represented by the following formula (DuPont product: Kevlar) has excellent properties such as flame retardancy, heat resistance, high tension and high elastic modulus. However, this aromatic polyamide does not have a clear glass transition temperature, has a thermal decomposition temperature of about 430 ° C, and is close to the processing temperature and the thermal decomposition temperature, so it is difficult to process it as a molding material. There were drawbacks. Therefore, it is only used in the field of fibers by wet spinning or pulp. Further, the water absorption rate is as high as 4.5%, and it is apparent that the use of the same as a base material for electric / electronic parts adversely affects dimensional stability, insulation properties, solder heat resistance, and the like.
("Latest heat-resistant polymer": Sogo Gijutsu Center)

[0006]

An object of the present invention is to provide an aromatic polyamide having excellent processability and low water absorption, in addition to the excellent heat resistance inherent to the aromatic polyamide, and a method for producing the same. is there. It is still another object of the present invention to provide a novel resin composition which improves the mechanical strength and dimensional stability of the aromatic polyamide and further has excellent processability.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above-mentioned objects, and as a result, have found a novel aromatic polyamide having desired performance and a resin composition thereof, thereby completing the present invention. Reached. That is, the present invention relates to (1) Formula (1)

[0008]

Embedded image (Wherein X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound represented by the formula

[0009]

Embedded image R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, a phenyl group, a represents 0, 1 or 2, and b represents 0.
Or, represents an integer of 1 to 4. N represents an integer of 1 to 1000. (2) Formula (2) (Formula 16)

[0010]

Embedded image 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindane and / or 5- (3-aminophenoxy) -3- [ 4- (3-
Aminophenoxy) phenyl] -1,1,3-trimethylindane and an aromatic dicarboxylic acid obtained by polycondensation in an organic solvent, characterized by the following formula (1): A method for producing an aromatic polyamide,

[0011]

Embedded image (Wherein X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound represented by the formula

[0012]

Embedded image R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, a phenyl group, a represents 0, 1 or 2, and b represents 0.
Or, represents an integer of 1 to 4. N represents an integer of 1 to 1000. (3) Formula (1)

[0013]

Embedded image (Wherein X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound represented by the formula:

[0014]

Embedded image R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, a phenyl group, a represents 0, 1 or 2, and b represents 0.
Or, represents an integer of 1 to 4. N represents an integer of 1 to 1000. Aromatic polyamide having good heat stability, having a repeating unit represented by formula (1) as a basic skeleton, and sealing the molecular terminal of the polymer with a monovalent amine or a monovalent carboxylic acid or a carboxylic acid derivative; Production method, (4) Formula (1)

[0015]

Embedded image (Wherein, X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound represented by the formula

[0016]

Embedded image R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, a phenyl group, a represents 0, 1 or 2, and b represents 0.
Or, represents an integer of 1 to 4. N represents an integer of 1 to 1000. ), And an aromatic polyamide resin composition comprising 100 parts by weight of the aromatic polyamide represented by the formula (1) and 5 to 100 parts by weight of the fibrous reinforcing material. The aromatic polyamide of the present invention has a diamine component represented by the formula (2):

[0017]

Embedded image 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindane and / or 5- (3-aminophenoxy) -3- [ 4- (3-
[Aminophenoxy) phenyl] -1,1,3-trimethylindane and polymerized with aromatic dicarboxylic acid or a derivative thereof. Further, 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 contain 5- (4-
Aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindane and / or 5-
It is characterized by using (3-aminophenoxy) -3- [4- (3-aminophenoxy) phenyl] -1,1,3-trimethylindane as a diamine component. In addition to the heat resistance inherent to aromatic polyamide, , With excellent workability,
A thermoplastic aromatic polyamide and a resin composition thereof.

Since the aromatic polyamide and the resin composition are thermoplastic in addition to excellent heat resistance, they can be extruded and injection-molded, and can be used as a base material for space and aircraft, and a base material for electric and electronic parts. Furthermore, it can be expected to be used for multipurpose applications as a raw material for high-strength, high heat-resistant fibers by the melt spinning method, and is extremely useful. The aromatic polyamide of the present invention is an aromatic polyamide using the above-mentioned diamine as a raw material, but other diamines may be mixed and used as long as good physical properties of the aromatic polyamide are not impaired.

Examples of the diamines that can be used in combination are, for example, 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'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfoxide, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 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] diphenylsulfone, bis [4-
{4- (4-aminophenoxy) phenoxy} phenyl] ketone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) -α , Α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, etc., and these may be used alone or as a mixture of two or more. You.

The method for producing the aromatic polyamide of the present invention is not particularly limited, and a conventionally known method can be employed. For example, (a) a method of polycondensing an aromatic diamine and an aromatic dicarboxylic acid in an organic solvent at a reaction temperature of 10 to 150 ° C. in the presence of a condensing agent, (a) an aromatic diamine and an aromatic dicarboxylic acid A method of performing polycondensation of dihalide with an organic solvent at a reaction temperature of 60 ° C. or lower in the presence of a dehydrohalogenating agent, (c) reacting an aromatic diamine with an aromatic dicarboxylic acid dialkylate and / or an aromatic dicarboxylic acid diallylate; Is subjected to polycondensation in an organic solvent at a reaction temperature of 100 to 300 ° C. The aromatic diamine used in this method is 5- (4-aminophenoxy) -3- [4- (4-
Aminophenoxy) phenyl] -1,1,3-trimethylindane and / or 5- (3-aminophenoxy) -3- [4-
(3-aminophenoxy) phenyl] -1,1,3-trimethylindane. As the aromatic dicarboxylic acids to be used, in the method (A), aromatic dicarboxylic acids are used. 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 acids, chloroisophthalic acids,
Bromoisophthalic acids, terephthalic acid, methylterephthalic acids, ethylterephthalic acids, methoxyterephthalic acids, ethoxyterephthalic acids, chloroterephthalic acids,
Bromoterephthalic acids and the like. Also, a is 1
Or in the case of 2, 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylsulfidedicarboxylic acid, 4,4'-benzophenonedicarboxylic acid 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,
Examples thereof include 4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. These aromatic dicarboxylic acids may be used alone or
Used as a mixture of more than one species.

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 dihalides are used alone or in combination of two or more.

In the method (c), a dialkyl aromatic dicarboxylic acid and / or a diallyl aromatic dicarboxylic acid are used. For example, each of the aromatic dicarboxylic acids has 1 to 10 carbon atoms such as dialkyl ester, diphenyl ester, di (fluorophenyl) ester, di (chlorophenyl) ester, di (bromophenyl) ester, di (methylphenyl) ester, Di (ethylphenyl) ester, di (propylphenyl) ester, di (isopropylphenyl) ester, di (butylphenyl) ester, di (isobutylphenyl) ester, di (t-butylphenyl) ester, di (methoxyphenyl) ester And di (ethoxyphenyl) ester, di (nitrophenyl) ester, di (phenylphenyl) ester, and dinaphthyl ester. These aromatic dicarboxylic diesters are 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. As the solvent used, 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, dimethylsulfoxide, dimethylsulfone, 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 1,4-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,
t-butanol, cyclohexanol, benzyl alcohol, water and the like. These solvents may be used alone or in combination of two or more, depending on the type of the reaction raw material monomer and the polymerization technique. When an aromatic dicarboxylic acid dihalide is used as a reaction raw material monomer, a dehydrohalogenating agent is usually used in combination. The dehydrohalogenating agents used include 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 include ethylene oxide and propylene oxide.

When an aromatic dicarboxylic acid is used as a 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 condensing agent, triphenylphosphine-hexachloroethane condensing agent, propyl phosphoric anhydride-N-methyl-2-pyrrolidone condensing agent And the like.

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 the reaction can be carried out at normal pressure. The reaction time varies depending on the type of the reaction raw 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, but usually, the aromatic polyamide represented by the formula (1) is used. The reaction is allowed to react for a time sufficient to complete the formation. Usually 10 minutes to 24
Time is enough. By such a reaction, the compound represented by the formula (1)

[0026]

Embedded image (Wherein X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound represented by the formula

[0027]

Embedded image R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, a phenyl group, a represents 0, 1 or 2, and b represents 0.
Or, represents an integer of 1 to 4. N represents an integer of 1 to 1000. An aromatic polyamide having a repeating unit represented by the formula (1) is obtained. That is, the aromatic polyamide of the present invention can be obtained by any method such as a known low-temperature solution polycondensation method or a direct polycondensation method as a method for synthesizing a polyamide.

The aromatic polyamide of the present invention is obtained by reacting 5- (4-aminophenoxy) -3- as a raw material monomer.
[4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindane and / or 5- (3-aminophenoxy)
-3- [4- (3-aminophenoxy) phenyl] -1,1,3-trimethylindane and aromatic dicarboxylic acid or an aromatic dicarboxylic acid derivative such as dicarboxylic dihalide are characterized by using .

However, in order to improve the thermal stability and moldability of the aromatic polyamide, the terminal of the polymer molecule is capped with a monovalent carboxylic acid or a carboxylic acid derivative or a monovalent amine. No problem. Such an aromatic polyamide is obtained by preparing 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindane and / or 5- (3-aminophenoxy) -3- [4-
(3-aminophenoxy) phenyl] -1,1,3-trimethylindane as a main component, an aromatic dicarboxylic acid or an aromatic dicarboxylic acid derivative, a monovalent carboxylic acid or a carboxylic acid derivative, or It is obtained by reacting in the presence of 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; 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 acid, bromobenzoic acid, methylbenzoic acid, ethylbenzoic acid, methoxybenzoic acid, ethoxybenzoic acid, nitrobenzoic acid,
Acetylbenzoic acids, acetoxybenzoic acids, hydroxybenzoic acids, biphenylcarboxylic acids, benzophenonecarboxylic acids, diphenylethercarboxylic acids, diphenylsulfidecarboxylic acids, diphenylsulfoncarboxylic acids, 2,2-diphenylpropanecarboxylic acids, 2,2-diphenyl-1 , 1,1,3,3,3-hexafluoropropanecarboxylic acids, naphthalenecarboxylic acids, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, nitroacetic acid, propionic acid, butyric acid, Valeric acid, caproic acid, cyclohexanecarboxylic acid and the like can be mentioned. These monocarboxylic acids are used alone or in combination of two or more.

Further, as the monocarboxylic acid halide,
For example, there may be mentioned the acid chlorides and acid bromides of the aforementioned monocarboxylic acids. These monocarboxylic acid halides may be used alone or in combination of two or more. Examples of the monocarboxylic acid ester include the above-mentioned monocarboxylic acid alkyl esters having 1 to 10 carbon atoms, phenyl ester, fluorophenyl ester, chlorophenyl ester, bromophenyl ester, methylphenyl ester, ethylphenyl ester, and propylphenyl. Examples include esters, isopropylphenyl esters, butylphenyl esters, isobutylphenyl esters, t-butylphenyl esters, methoxyphenyl esters, ethoxyphenyl esters, nitrophenyl esters, phenylphenyl esters, naphthyl esters, and the like.
These monocarboxylic acid esters are used alone or in combination of two or more.

The amount of the monocarboxylic acid used is from 0.001 to 1.0 mol per mol of the aromatic diamine.
If the amount is less than 0.001 mol, the viscosity increases during high-temperature molding, which causes a reduction in moldability. On the other hand, if it exceeds 1.0 mol, the mechanical properties deteriorate. The preferred amount is
The ratio is 0.01 to 0.5 mol.

When a monovalent amine is used, for example, aniline, o-toluidine, m-toluidine, p-toluidine,
-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-aminobiphenyl
Aminophenylphenyl ether, 4-aminophenylphenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminobenzophenone
Aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide, 4-aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfide
Aminophenylphenylsulfone, 4-aminophenylphenylsulfone, 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,
Cyclopentylamine, cyclohexylamine and the like can be mentioned. These monoamines are used alone or in combination of two or more.

The amount of the monoamine used is from 0.001 to 1.0 mol per mol of aromatic dicarboxylic acids.
If the amount is less than 0.001 mol, the viscosity increases during high-temperature molding, which causes a reduction in moldability. On the other hand, if it exceeds 1.0 mol, the mechanical properties deteriorate. The preferred amount is
The ratio is 0.01 to 0.5 mol.

The aromatic polyamide and the resin composition of the present invention can be subjected to melt molding. In this case, other thermoplastic resins can be blended in an appropriate amount according to the purpose within a range that does not impair the purpose of the present invention. As thermoplastic resins that can be blended, polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polyimide, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyphenylenesulfide, polyamideimide, polyetherimide, modified And polyphenylene oxide. It is also possible to mix a thermosetting resin or a filler to such an extent that the object of the invention is not impaired. Examples of the thermosetting resin include a phenol resin and an epoxy resin. Fillers include abrasion-resistant materials such as graphite, carborundum, silica stone powder, molybdenum disulfide, and fluororesin, glass fibers, carbon fibers, boron fibers, silicon carbide fibers, carbon whiskers, asbestos, metal fibers, and ceramic fibers. Reinforcement material such as antimony trioxide, magnesium carbonate, calcium carbonate, etc., electrical property improving material such as clay, mica, asbestos, silica, graphite and other tracking resistance improving material, barium sulfate, silica, Acid resistance improving materials such as calcium metasilicate, thermal conductivity improving materials such as iron powder, zinc powder, aluminum powder, and copper powder, other glass beads, talc, diatomaceous earth, alumina, silasbarn, hydrated alumina, metal oxides , Coloring agents and the like.

As the fibrous reinforcing material used in the present invention, various materials are used, for example, glass fiber, carbon fiber,
Potassium titanate fiber, aromatic polyamide fiber, silicon carbide fiber, alumina fiber, boron fiber, ceramic fiber, etc. are exemplified, but glass fiber, carbon fiber, potassium titanate fiber, and aromatic polyamide fiber are particularly preferably used. It is.

The glass fiber used in the present invention is obtained by quenching molten glass while stretching it by various methods to form a thin fiber having a predetermined diameter. A strand in which single fibers are bundled with a sizing agent, It means roving or the like in which strands are uniformly aligned to form a bundle, and any of them can be used in the present invention. The glass fiber is a silane coupling agent such as aminosilane and epoxy silane, chromic chloride, in order to have an affinity with the base resin of the present invention.
Other surface treatment agents suitable for the purpose can be used. The length of the glass fiber in the present invention greatly affects the physical properties of the obtained molded article and the workability during the production of the molded article. Generally, as the glass fiber length increases, the physical properties of the molded article improve, but conversely, the workability during the production of the molded article deteriorates. For this reason, the length of the glass fiber is 0.1 to 6 in the present invention.
mm, preferably in the range of 0.3-4 mm,
This is preferable because the physical properties and workability of the molded article are well balanced.

The carbon fibers used in the present invention are high elasticity and high strength fibers obtained by carbonizing polyacrylonitrile, petroleum pitch or the like as a main raw material. In the present invention, both polyacrylonitrile and petroleum pitch can be used. Carbon fibers having an appropriate diameter and an appropriate aspect ratio (length / diameter ratio) are used depending on the reinforcing effect and the mixing property. The diameter of the carbon fiber is usually 5 to 20 μm,
Particularly, those having a thickness of about 8 to 15 μm are preferable. Further, the aspect ratio is 1 to 600, and especially 1 due to the reinforcing effect and the mixing property.
About 00 to 350 is preferable. If the aspect ratio is small, there is no reinforcing effect, and if the aspect ratio is large, the mixing property is poor, and a good molded product cannot be obtained. In addition, those obtained by treating the surface of the carbon fiber with various treatment agents, for example, an epoxy resin, a polyamide resin, a polycarbonate resin, a polyacetal resin, and the like, and those using a known surface treatment agent depending on the purpose are also used.

The potassium titanate used in the present invention
Fiber is a kind of high strength fiber (whisker),
K_TwoO ・ 6TiO_Two, K_TwoO ・ 6TiO_Two・ 1 /
2 H _TwoIt is a needle-like crystal based on O and has a typical melting point of 1.
300-1350 ° C. Average fiber length is 5-50μ
m, average fiber diameter is 0.05 ~ 1.0μm
The average fiber length is 20-30 μm and the average fiber diameter is
Those having a thickness of 0.1 to 0.3 μm are preferred. The potassium titanate
Um fiber can be used without any treatment.
Aminosilane, epoxy, etc.
Silane coupling agents such as silane
Use a surface treatment agent suitable for riding and other purposes
Can be. Also, the aromatic polyamide fiber used in the present invention
Fiber is a relatively newly developed heat-resistant organic fiber,
Expected to expand into various fields by utilizing many unique characteristics
Have been. For example, a typical example is the following structural formula.
And at least one of these.
Alternatively, a mixture of two or more kinds is used.

[0041]

Embedded image In addition, there are aromatic polyamide fibers having various skeletons due to ortho, meta, and para position structural isomers. Among them, those having a high softening point and a high melting point in the present invention are those having a high softening point and melting point. Most preferred.

In the case of glass fiber and carbon fiber, if it is less than 5 parts by weight, the reinforcing effect specific to glass fiber or carbon fiber characteristic of the present invention cannot be obtained. Conversely, if it is used in an amount of 100 parts by weight or more, the fluidity during molding of the composition becomes poor, and it becomes difficult to obtain a satisfactory molded product. If the amount of potassium titanate fiber is less than 5 parts by weight, the improvement of the mechanical properties at high temperatures, which is a feature of the present invention, is insufficient. Conversely, if the amount is large, dispersion in melt mixing becomes insufficient, and further, the fluidity becomes low, and molding under ordinary conditions becomes difficult, which is not preferable. The preferred amount is 10 to 100 parts by weight. When the amount of the aromatic polyamide fiber is 5 parts by weight or less, a composition excellent in moldability and mechanical strength, which is a feature of the present invention, cannot be obtained. If it is used in an amount of 100 parts by weight or more, the fluidity of the composition at the time of molding deteriorates, and it becomes difficult to obtain a satisfactory molded product. The preferred amount is 10 to 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 using a mortar, a Henshall mixer, a drum blender, a tumbler blender, a ball mill, a ribbon blender, and the like, and then, using a generally known melt mixer, a hot roll, or the like. After kneading, pelletize or powder. (2) The 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-dimethylacetamide
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, dimethylsulfoxide, dimethylsulfone, 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 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 is provided for practical use.

[0044]

EXAMPLES Hereinafter, the production examples of the aromatic polyamide of the present invention and the physical properties and performance of the obtained aromatic polyamide 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: Measured at 35 ° C. after dissolving 0.50 g of polyamide powder in 100 ml of hexamethylphosphoric triamide.

Glass transition temperature (Tg): Measured by DSC (Shimadzu DT-40 series, DSC-41M). 5% weight loss temperature: Measured by DTA-TG (Shimadzu DT-40 series, DTG-40M) in air. Melt viscosity: Measured with a load of 100 kg using Shimadzu Koka type flow tester CFT500A.

Example 1 In a vessel equipped with a stirrer and a nitrogen inlet tube, under a nitrogen atmosphere, 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3- Trimethylindane 45.06
g (0.10 mol) and N-methyl-2-pyrrolidone (500 g) were charged and dissolved, and then triethylamine (24.29 g, 0.24 mol) was added, and the mixture was cooled to 5 ° C. Thereafter, the stirring was increased and 20.30 g (0.10 mol) of terephthalic acid chloride was charged, followed by stirring at room temperature for 3 hours. The viscous polymer solution thus obtained was discharged into vigorously stirred methanol to precipitate a white powder. This white powder was separated by filtration, washed with methanol, and dried under reduced pressure at 180 ° C. for 12 hours to obtain 56.37 g (yield 9
(7.1%). The logarithmic viscosity of this polyamide powder is 0.81 dl / g, the glass transition temperature is 261 ° C., 5%
The weight loss temperature was 496 ° C. The results of elemental analysis of the obtained polyamide powder are as follows. FIG. 1 shows an infrared absorption spectrum of the obtained polyamide powder. This spectrum diagram, in the vicinity of 1650 cm ^-1 and near 1510 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed.

Further, the obtained polyamide powder was N-methyl
After dissolving in 2-pyrrolidone, it was cast on a glass plate and heated at 150 ° C for 1 hour and at 250 ° C for 2 hours to obtain a colorless and transparent polyamide film. This polyamide film had a tensile strength of 1273 kg / cm ² and a tensile elongation of 12%. Both measurement methods are based on ASTM D-882. The water absorption of this film was 1.29%. Measurement method is ASTM D-750-63
It depends on.

Example 2 The procedure of Example 1 was repeated, except that terephthalic acid chloride was replaced by isophthalic acid chloride. 56.27 g (yield 96.9%) of a polyamide powder having an logarithmic viscosity of 0.92 dl / g
I got The glass transition temperature of this polyamide powder is 241
° C, 5% weight loss temperature was 501 ° C. The results of elemental analysis of the obtained polyamide powder are as follows. FIG. 2 shows an infrared absorption spectrum of the obtained polyamide powder. This spectrum diagram, in the vicinity of 1660 cm ^-1 and near 1510 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed. Further, a colorless and transparent polyamide film was obtained in the same manner as in Example 1 using the obtained polyamide powder. The tensile strength of this polyamide film is
1100kg / cm ² , tensile elongation 14%, water absorption 1.27%
Met.

Example 3 The procedure of Example 1 was repeated except that terephthalic acid chloride in Example 1 was replaced by 20.30 g (0.10 mol) with 10.15 g (0.05 mol) of terephthalic chloride and 10.15 g (0.05 mol) of isophthalic chloride. As a result, 56.59 g (97.5% yield) of a polyamide powder having a logarithmic viscosity of 0.88 dl / g was obtained.

The glass transition temperature of this polyamide powder is 2
The temperature at 43 ° C. and 5% weight loss was 500 ° C. Poly obtained
Using amide powder, colorless and transparent in the same manner as in Example 1.
Was obtained. This polyamide film
Has a tensile strength of 1180kg / cm ^Two, Tensile elongation is 14%,
The water content was 1.27%.

Example 4 5- (4-aminophenoxy) -3- [4-
(4-Aminophenoxy) phenyl] -1,1,3-trimethylindane to 5- (3-aminophenoxy) -3- [4- (3-aminophenoxy) phenyl] -1,1,3-trimethylindane Except having changed, it carried out similarly to Example 1 and logarithmic viscosity 0.66d
56.49 g (97.3% yield) of 1 / g polyamide powder were obtained.
The glass transition temperature of this polyamide powder was 218 ° C, and the 5% weight loss temperature was 499 ° C. The results of elemental analysis of the obtained polyamide powder are as follows. FIG. 3 shows an infrared absorption spectrum of the obtained polyamide powder. This spectrum diagram, in the vicinity of 1670 cm ^-1 and near 1510 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed. Further, a colorless and transparent polyamide film was obtained in the same manner as in Example 1 using the obtained polyamide powder. The tensile strength of this polyamide film is
1080 kg / cm ² , tensile elongation 15%, water absorption 1.23%
Met.

Example 5 The procedure of Example 4 was repeated, except that terephthalic acid chloride was replaced with isophthalic acid chloride. 56.59 g (yield: 97.5%) of polyamide powder having an logarithmic viscosity of 0.65 dl / g
I got The glass transition temperature of this polyamide powder is 206
° C, 5% weight loss temperature was 501 ° C. The results of elemental analysis of the obtained polyamide powder are as follows. FIG. 4 shows an infrared absorption spectrum of the obtained polyamide powder. 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. Further, a colorless and transparent polyamide film was obtained in the same manner as in Example 1 using the obtained polyamide powder. The tensile strength of this polyamide film is
1070 kg / cm ² , tensile elongation 15%, water absorption 1.25%
Met.

Example 6 In the same manner as in Example 4 except that 20.30 g (0.10 mol) of terephthalic chloride in Example 4 was replaced with 10.15 g (0.05 mol) of terephthalic chloride and 10.15 g (0.05 mol) of isophthalic chloride. As a result, 56.57 g (yield: 97.4%) of polyamide powder having a logarithmic viscosity of 0.67 dl / g was obtained. This polyamide powder has a glass transition temperature of 210 ° C and a 5% weight loss temperature of 500.
° C. A colorless and transparent polyamide film was obtained in the same manner as in Example 1 using the obtained polyamide powder. The tensile strength of this polyamide film is 1060kg / c
m ² , tensile elongation was 15%, and water absorption was 1.24%.

Example 7 In a vessel equipped with a stirrer and a nitrogen inlet tube, under a nitrogen atmosphere, 16.62 g (0.10 mol) of terephthalic acid, lithium chloride 2
0.0 g, 60.0 g of calcium chloride, 200 g of pyridine, 62.0 g (0.20 mol) of triphenyl phosphite, and 750 g of N-methyl-2-pyrrolidone were charged and dissolved, and the temperature was raised to 120 ° C. Thereto, 45.06 g (0.10 mol) of 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindane was charged, and the mixture was heated at 120 ° C. for 2 hours. Stirred. The viscous polymer solution thus obtained was discharged into vigorously stirred methanol to precipitate a white powder. After the white powder is filtered off, washed with methanol, 180
Drying under reduced pressure at 12 ° C. for 12 hours gave 56.93 g (yield 98.0%) of polyamide powder. The logarithmic viscosity of this polyamide powder is 0.
83dl / g, glass transition temperature is 261 ℃, 5% weight loss temperature is 4
It was 96 ° C. The results of elemental analysis of the obtained polyamide powder are as follows. FIG. 5 shows an infrared absorption spectrum of the obtained polyamide powder. The spectrogram is exactly the same as the polyamide powder obtained in Example 1, in the vicinity of 1670 cm ^-1 and near 1520 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed.

Example 8 In a container equipped with a stirrer and a nitrogen inlet tube, under a nitrogen atmosphere, 19.42 g (0.10 mol) of dimethyl terephthalate, 5- (4-
Aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindane (45.06 g (0.10 mol) and diphenyl ether (1100 g) were charged and stirred at 250 ° C. for 8 hours. The reaction thus obtained was discharged into vigorously stirred methanol to give a white powder. This white powder was separated by filtration, washed with methanol, and dried under reduced pressure at 180 ° C. for 12 hours to obtain 54.40 g (yield 93.7%) of a polyamide powder. The logarithmic viscosity of this polyamide powder is 0.69 dl /
g, glass transition temperature is 259 ℃, 5% weight loss temperature is 466 ℃
Met. The results of elemental analysis of the obtained polyamide powder are as follows. FIG. 6 shows an infrared absorption spectrum of the obtained polyamide powder. The spectrogram is exactly the same as the polyamide powder obtained in Example 1, in the vicinity of 1660 cm ^-1 and near 1510 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed.

Example 9 In a vessel equipped with a stirrer and a nitrogen inlet tube, under a nitrogen atmosphere, 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3- Trimethylindane 45.06
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. Thereafter, the stirring was strengthened and 19.29 g (0.095 mol) of terephthalic acid chloride was charged, and stirring was continued at room temperature for 2 hours. Then 2.11 g of benzoyl chloride
(0.015 mol) and stirring was continued at room temperature for 2 hours. The resulting polymer solution was discharged into vigorously stirred methanol to precipitate a white powder. This white powder was separated by filtration, washed with methanol, and dried under reduced pressure at 180 ° C. for 12 hours to obtain 55.26 g (yield 95.2%) of a polyamide powder.
The logarithmic viscosity of this polyamide powder was 0.43 dl / g. When the melt viscosity of the obtained polyamide powder was measured, it was 7000 poise at 360 ° C. In addition, the obtained strand was pale yellow, transparent, highly flexible, and very 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 was performed at 360 ° C. The results are shown in FIG. Even if the residence time in the cylinder becomes longer, the melt viscosity hardly changes, indicating that the thermal stability is good. The polyamide powder was heated at 340 ° C and 150K.
The heat distortion temperature of a molded product obtained by compression molding at 15 g / cm ² for 15 minutes was 236 ° C. ASTM D
-648, due to the load 18.6Kg / cm ^2.

Example 10 In a vessel equipped with a stirrer and a nitrogen inlet tube, under a nitrogen atmosphere, 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3- Trimethylindane 42.81
g (0.095 mol) and N-methyl-2-pyrrolidone (500 g) were charged and dissolved, and then triethylamine (24.29 g (0.24 mol))
Was added and cooled to 5 ° C. After that, stirring was increased and 20.30 g (0.10 mol) of terephthalic acid chloride was charged.
Stirring was continued for hours. Thereafter, 1.40 g (0.015 mol) of aniline was charged, and stirring was continued at room temperature for 2 hours. The resulting polymer solution was discharged into vigorously stirred methanol to precipitate a white powder. After filtering off this white powder,
Wash with methanol and dry under reduced pressure at 180 ° C for 12 hours.
5.17 g (95.0% yield) of polyamide powder was obtained. The logarithmic viscosity of this polyamide powder was 0.41 dl / g. When the melt viscosity of the obtained polyamide powder was measured, 360
It was 6400 poise at ° C. In addition, the obtained strand was pale yellow, transparent, highly flexible, and very tough.

Comparative Example 1 2.16 g (0.020 mol) of p-phenylenediamine and N-methyl were placed in a vessel equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere.
After 56.2 g of 2-pyrrolidone was charged and dissolved, 4.86 g (0.048 mol) of triethylamine was added, and the mixture was cooled to 5 ° C. Then, increase the agitation to 3.86 g of terephthalic acid chloride.
(0.019 mol) was charged at once, and stirring was continued at room temperature for 2 hours. Then, 0.443 g (0.003 mol) of benzoyl chloride
And stirring was continued at room temperature for 2 hours. The resulting polymer solution was discharged into vigorously stirred methanol to precipitate a white powder. This white powder was separated by filtration, washed with methanol, and dried under reduced pressure at 180 ° C. for 12 hours.
g (97.7% yield) of polyamide powder was obtained. When the glass transition temperature of this polyamide powder was measured, no clear value was shown. The melt viscosity was measured at 360 ° C. and 400 ° C., but no melt flow occurred at any temperature.

Comparative Example 2 A polyamide powder was synthesized in the same manner as in Example 9 except that benzoyl chloride was not used. The logarithmic viscosity of the polyamide powder was 0.44 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, as shown in FIG.
The melt viscosity increased as the residence time became longer, and the polyamide was inferior in heat stability to the polyamide obtained in Example 9.

Examples 11 and 12 Each of the polyamides obtained in Examples 1 and 4 was 10
0 parts by weight of silane-treated glass fiber having a fiber length of 3 mm and a fiber diameter of 13 μm (Nitto Boseki Co., Ltd .: CS-
3PE-476S) was added in the amount shown in Table 1, mixed with a drum blender mixer (manufactured by Kawada Seisakusho), melt-kneaded at a temperature of 360 ° C. with a single-screw extruder having a diameter of 30 mm, and then the strand was air-cooled. And cut to obtain pellets.

The obtained pellets were injection-molded (Arburg molding machine, maximum clamping force 35 tons, injection pressure 500 kg /
cm ² , cylinder temperature 360 ° 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 (with notch) (ASTM D-256), heat distortion temperature (ASTM D-648), molding Shrinkage (AST
(MD-955) is shown in Table 1.

[0063]

[Table 1] Comparative Examples -3 and 4 The polyamides obtained in Examples -1 and 4 were each 10
Table 2 shows the results obtained by using the same glass fibers as in Examples 11 and 12 for 0 parts by weight, except for the scope of the present invention.

[0064]

[Table 2] Examples -13 and 14 The polyamides obtained in Examples -1 and 4 were each 10
To 0 parts by weight, carbon fibers having an average diameter of 12 μm, a length of 3 mm, and an aspect ratio of 250 (trade name of Toray Co., Ltd.) were added 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.

[0065]

[Table 3] Comparative Examples -5 and 6 The polyamides obtained in Examples -1 and 4 were each 10
120 parts by weight of the same carbon fibers as in Examples 13 and 14 were added to 0 parts by weight, and an extrusion strand was tried in the same manner as in Examples 13 and 14, but none of the strands could be formed. Was.

Examples 15 and 16 Each of the polyamides obtained in Examples 1 and 4 was 10
With respect to 0 parts by weight, the cross-sectional diameter is 0.2 μm and the average fiber length is
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.
And 12, the results shown in Table 4 were obtained.

[0067]

[Table 4] Examples 17 and 18 The polyamides obtained in Examples -1 and 4 were each 10
To 0 parts by weight, an aromatic polyamide fiber having an average fiber length of 3 mm (trade name: Kevlar, DuPont) was added in the amount shown in Table 5, and the same as in Examples 11 and 12, and shown in Table 5. The result was obtained.

[0068]

[Table 5]

[0069]

The present invention provides a completely novel aromatic polyamide having excellent processability or heat stability in addition to the excellent heat resistance inherent to the aromatic polyamide. Furthermore, the aromatic polyamide resin composition of the present invention has excellent dimensional stability and mechanical strength, and has extremely good workability.
It is an extremely useful material used for electric / electronic parts, automobile parts, precision machine parts, medical equipment parts, base materials for spacecraft, etc., which require these physical properties. .

[Brief description of the 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 in Example 5 according to the present invention.

FIG. 5 is a diagram of an infrared absorption spectrum of a polyamide powder obtained according to Example 7 of the present invention.

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

FIG. 7 is a graph for comparing the thermal stability of each polyamide powder obtained in Example 9 and Comparative Example 2 according to the present invention.
This is the result of measuring the melt viscosity at a measurement temperature of 360 ° C. and a load of 100 kg while changing the resin residence time in the cylinder of the flow tester.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-64-2453 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 69/00-69/42 C08L 77 / 00-77/12

Claims (10)

(57) [Claims] 1. A compound represented by the following formula (1): (Wherein X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound represented by the formula (2)) R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, a phenyl group, a represents 0, 1 or 2, and b represents 0.
Or, represents an integer of 1 to 4. N represents an integer of 1 to 1000. The aromatic polyamide represented by). 2. A compound represented by the following formula (2): 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindane and / or 5- (3-aminophenoxy) -3- [ 4- (3-
[Aminophenoxy) phenyl] -1,1,3-trimethylindan 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 at a polycondensation. Characterized by the fact that
A method for producing the aromatic polyamide according to claim 1. 3. A compound of the formula (2) 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindane and / or 5- (3-aminophenoxy) -3- [ 4- (3-
Aminophenoxy) phenyl] -1,1,3-trimethylindane 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. by polycondensation. The method for producing an aromatic polyamide according to claim 1, characterized in that: 4. A compound of the formula (2) 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindane and / or 5- (3-aminophenoxy) -3- [ 4- (3-
[Aminophenoxy) phenyl] -1,1,3-trimethylindan and polycondensation of an aromatic dicarboxylic acid dialkylate and / or an aromatic dicarboxylic acid diallylate at a reaction temperature of 100 to 300 ° C. in an organic solvent. The method for producing an aromatic polyamide according to claim 1, wherein the aromatic polyamide is obtained by: 5. An aromatic compound having good thermal stability represented by the following formula (1), wherein the molecular terminal is sealed with a monovalent carboxylic acid, the carboxylic acid derivative or a monovalent amine. polyamide. Embedded image (Wherein X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound represented by the formula (7)) R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, a phenyl group, a represents 0, 1 or 2, and b represents 0.
Or, represents an integer of 1 to 4. N represents an integer of 1 to 1000. ) 6. An aromatic polyamide obtained by reacting a diamine with a dicarboxylic acid or a dicarboxylic acid derivative, wherein the aromatic polyamide is represented by the following formula (1). (Wherein, X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound represented by the formula: R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, a phenyl group, a represents 0, 1 or 2, and b represents 0.
Or, represents an integer of 1 to 4. N represents an integer of 1 to 1000. ) As a basic skeleton, the polycondensation reaction is carried out in the presence of a monovalent carboxylic acid or a carboxylic acid derivative, and the amount of the aromatic dicarboxylic acid or the aromatic dicarboxylic acid derivative is reduced to the aromatic diamine. The amount of the monovalent carboxylic acid or carboxylic acid derivative reacts at a ratio of 0.001 to 1.0 mol with respect to 1 mol of the aromatic diamine per mol. 6. The method for producing an aromatic polyamide having good thermal stability according to claim 5, wherein 7. An aromatic polyamide obtained by reacting a diamine with a dicarboxylic acid or a dicarboxylic acid derivative, wherein the aromatic polyamide is represented by the following formula (1). (Wherein, X is a condensed polycyclic aromatic group having 20 or less carbon atoms or a compound represented by the formula: R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, a phenyl group, a represents 0, 1 or 2, and b represents 0.
Or, represents an integer of 1 to 4. N represents an integer of 1 to 1000. ) As a basic skeleton, and the polycondensation reaction is carried out in the presence of a monovalent amine;
The amount of the aromatic diamine is 0.7 to 1.0 mol per 1 mol of the aromatic dicarboxylic acid or the aromatic dicarboxylic acid derivative, and the amount of the monovalent amine is the aromatic dicarboxylic acid or the aromatic dicarboxylic acid. 0.0 per mole of derivative
6. The method for producing an aromatic polyamide having good thermal stability according to claim 5, wherein the aromatic polyamide is obtained by reacting at a ratio of 01 to 1.0 mol. 8. The aromatic polyamide of claim 1 and / or 5 parts by weight and a fibrous reinforcing material of 5 to 100 parts by weight.
An aromatic polyamide resin composition comprising parts by weight. 9. The aromatic polyamide resin composition according to claim 8, wherein the fibrous reinforcing material is selected from the group consisting of glass fiber, carbon fiber, potassium titanate fiber and aromatic polyamide fiber. 10. An aromatic polyamide fiber represented by the following formula:
The aromatic polyamide resin composition according to claim 9, which is selected from the group consisting of aromatic polyamides having the structure of 2). Embedded image