JPH05170898A - Novel polyamide and production thereof - Google Patents

Abstract

PURPOSE:To obtain an amorphous polyamide which exhibits a high glass transition temperature and is excellent in the resistance to thermal decomposition and moldability by polymerizing a diamine compound and a specific norbornaned-icarboxylic acid or a derivative thereof. CONSTITUTION:A diamine compound of formula I wherein R is an aliphatic, alicyclic or aromatic divalent 2-16C organic group (e.g. ethylenediamine) and norbornanedicarboxylic acid or a derivative thereof represented by formula II(wherein M is hydroxyl, halogen or 1-4C alkoxy) (e.g. diethyl norbornanedicarboxylate) are subjected to polycondensation reaction which may be performed by heating in a molten state, or at a temperature of room temperature to 100 deg.C, or in an organic solvent with a high boiling point. Thus, a polyamide comprising repeating units of formula III is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel melt-moldable polyamide having heat resistance and a method for producing the same. More specifically, it relates to a novel polyamide with little coloration and a method for producing the polyamide by mixing norbornanedicarboxylic acid or a derivative thereof with a diamine compound and reacting the mixture under normal pressure.

[0002]

BACKGROUND OF THE INVENTION Polyamides have heretofore been obtained by reacting an aromatic diamine or aromatic diisocyanate with an aromatic dicarboxylic acid dichloride, an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid dichloride or an aliphatic dicarboxylic acid or a derivative thereof. Has been. These various polyamides have various excellent physical properties and good heat resistance. Furthermore, it is expected that a polyamide that takes advantage of such characteristics will be developed and widely used in the field where heat resistance is particularly required.

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. .. For example, the following formula (4)

[Chemical 4] A wholly aromatic polyamide having a basic skeleton represented by (DuPont; trade name Kevlar) has excellent characteristics such as flame resistance, heat resistance, high strength and high elastic modulus, but is a clear glass. It has no transition temperature and a thermal decomposition temperature of 43.
Since it is about 0 ° C., the processing temperature and the thermal decomposition temperature are close to each other, it is difficult to process when used as a molding material, and it is only used in the field of fibers or pulp by the wet spinning method. In order to improve these drawbacks, an attempt is made to improve moldability by using an aliphatic diamine or an aliphatic dicarboxylic acid and introducing it into the molecular chain. For example, a polyamide obtained by the reaction of an aliphatic diamine and an aromatic dicarboxylic acid, that is, the following formula (5)

[Chemical 5] Polyamides of which half of the repeating structure consisting of a basic skeleton as represented by U. S. P. 2,715,
620 and U.S.P. S. P. No. 2,742,496. However, these polyamides have been unsatisfactory for many applications in terms of dimensional stability at high temperatures.

The polyamide obtained by the reaction of an alicyclic diamine and an aliphatic dicarboxylic acid is, for example, the following formula (6)

[Chemical 6] Polyamide (trade name: RENY, manufactured by Mitsubishi Gas Chemical Co., Inc.) containing a repeating alicyclic structure consisting of a basic skeleton has a glass transition temperature of 93 ° C. and a melting point of 243 ° C. and has an oxygen gas barrier property. Has been reported to be excellent. In this way, by skillfully combining the starting material diamine and dibasic acid, the glass transition temperature,
Since a large difference occurs in the melting point, the thermal decomposition temperature and the processability of the polyamide resin, various new polyamides each having its own performance have been developed.

[0005]

The object of the present invention is to use a novel alicyclic dicarboxylic acid or a derivative thereof as a dibasic acid, in addition to the excellent heat resistance and molding processability originally possessed by an aromatic polyamide. It is to provide a completely novel polyamide which is amorphous and colorless and transparent and can be used for various purposes.

[0006]

Means for Solving the Problems The inventors of the present invention have made extensive studies to achieve the above-mentioned objects, and as a result, have found a novel polyamide. That is, the present invention has the general formula (1)

[Chemical 7] (Wherein R represents a divalent organic group selected from the group consisting of an aliphatic group having 2 to 16 carbon atoms, an alicyclic group and an aromatic group) and a polyamide having the repeating unit Is represented by the general formula (2)

[Chemical 8] (In the formula, R represents a divalent organic group selected from the group consisting of an aliphatic group having 2 to 16 carbon atoms, an alicyclic group and an aromatic group) and a general formula (3).

[Chemical 9] (In the formula, M is a hydroxyl group, a halogen atom, or 1 to 4 carbon atoms.
Of the norbornanedicarboxylic acid or a derivative thereof represented by the formula (1).

The norbornanedicarboxylic acid represented by the general formula (3) or its derivative used in the production method of the present invention is specifically 2,5-norbornanedicarbonitrile or 2,6-norbornanedicarbonitrile. And easily obtained by hydrolyzing these mixtures with an acid or an alkali under normal conditions, and heating the obtained norbornanedicarboxylic acid in alcohol in the presence of an acid catalyst. Thus, an esterified product can be easily obtained. These can also be used as a mixture.

As the norbornanedicarboxylic acid derivative, an acid halide can be used in addition to the esterified product. As the halogen constituting the halide, any of fluorine, chlorine, bromine and iodine can be used. Particularly preferred is chlorine.

Specific examples of the diamine used in the production method of the present invention are ethylenediamine, 1,3-propylenediamine, 1,4-butanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and pepta. Aliphatic diamines such as methylenediamine, octamethylenediamine, nonamethylenediamine, dodecamethylenediamine, p-phenylenediamine, m-
Phenylenediamine, p-xylylenediamine, m-xylylenediamine, m-aminobenzylamine, α-
(3-Aminophenyl) methylamine, α- (3-aminophenyl) ethylamine, α- (3-aminophenyl) propylamine, 4,4-diaminodiphenylpropane, 4,4-diaminodiphenylmethane, 3,3 Aromatic diamines such as diaminodiphenyl sulfone, 3,4-diaminodiphenyl ether, and 1,4-diaminocyclohexane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bisaminomethylcyclohexane, 1 , 4-bisaminomethylcyclohexane, α- (3-aminocyclohexyl) methylamine, α- (3-aminocyclohexyl) ethylamine, α- (3-aminocyclohexyl) propylamine, α- (3-aminocyclohexyl) butylamine,
Examples thereof include alicyclic diamines such as norbornanediaminomethyl and tricyclodecanediaminomethyl. Further, these diamines may be used alone or in combination of two or more. Norbornane dicarboxylic acid or its derivative and diamine may be used in an approximately equivalent ratio.

In the present invention, a polyamide is obtained by reacting the above diamine with norbornane dicarboxylic acid or its derivative, but the method of reacting is not particularly limited, and a method known per se can be adopted. For example, a solution polycondensation method in which a polycondensation reaction is carried out in a liquid phase homogeneous system by heating at a temperature above the melting point and melting, and when the resulting polymer has a remarkably high melting point or a double bond or a side chain that is easily decomposed, room temperature To low-temperature polycondensation method in which polycondensation reaction is carried out at a temperature of 100 to 100 ° C. or below, and solid-phase condensation method in which polycondensation reaction is carried out by heating in a solid phase in a crystalline state at a temperature around 20 to 30 ° C. below the melting points of monomers and polymers. There is a method such as a solution polycondensation method in which a polycondensation reaction is carried out in a high boiling point organic solvent under a nitrogen stream at a temperature of 200 to 300 ° C., and then the polymer is precipitated in methanol or acetone.

The high boiling organic solvent used in this method is, for example, N, N-dimethylformamide,
N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N
-Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazoline, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, hexamethylphosphoramide, isoquinoline, 2,4-lutidine, pyridine, γ
-Picoline, β-picoline, α-picoline, 2,6-lutidine, quinoline, triethylamine, tributylamine, tripentylamine, N, N-dimethylaniline,
N, N-diethylaniline, dichloromethane, chloroform, carbon tetrachloride, methyl ethyl ketone, acetone, cyclohexanone, acetophenone, tetrahydrofuran, benzene, toluene, xylene, nitrobenzene,
Phenol, cresylic acid, o-cresol, m-cresol, p-chlorophenol, o-chlorophenol and the like can be mentioned.

The amount of the solvent used is selected in consideration of the solubility and viscosity of the produced polymer, but is usually 2 with respect to the raw material amine.
A weight ratio of 0 times or more is preferable. If it is less than 20 times, the precipitation of the amine hydrochloride is large and stirring becomes difficult. The upper limit is not particularly limited, but if used in a large amount, the volumetric efficiency of the reactor decreases. Therefore, the upper limit is about 30 times, and it is preferable to use it in the range of 20 to 30 times the weight ratio of the starting amine.

When a norbornanedicarboxylic acid halide is used as the starting material monomer in the method of the present invention, a dehalogenating agent is usually used in combination. Examples of the dehalogenating agent used include triethylamine, tributylamine, tripentylamine, N, N-dimethylaniline, N, N-diethylaniline, pyridine, α-picoline, β-picoline, γ-picoline, 2,4. -Lutidine, 2,6-lutidine, quinoline, isoquinoline, sodium hydroxide, potassium hydroxide, sodium carbonate, lithium carbonate, potassium carbonate, sodium hydrogen carbonate, calcium oxide, lithium oxide, ethylene oxide, propylene oxide and the like. The dehalogenating agent may be used in a stoichiometric amount. For example, when triethylammine is used as the dehalogenating agent, the amount may be 2 times the mole of the dibasic acid halide which is the reaction raw material.

When norbornane dicarboxylic acid is used as the reaction raw material monomer in the method of the present invention, a condensing agent is usually used. As the condensing agent used, sulfuric anhydride, thionyl chloride, sulfite ester, picryl chloride, phosphorus pentoxide, phosphite-pyridine-based condensing agent, triphenylphosphine-hexachloroethane-based condensing agent, propylphosphoric anhydride- Examples thereof include N-methyl-2-pyrrolidone-based condensing agents. The amount of condensing agent used is
Any stoichiometry will do. For example, when a propylphosphoric anhydride-N-methyl-2-pyrrolidone solution is used as the condensing agent, it may be used in a 2-fold molar amount with respect to the reaction raw material norbornanedicarboxylic acid.

The reaction temperature and reaction time in the present invention are as follows: the type of reaction raw material monomer, the polymerization method, the type of solvent,
It depends on the type of dehalogenating agent and the type of condensing agent, and is usually at a temperature in the range of −15 to 340 ° C. for about 1 to 20 hours. The reaction temperature and reaction time are, specifically,
It is as follows depending on the kind of the reaction raw material monomer.

When a norbornane dicarboxylic acid halide is used as a reaction raw material, the reaction is preferably carried out in a temperature range of −15 to 80 ° C. under a nitrogen stream. In this case, since heat is generated when charging the raw materials, the first half of the reaction with heat generation is performed at a relatively low temperature, and the temperature is raised from the latter half of the reaction,
It is preferable to complete the reaction sufficiently. Therefore,
In order to carry out the reaction properly at the above-mentioned temperature, it is preferable that the temperature of the reaction system is previously cooled to about 30 to 0 ° C. in some cases, and 2 to 10 at a temperature range of −10 to 10 ° C. About an hour, then 20 to 60 ° C., preferably 2
The reaction is carried out at 0 to 30 ° C for about 3 to 15 hours.

When norbornane dicarboxylic acid ester is used as a reaction raw material, the reaction is carried out while mixing or after mixing the reaction raw materials under a nitrogen stream, and then 50 to 300.
It is carried out in the temperature range of ° C for about 5 to 20 hours.

Further, when norbornane dicarboxylic acid is used as a reaction raw material, diamine is charged under a nitrogen stream while maintaining fluidity at a temperature below the melting point. The diamine is charged in about 2 to 10 hours, preferably about 3 to 5 hours. At this time, the dropping temperature is preferably within a range not exceeding 50 ° C. from the melting point of norbornanedicarboxylic acid.
It is not preferable to drop the solution by drastically exceeding the melting point temperature from the viewpoint of the thermal stability of norbornanedicarboxylic acid. After the addition of the diamine, the reaction is carried out in the temperature range of 240 to 350 ° C. until the reaction product water is no longer distilled, but it is generally 2 to 10.
It is carried out in about an hour. Alternatively, norbornane dicarboxylic acid is heated to a temperature equal to or higher than the melting point to be melted, and then diamine is charged under a nitrogen stream, and the reaction is carried out at a temperature range of 240 to 350 ° C. until distilling of reaction product water is completed. Good.

After the reaction as described above, the reaction liquid is usually a viscous polymer solution, so that when the polymerization reaction is carried out in an organic solvent, it may be precipitated after the reaction if necessary. After the salt of the dehalogenating agent is filtered off, or if the reaction solvent dissolves the salt of the dehalogenating agent, the polymer solution is immediately discharged into the precipitation solvent to precipitate the crystals of polyamide, and filtered, The polyamide can be isolated by washing and drying. In addition, the viscous polymer solution after the reaction may be discharged and solidified, and then pulverized to obtain a polyamide powder.

Examples of the solvent used for precipitating the above-mentioned polyamide crystals include water, methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, and tert.
Alcohols such as butanol or ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone are commonly used.

The polyamide of the present invention has an inherent viscosity of 0.5 to 0.8 dl / g as measured under the conditions described below, has excellent heat resistance and thermoplasticity, and is amorphous and has a glass transition temperature of 200. Since it is as high as ~ 280 ° C and has excellent stability against thermal decomposition, it is a completely novel polyamide that is melt-spinnable, melt-moldable for plastics, films, etc. and can be expected to be used for multipurpose applications. ..

When the polyamide of the present invention is subjected to melt molding, other thermoplastic resins such as polyethylene, polypropylene, polycarbonate, polyarylate, polyimide, polysulfone, polyether sulfone, polyether are used as long as the object of the present invention is not impaired. Ketone, polyetheretherketone, polyphenylene sulfide,
Polyamideimide, polyetherimide, modified polyphenylene oxide and the like may be added in an appropriate amount depending on the purpose.

Further, the following fillers used in ordinary resin compositions may be used to such an extent that the object of the present invention is not impaired. That is, graphite, carbon random, silica powder, molybdenum disulfide, wear resistance improving materials such as fluororesin, glass fiber, carbon fiber, boron fiber, silicon carbide fiber, carbon whiskers, asbestos, metal fibers, ceramic fibers and the like reinforcement Materials, antimony trioxide, magnesium carbonate, calcium carbonate, etc. flame retardant improvers, clay, mica, etc. electrical property improvers, asbestos, silica, graphite, etc. acid resistance improvers, iron powder, zinc powder, aluminum powder , Thermal conductivity improver such as copper powder, other glass beads, glass balls, talc,
Examples include diatomaceous earth, alumina, silasbaln, hydrated alumina, metal oxides, and colorants.

[0024]

EXAMPLES The present invention will now be described in more detail with reference to examples. The physical properties of the examples were measured by the following methods. Logarithmic viscosity: 0.50 g of polyamide powder was dissolved in 20 ml of concentrated sulfuric acid and then measured at 35 ° C. with an Ubbelohde viscosity tube. Glass transition temperature (Tg); measured by DSC (Shimadzu DT-40 series, DSC-41M). 5% weight loss temperature; in air, DTA-TG (Shimadzu D
T-40 series, DSC-40M).

Example 1 18.4 g (0.1 mol) of norbornanedicarboxylic acid was charged into a container equipped with a stirrer and a nitrogen introducing tube under a nitrogen atmosphere, and then heated to 245 ° C. to dissolve it. Next, 14.2 g (0.1 mol) of m-aminophenylethylamine was charged over 2 hours. After stirring at the same temperature for 2 hours, the temperature was raised to 265 ° C. and the reaction was performed at the same temperature for 3 hours (distilled water 3.24 g, 90% theoretical amount of distillation). After the reaction, the viscous polymer was discharged onto a porcelain flat plate, dried, and then pulverized. Yield 24.1 g, yield 85.0%. The logarithmic viscosity of this polyamide powder is 0.72 dl / g,
The glass transition temperature was 230 ° C, and the 5% weight loss temperature in air was 400 ° C. The elemental analysis results of the polyamide obtained here are as follows. Elemental analysis _{(%) (C 17 H 20} N 2 calculated as O ₂₎ C H N Theoretical values 71.81 7.09 9.85 Analytical values 71.75 7.01 9.83

A film was prepared using the obtained polyamide powder with a hot press machine. Prepare 3 pieces of Upilex film (thickness 20 mm, length x width 15 x 15 cm),
In order to adjust the thickness of the polyamide film to be prepared, one of them was cut out at a center of 6 × 6 cm. A piece of Upilex film is placed on the lower hot plate (temperature of 250 ° C.) of the hot press machine, and a piece of cut Upilex film is placed on it, and then the sample polyamide powder 0.8.
g was placed in the center of the cutout. Further, one UPILEX film was placed on top of it, and an upper hot plate (260 ° C.) was placed on it, and pressed under pressure (180 kg / cm ² ) for 2 minutes. After cooling to 30 ° C., the film was peeled off from the Upilex film to obtain a polyamide film. The obtained film was almost colorless and transparent.

Example 2 18.4 g (0.1 mol) of norbornanedicarboxylic acid was charged into a container equipped with a stirrer and a nitrogen introducing tube under a nitrogen atmosphere, and then heated to 245 ° C. to dissolve it. Next, 15.4 g (0.1 mol) of norbornanediaminomethyl
Was charged in 2 hours. After stirring at the same temperature for 2 hours, the temperature was raised to 265 ° C. and the reaction was carried out at the same temperature for 3 hours (distilled water 3.28 g, 91.1% theoretical amount of distillation). After the reaction, the viscous polymer was discharged onto a porcelain flat plate, dried, and then pulverized. Yield 26.9 g, yield 89.1%. The logarithmic viscosity of this polyamide powder is 0.58 dl / g,
The glass transition temperature was 220 ° C, and the 5% weight loss temperature in air was 420 ° C. The elemental analysis results of the polyamide obtained here are as follows. Elemental analysis value (%) (calculated as C ₁₈ H ₂₆ N ₂ O ₂ ) C H N theoretical value 71.49 8.67 9.26 Analytical value 71.45 8.59 9.22 As in Example 1, A film was prepared using the obtained polyamide powder. The obtained film has almost no color,
It was transparent.

Example 3 18.4 g (0.1 mol) of norbornanedicarboxylic acid was charged in a vessel equipped with a stirrer and a nitrogen introducing tube under a nitrogen atmosphere, and then heated to 245 ° C. to dissolve it. Next, 17.0 g (0.1 mol) of isophoronediamine was charged over 2 hours. After stirring at the same temperature for 2 hours, 265
The temperature was raised to ℃ and reacted at the same temperature for 3 hours (distilled water 3.3.
8 g, 93.9% theoretical distillate). After the reaction, the viscous polymer was discharged onto a porcelain flat plate, dried, and then pulverized. Yield 26.9 g, 84.6%. The logarithmic viscosity of this polyamide powder is 0.60 dl / g,
The glass transition temperature was 269 ° C, and the 5% weight loss temperature in air was 415 ° C. The elemental analysis results of the polyamide obtained here are as follows. Elemental analysis value (%) (calculated as C ₁₉ H ₃₀ N ₂ O ₂ ) C H N theoretical value 71.66 9.50 8.80 Analytical value 71.65 9.49 8.78 As in Example 1, A film was prepared using the obtained polyamide powder. The obtained film has almost no color,
It was transparent.

Example 4 180 g (10 times amount) of methanol and 18.4 g (0.1 mol) of norbornanedicarboxylic acid were charged into a container equipped with a stirrer and a nitrogen introducing tube in a nitrogen atmosphere,
After charging 11.6 g (0.1 mol) of 1.6-hexanediamine to form a salt of norbornanedicarboxylic acid and 1.6-hexanediamine, the temperature was raised to 245 ° C. while distilling off methanol. The mixture was stirred at the same temperature for 3 hours. Furthermore, the temperature was raised to 265 ° C. and the reaction was carried out at the same temperature for 2 hours (distilled water 2.88 g, 80.0% theoretical amount of distillation). After the reaction, the viscous polymer was discharged onto a porcelain flat plate, dried, and then pulverized. Yield 15.9 g Yield 60.7%. The logarithmic viscosity of this polyamide powder is 0.68 dl / g,
The glass transition temperature was 118 ° C, and the 5% weight loss temperature in air was 360 ° C. The elemental analysis results of the polyamide obtained here are as follows. Elemental analysis value (%) (calculated as C ₁₅ H ₂₂ N ₂ O ₂ ) C H N theoretical value 68.67 8.45 10.68 Analytical value 68.55 8.38 10.56 As in Example 1, A film was prepared using the obtained polyamide powder. The obtained film has almost no color,
It was transparent.

Example 5 21.2 g of norbornane dimethyl ester (0.
(1 mol), the temperature was raised to 100 ° C., and 13.6 g (0.1 mol) of m-xylylenediamine was charged at the same temperature over 2 hours. Raise the temperature to 160 ° C and keep at the same temperature for 2
After stirring for an hour, the temperature was raised to 190 ° C., and the mixture was stirred at the same temperature for 3 hours (distilled methanol 5.0 g, 78% theoretically distilled amount). After the reaction, the viscous polymer was discharged onto a porcelain flat plate, dried, and then pulverized. Yield 24.1 g Yield 85.0%. The logarithmic viscosity of this polyamide powder is 0.69 dl / g,
The glass transition temperature was 102 ° C, and the 5% weight loss temperature in air was 400 ° C. The elemental analysis results of the polyamide obtained here are as follows. Elemental analysis value (%) (calculated as C ₁₉ H ₂₄ N ₂ O ₂ ) C H N theoretical value 73.05 7.74 8.97 analytical value 73.01 7.69 8.93 As in Example 1, A film was prepared using the obtained polyamide powder. The obtained film has almost no color,
It was transparent.

Example 6 In a container equipped with a stirrer and a nitrogen introducing tube, 21.2 g (0.
(1 mol), the temperature was raised to 60 ° C, and at the same temperature, m
10.8 g (0.1 mol) of phenylenediamine were charged. The temperature was raised to 160 ° C. over 2 hours, the mixture was stirred at the same temperature for 2 hours, then heated to 190 ° C., and stirred at the same temperature for 3 hours (distilled methanol 5.5 g, 85.8% theoretical distillation amount). After the reaction, the viscous polymer was discharged onto a porcelain flat plate, dried, and then pulverized. Yield 19.9 g Yield 70.1% The polyamide powder has an inherent viscosity of 0.72 dl / g,
The glass transition temperature was 295 ° C, and the 5% weight loss temperature in air was 459 ° C. The elemental analysis results of the polyamide obtained here are as follows. Elemental analysis value (%) (calculated as C ₁₇ H ₂₀ N ₂ O ₂ ) CH N theoretical value 71.81 7.09 9.85 analytical value 71.71 7.05 9.84 As in Example 1, A film was prepared using the obtained polyamide powder. The obtained film has almost no color,
It was transparent.

[0032]

INDUSTRIAL APPLICABILITY In addition to the excellent heat resistance inherent in aromatic polyamides, the present invention provides polyamides obtained by reacting alicyclic diamines, aliphatic diamines and / or aromatic diamines with norbornane dicarboxylic acid and its derivatives. , Amorphous, high glass transition temperature, and excellent stability against thermal decomposition, so melt spinning, plastic,
The present invention provides a completely novel polyamide that can be melt-molded into a film and can be used for various purposes.

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

Claims (2)

[Claims] 1. A compound represented by the general formula (1): (In the formula, R represents a divalent organic group selected from the group consisting of an aliphatic group having 2 to 16 carbon atoms, an alicyclic group, and an aromatic group), and a polyamide having a repeating unit. 2. A general formula (2): (Wherein R represents a divalent organic group selected from the group consisting of an aliphatic group having 2 to 16 carbon atoms, an alicyclic group and an aromatic group) and a diamine represented by the general formula (3): Chemical 3] (In the formula, M is a hydroxyl group, a halogen atom or a carbon number of 1 to
4. The method for producing a polyamide according to claim 1, wherein a norbornane dicarboxylic acid represented by the formula (4) or a derivative thereof is polymerized.