JP2010077420A - Polyamide resin and polyamide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high heat-resistant polyamide resin mainly consisting of pentamethylenediamine, and a composition of the same. <P>SOLUTION: The polyamide resin is obtained by polycondensation of: an aliphatic diamine containing ≥25 wt.% of pentamethylenediamine; and dicarboxylic acid derivatives containing a total quantity of ≥65 wt.% of a terephthalic acid derivative and isophthalic acid derivative as essential ingredients. Relative viscosity at 25°C of the polyamide resin of 0.01 g/ml of 98% sulfuric acid solution is 1.5-4.0. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a high heat-resistant polyamide resin containing pentamethylenediamine as a constituent component and a composition thereof.

  Pentamethylenediamine is expected as a non-petroleum raw material, a synthetic raw material for pharmaceutical intermediates and the like, and a polymer raw material. As a high heat-resistant polyamide comprising aliphatic diamine and aromatic dicarboxylic acid as constituent components, Patent Document 1 discloses polyamide 6T / 6I composed of hexamethylenediamine (6), terephthalic acid (T), and isophthalic acid (I). It is disclosed. However, since it has a high melting point, there is a problem that it is inferior in molding processability.

  Patent Document 2 discloses polyamide 6T / 6I which is excellent in melt residence stability and exemplifies pentamethylenediamine as an aliphatic diamine component. However, the 5T / 5I of the present invention using pentamethylenediamine as the aliphatic diamine component exhibits a unique effect that the glass transition temperature becomes higher despite the melting point being lower than that of 6T / 6I. Is not known.

  On the other hand, Patent Document 3 discloses M5T / 6T composed of terephthalic acid (T), hexamethylenediamine (6), and 2-methylpentamethylenediamine (M5). This polyamide also has a problem that it is inferior in molding processability like 6T / 6I.

  Further, Patent Document 4 discloses a polyamide resin 5T / 6T having an aliphatic diamine and terephthalic acid derivative as main components, which are aliphatic pentamethylenediamine and hexamethylenediamine as main components. 5T / 6T uses pentamethylenediamine as an aliphatic diamine component, but has a high melting point and poor molding processability due to the high content of terephthalic acid derivative in the dicarboxylic acid derivative. .

JP 60-158220 A JP 63-161021 A Japanese National Patent Publication No. 8-500150 JP 2003-292613 A

  An object of the present invention is to provide a polyamide resin having pentamethylenediamine as a constituent component, excellent in molding processability and melt residence stability, and having a high glass transition temperature.

  The present inventors use pentamethylenediamine as an aliphatic diamine component in order to impart molding processability, heat resistance, and melt retention stability in polyamides mainly composed of terephthalic acid derivatives and isophthalic acid derivatives. Has been found to be effective, and the present invention has been achieved.

That is, the present invention
(I) A diamine containing 25% by weight or more of pentamethylenediamine with respect to the total weight of the diamine, terephthalic acid or a derivative thereof, and isophthalic acid or a derivative thereof as essential components, and the total amount of these is the total weight of a dicarboxylic acid or a derivative thereof 98% sulfuric acid solution obtained by polycondensation of 65% by weight or more of a dicarboxylic acid or derivative thereof, having a chemical structure consisting of amide group repeating units derived from these compounds, and 0.01 g / ml A polyamide resin having a relative viscosity of 1.5 to 4.0 at 25 ° C.,
(Ii) a polyamide resin according to (i), which has a melting point of 315 ° C. or lower, or amorphous;
(Iii) The polyamide resin according to (i) or (ii), wherein the glass transition temperature is 120 ° C. or higher,
(Iv) Y / X is 0.7 or more and 1.5 or less, where Y is the sulfuric acid solution viscosity when retained at melting point + 20 ° C. for 30 minutes and X is the relative viscosity of sulfuric acid before retention (X) (Iii) The polyamide resin according to any one of (v) the weight of the repeating unit derived from terephthalic acid or a derivative thereof relative to the total weight of the repeating unit derived from a dicarboxylic acid or a derivative thereof is from 20% by weight to 80% by weight The polyamide resin according to any one of (i) to (iv),
(Vi) A polyamide resin composition obtained by blending 0.1 to 200 parts by weight of an inorganic filler with respect to 100 parts by weight of the polyamide resin according to any one of (i) to (v),
(Vii) The polyamide resin composition according to (vi), which is formed by blending an inorganic filler into which an organic functional group has been introduced,
(Viii) a polyamide resin composition comprising 5 to 100 parts by weight of an impact resistance improver based on 100 parts by weight of the polyamide resin according to any one of (i) to (v),
(Ix) 0.1 to 200 parts by weight of an inorganic filler and 5 to 100 parts by weight of an impact resistance improver are blended with 100 parts by weight of the polyamide resin according to any one of (i) to (v). It is a polyamide resin composition.

  According to the present invention, a polyamide resin having pentamethylenediamine as a constituent component and excellent in heat resistance, molding processability, and melt residence stability can be provided.

  The polyamide resin of the present invention needs to contain 25% by weight or more of pentamethylenediamine as a diamine component with respect to the total weight of the diamine. More preferably, it is 35% by weight or more, more preferably 45% by weight, and most preferably 50% by weight or more. By setting the pentamethylenediamine to 25% by weight or more, a polyamide resin excellent in moldability, heat resistance (high glass transition temperature), and melt residence stability can be obtained.

  Examples of copolymer components other than pentamethylenediamine that can be contained as less than 75% by weight as diamine components include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,7- Diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diamino Tetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 2-methyl Aliphatic diamines such as -1,5-diaminopentane, Hexanediamine, bis - (4-aminocyclohexyl) cycloaliphatic diamines, such as methane, and aromatic diamines such as xylylenediamine.

  The polyamide resin of the present invention contains terephthalic acid or a derivative thereof and isophthalic acid or a derivative thereof as essential components as a dicarboxylic acid or a derivative thereof, and the total amount thereof is 65% by weight based on the total weight of the dicarboxylic acid or the derivative thereof. % Or more. More preferably, it is 70 weight% or more, More preferably, it is 80 weight% or more. By setting these aromatic dicarboxylic acids or their derivatives to 65% by weight or more, a polyamide resin having a high glass transition temperature can be obtained.

  The higher the content of terephthalic acid or its derivative in the dicarboxylic acid or its derivative, the higher the glass transition temperature of the resulting polyamide resin, so 20% by weight of terephthalic acid or its derivative component relative to the total weight of the dicarboxylic acid or its derivative. The above is preferable.

  However, if the content of terephthalic acid or its derivative is too large, the melting point of the polyamide resin tends to be too high and the molding processability tends to be inferior, so terephthalic acid or its derivative component relative to the total weight of the dicarboxylic acid or its derivative Is preferably 80% by weight or less. More preferably, it is 75 weight% or less.

  The polyamide resin of the present invention becomes crystalline or amorphous depending on the constituent components and their blending ratio. When terephthalic acid or its derivative is 55% by weight or more with respect to the total weight of dicarboxylic acid or its derivative, the resulting polyamide resin tends to be crystalline, and when it is less than 55% by weight, it tends to be amorphous. There is.

  Copolymerization components other than terephthalic acid or its derivative and isophthalic acid or its derivative, which can be contained as dicarboxylic acid or its derivative in an amount of less than 35% by weight, include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , Pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, tetradecanedioic acid, pentadecanedioic acid, aliphatic dicarboxylic acid such as octadecanedioic acid, fat such as cyclohexanedicarboxylic acid Examples thereof include aromatic dicarboxylic acids such as cyclic dicarboxylic acid, phthalic acid, and naphthalenedicarboxylic acid.

  Further, the polyamide resin of the present invention comprises amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, and lactams such as ε-caprolactam and ω-laurolactam, all constituting components. On the other hand, 20% by weight or less can be blended and copolymerized. Preferably it is 15 weight% or less, More preferably, it is 10 weight% or less.

As described above, when the content of terephthalic acid or its derivative exceeds 80% by weight with respect to the total weight of the dicarboxylic acid or its derivative, the resulting polyamide resin tends to have a melting point higher than 320 ° C. Actual molding processing must be performed at a temperature close to the decomposition temperature of the polyamide resin. In the present invention, since a polyamide resin excellent in moldability is obtained, the melting point is preferably 315 ° C. or lower. More preferably, it is 305 degrees C or less. A polyamide resin having a melting point higher than 315 ° C. can lower the melting point by copolymerizing an amino acid or lactam. However, when the amount of copolymerization is large, the glass transition temperature of the resulting polyamide resin becomes low, so that the amount of copolymerization of amino acids and lactams relative to all components is preferably 20% by weight or less. In this case, the melting point can be appropriately lowered while maintaining a high glass transition temperature. The melting point here refers to a temperature increase of 20 ° C./min after the polyamide resin is cooled from the molten state to 30 ° C. at a temperature decrease rate of 20 ° C./min using a differential scanning calorimeter. The temperature of the endothermic peak that appears when the temperature is increased at a rate (melting point: Tm ₂ ) is shown.

  Although there is no restriction | limiting in the manufacturing method of the pentamethylenediamine which comprises this invention, For example, it converts from lysine using the method of synthesize | combining from lysine using vinyl ketones, such as 2-cyclohexen-1-one, and a lysine decarboxylase. Methods have already been proposed. In the former method, the reaction temperature is as high as about 150 ° C., whereas the latter method is less than 100 ° C., and it is considered that side reactions can be further reduced by using the latter method. It is preferable to use pentamethylenediamine obtained by the method.

  The lysine decarboxylase used in the latter method is an enzyme that converts lysine to pentamethylenediamine, and is known to exist in many organisms as well as Escherichia microorganisms including Escherichia coli K12 strain. .

  As the lysine decarboxylase preferably used in the present invention, those existing in these organisms can be used, and those derived from recombinant cells in which the intracellular activity of lysine decarboxylase is increased can also be used. .

  As the recombinant cell, those derived from microorganisms, animals, plants, or insects can be preferably used. For example, when animals are used, mice, rats and cultured cells thereof are used. When plants are used, for example, Arabidopsis thaliana, tobacco and cultured cells thereof are used. In addition, when insects are used, for example, silkworms and cultured cells thereof are used. In addition, when microorganisms are used, for example, E. coli is used.

  Further, a plurality of lysine decarboxylases may be used in combination.

Examples of microorganisms having such a lysine decarboxylase include Bacillus halodurans, Bacillus subtilis, Escherichia coli, Selenomonas luminobirium, and Selenomonas luminobium. , Vibrio parahaemolyticus, Streptomyces coelikara, Streptomyces pilosus, Ekenella colodell, Ekenella Eumactamino acidum (Eubacterium acidaminophilum), Salmonella typhimurium (Hafnia albei), Neisseria meningocide (Neisseria terumidosidum) abyssi) or Corynebacterium glutamicus (Corynebacterium)
glutamicum) and the like.

  The method for obtaining lysine decarboxylase is not particularly limited. For example, a microorganism having lysine decarboxylase or a recombinant cell having increased intracellular lysine decarboxylase activity is cultured in an appropriate medium. The proliferated cells can be collected and used as resting cells, and the cells can be disrupted to prepare a cell-free extract and used as necessary. It is also possible to use it.

  In order to extract lysine decarboxylase, there is no particular limitation on the method of culturing microorganisms or recombinant cells having lysine decarboxylase. For example, when culturing microorganisms, the medium used is a carbon source, nitrogen source, A medium containing inorganic ions and other organic components as required is used. For example, E.I. In the case of E. coli, LB medium is often used. Carbon sources include glucose, lactose, galactose, fructose, arabinose, maltose, xylose, trehalose, sugars such as ribose and starch hydrolysates, alcohols such as glycerol, mannitol and sorbitol, gluconic acid, fumaric acid, citric acid And organic acids such as succinic acid can be used. As the nitrogen source, inorganic ammonium salts such as ammonium sulfate, ammonium chloride and ammonium phosphate, organic nitrogen such as soybean hydrolysate, ammonia gas, aqueous ammonia and the like can be used. As organic micronutrients, it is desirable to contain appropriate amounts of various substances, required substances such as vitamins such as vitamin B1, nucleic acids such as RNA, yeast extract and the like. In addition to these, a small amount of calcium phosphate, calcium sulfate, iron ion, manganese ion or the like is added as necessary.

  There are no particular restrictions on the culture conditions. In the case of E. coli, it is preferable to carry out for about 16 to 72 hours under aerobic conditions, the culture temperature is 30 ° C. to 45 ° C., particularly preferably 37 ° C., the culture pH is 5 to 8, particularly preferably pH 7. It is good to control. In addition, an inorganic or organic acidic or alkaline substance, ammonia gas or the like can be used for pH adjustment.

  Proliferated microorganisms and recombinant cells can be recovered from the culture solution by centrifugation or the like. In order to prepare a cell-free extract from the collected microorganisms or recombinant cells, a normal method is used. That is, a cell-free extract can be obtained by crushing microorganisms and recombinant cells by a method such as ultrasonic treatment, dynomill, French press, etc., and removing cell residue by centrifugation.

  To purify lysine decarboxylase from cell-free extracts, ammonium sulfate fractionation, ion exchange chromatography, hydrophobic chromatography, affinity chromatography, gel filtration chromatography, isoelectric precipitation, heat treatment, pH treatment, etc. The methods usually used are combined with each other as appropriate. The purification does not necessarily have to be complete purification, and it is sufficient that impurities other than lysine decarboxylase, such as an enzyme involved in the degradation of lysine and a product degrading enzyme of pentamethylenediamine, can be removed.

  The conversion from lysine to pentamethylenediamine by lysine decarboxylase can be performed by bringing the lysine decarboxylase obtained as described above into contact with lysine.

  There is no particular limitation on the concentration of lysine in the reaction solution.

  The amount of lysine decarboxylase may be sufficient to catalyze the reaction of converting lysine to pentamethylenediamine.

  The reaction temperature is usually 28 to 55 ° C, preferably around 40 ° C.

  The reaction pH is usually 5-8, preferably about 6. As pentamethylenediamine is produced, the reaction solution changes to alkaline. Therefore, it is preferable to add an inorganic or organic acidic substance in order to maintain the reaction pH. Preferably hydrochloric acid can be used.

  Any method of standing or stirring may be employed for the reaction.

  The lysine decarboxylase may be immobilized.

  The reaction time varies depending on conditions such as enzyme activity and substrate concentration to be used, but is usually 1 to 72 hours. The reaction may be continuously performed while supplying lysine.

  The method of collecting the pentamethylenediamine thus produced from the reaction solution after completion of the reaction includes a method using an ion exchange resin, a method using a precipitating agent, a method of solvent extraction, a method of simple distillation, and other normal collection and separation. The method can be adopted.

  Specific examples of terephthalic acid or a derivative thereof which is the dicarboxylic acid or derivative component of the present invention include terephthalic acid, terephthalic acid chloride, dimethyl terephthalate, diethyl terephthalate and the like. Specific examples of isophthalic acid or derivatives thereof include isophthalic acid, isophthalic acid chloride, dimethyl isophthalate, and diethyl isophthalate.

  The polyamide resin of the present invention preferably has a melting point of 315 ° C. or lower or is amorphous so as to have excellent moldability. In order to make the melting point range or amorphous, the terephthalic acid or its derivative component is preferably 80% by weight or less based on the total amount of the dicarboxylic acid or its derivative. More preferably, it is 75 weight% or less.

  In the present invention, since a polyamide resin having excellent heat resistance is to be obtained, the glass transition temperature is preferably 120 ° C. or higher. More preferably, it is 130 degreeC or more. In order to set the glass transition temperature of the polyamide resin of the present invention to 120 ° C. or more, it can be achieved by setting the terephthalic acid derivative component to 20% by weight or more with respect to the total amount of the dicarboxylic acid derivative. Furthermore, the polyamide resin which has a glass transition temperature of 130 degreeC or more can be obtained by setting it as 50 weight% or more.

  As a method for producing the polyamide resin of the present invention, a known method can be applied. For example, a method disclosed in “Polyamide Resin Handbook” (Fukumoto Shushu) or the like can be used. A mixture of pentamethylenediamine, terephthalic acid, isophthalic acid (and other copolymerization components) is heated at a high temperature to cause a dehydration reaction, and a pentamethylenediamine (and other copolymerization components) Dissolving in water, dissolving terephthalic acid chloride and isophthalic acid chloride (and other copolymerization components) in an organic solvent that is not mixed with water, and polycondensing at the interface between these aqueous and organic phases (interfacial polymerization method) ) And the like. Here, the heat polycondensation is defined as a production process in which the maximum temperature of the polyamide resin during production is increased to 200 ° C. or higher. The interfacial polymerization method is complicated by using an organic solvent and neutralizing hydrochloric acid, which is a by-product during polycondensation. It is preferable to use it.

In the heat polycondensation of polyamide resin, it is necessary to go through a step of maintaining the polymerization system in a pressurized state and generating a prepolymer, which is usually required in melt polymerization, and is performed in the presence of water. It is necessary. The amount of water charged is preferably 10 to 70% by weight with respect to the total amount of raw material and water combined. When the water content is less than 10% by weight, it takes a long time to uniformly dissolve the nylon salt, and an excessive heat history tends to be applied. On the other hand, when the amount of water is more than 70% by weight, a great amount of heat energy is consumed for removing the water, and it takes time to produce the prepolymer. Furthermore, it is preferable that the pressure hold | maintained in a pressurized state shall be 10-40 kg / cm < ² >. In the case where it is kept below 10 kg / cm ^2, it is not preferable because pentamethylenediamine easily volatilizes out of the polymerization system. Moreover, when it hold | maintains higher than 40 kg / cm < ² >, it is necessary to make temperature inside a polymerization system high, and since pentamethylenediamine volatilizes out of a system easily as a result, it is unpreferable.

  As the heat polymerization method, for example, a salt of pentamethylenediamine and terephthalic acid, a salt of pentamethylenediamine and isophthalic acid (and salts of other copolymerization components) are prepared, and these are mixed and heated in the presence of water. Thus, a method of allowing the dehydration reaction to proceed is preferably used. It is also possible to change the copolymer composition ratio in polyamide by changing the mixing ratio of pentamethylene diamine and terephthalic acid salt, pentamethylene diamine and isophthalic acid salt (and other copolymer component salts). it can. Furthermore, the molecular weight of the polyamide resin of the present invention can also be increased by solid-state polymerization after heat polycondensation or by melt retention in an extruder. The solid phase polymerization is performed on the crystalline polyamide resin and proceeds by heating in a vacuum or in an inert gas in a temperature range of 100 ° C. to a melting point. Further, the melt residence in the extruder proceeds by melting and staying at a temperature equal to or higher than the melting point of the polyamide resin, or in the case of amorphous, to a temperature equal to or higher than the glass transition temperature. In particular, the reduced pressure from the vent portion is preferable because water during polycondensation can be efficiently removed and the effect of increasing the molecular weight is great.

  In the heat polycondensation of polyamide resin, since the polymerization reaction is performed at a high temperature, the polymerization proceeds with the progress of the polymerization because pentamethylenediamine volatilizes from the polymerization system and / or cyclizes by the deammonia reaction. In the system, there is a possibility that the total amino group amount with respect to the total carboxyl group amount is decreased. Therefore, it is preferable to synthesize a high molecular weight polyamide resin by adding an excessive amount of a specific amount of pentamethylenediamine in advance to control the amount of amino groups in the polymerization system at the stage of charging the raw materials. The raw material composition ratio can be adjusted so that the ratio a / b is 1.005 to 1.10, where a is the number of moles of the aliphatic diamine used as the raw material and b is the number of moles of the dicarboxylic acid derivative. Preferably, the raw material composition ratio is adjusted to be 1.01 to 1.05. More preferably, it is 1.015 to 1.04. When a / b is less than 1.005, the total amount of amino groups in the polymerization system is extremely smaller than the total amount of carboxyl groups, making it difficult to obtain a sufficiently high molecular weight polymer. On the other hand, when a / b is larger than 1.10, the total amount of carboxyl groups in the polymerization system is extremely smaller than the total amount of amino groups, and it becomes difficult to obtain a sufficiently high molecular weight polymer. Furthermore, the volatilization amount of the diamine component increases, which is not preferable from the viewpoint of productivity and environment.

  The degree of polymerization of the polyamide resin of the present invention requires that the relative viscosity at 25 ° C. of a 98% sulfuric acid solution of 0.01 g / ml is 1.5 to 4.0. More preferably, it is 1.8-3.5. Most preferably, it is 2.0-3.0. When the relative viscosity is less than 1.5, the practical strength is insufficient, and when the relative viscosity is 4.0 or more, the fluidity is lowered and the moldability tends to be impaired.

  In the present invention, a polymerization accelerator can be added as necessary. As the polymerization accelerator, for example, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid and inorganic phosphorus compounds such as alkali metal salts and alkaline earth metal salts thereof are preferable, and sodium phosphite is particularly preferable. Sodium hypophosphite is preferably used. The polymerization accelerator is preferably used in the range of 0.001 to 1 part by weight with respect to 100 parts by weight of the raw material. When the amount of the polymerization accelerator used is less than 0.001 part by weight, the addition effect is hardly recognized, and when it exceeds 1 part by weight, the degree of polymerization of the resulting polyamide resin is excessively increased. There is a tendency that melt molding becomes difficult.

  Generally, a polyamide resin composed of a diamine and a dicarboxylic acid has a secondary amine produced by a deammonification reaction between terminal amino groups as described in Encyclopedia of Polymer Science and Technology, Vol. 10, p546. It is known that it becomes a crosslinking point and gels. For example, it is known that a polyamide resin composed of a hexamethylene terephthalamide unit and a hexamethylene isophthalamide unit tends to form a gel when melted and stays and is inferior in melt and stay stability. The pentamethylenediamine used in the present invention has the property of causing an intramolecular cyclization reaction, and the reason why the polyamide resin of the present invention has excellent residence stability is that the cyclization reaction of pentamethylenediamine during melt residence It is thought that this is because the deammonia reaction between terminal diamines has progressed and the generation of secondary amines has been delayed.

In the present invention, since it is intended to obtain a polyamide resin excellent in melt residence stability, Y represents the sulfuric acid solution viscosity when retained for 30 minutes at melting point (Tm ₁ ) + 20 ° C., and X represents the relative viscosity of sulfuric acid before retention. Y / X is preferably 0.7 or more and 1.5 or less. More preferably, it is 0.8 or more and 1.3 or less, More preferably, it is 0.9 or more and 1.2 or less. When Y / X is less than 0.7, the polyamide resin may be significantly decomposed during melt processing, which is not preferable. Also. When Y / X is larger than 1.5, the viscosity increases due to melting, so that the workability tends to be inferior. The melting point here refers to an endothermic peak observed when the polyamide resin used for the melt residence test is heated to a melting point + 40 ° C. in an inert gas atmosphere using a differential scanning calorimeter as described in the Examples. Temperature (melting point: Tm ₁ ).

  The polyamide resin obtained in the present invention can further contain an inorganic filler and other types of polymers. As an inorganic filler, the well-known thing generally used as a filler for resin can be used. For example, glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, wollastonite, zeolite, Sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, hectorite, synthetic mica, asbestos, aluminosilicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, Examples thereof include magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide, and silica. These may be hollow, and it is also possible to use two or more of these inorganic fillers. For swellable layered silicates such as bentonite, montmorillonite, hectorite, and synthetic mica, organic montmorillonite obtained by cation exchange of interlayer ions with an organic ammonium salt may be used. In order to reinforce the polyamide resin, glass fibers and carbon fibers are particularly preferable among the fillers. In order to make the surface appearance of the polyamide resin composition excellent, it is preferable that the average particle size of the inorganic filler is 0.001 to 10 μm. When the average particle diameter is less than 0.001 μm, the melt processability of the obtained polyamide resin is remarkably lowered, which is not preferable. On the other hand, when the particle diameter exceeds 10 μm, the surface appearance of the molded product tends to deteriorate. The average particle diameter is preferably 0.01 to 5 μm, more preferably 0.05 to 3 μm. These average particle diameters are measured by a sedimentation method. In order to achieve both the reinforcement of the polyamide resin and the good surface appearance, it is preferable to use talc, kaolin, or wollastonite as the inorganic filler.

  In addition, when the inorganic filler is pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound, it can obtain better mechanical strength. Preferred in meaning. Particularly preferred are organosilane compounds, and specific examples thereof include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyl. Epoxy group-containing alkoxysilane compounds such as trimethoxysilane, γ-mercaptopropyltrimethoxysilane, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxy Silane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane and other ureido group-containing alkoxysilane compounds, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyana Isocyanato group-containing alkoxysilane compounds such as topropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane Amino group-containing alkoxysilane compounds such as γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxypropyltri Hydroxyl-containing alkoxysilane compounds such as methoxysilane and γ-hydroxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N-β- (N-bi Nylbenzylaminoethyl) -γ--minopropyltrimethoxysilane / hydrocarbon-containing alkoxysilane compounds such as hydrochloride, and acid anhydride group-containing alkoxysilane compounds such as 3-trimethoxysilylpropylsuccinic anhydride. It is done. In particular, γ-methacryloxypropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-tri Methoxysilylpropyl succinic anhydride is preferably used. These silane coupling agents are preferably used in accordance with a conventional method in which a filler is surface-treated in advance and then melt-kneaded with a polyamide resin, but the filler and the polyamide resin are not subjected to a surface treatment of the filler in advance. When melt kneading, a so-called integral blend method in which these coupling agents are added may be used.

  The treatment amount of these coupling agents is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the inorganic filler. More preferably, it is 0.1-5 weight part, Most preferably, it is 0.5-3 weight part. When the amount is less than 0.05 parts by weight, the effect of improving the mechanical properties due to the treatment with the coupling agent is small. When the amount exceeds 10 parts by weight, the inorganic filler tends to aggregate and poor dispersion in the polyamide resin. Tend to be.

  The compounding quantity of the inorganic filler in this invention is 0.1-200 weight part with respect to 100 weight part of polyamide resins. More preferably, it is 1-100 weight part, More preferably, it is 1.1-60 weight part, Most preferably, it is 5-50 weight part. If the amount is less than 0.1 parts by weight, the effect of improving the rigidity and strength is small. If the amount exceeds 200 parts by weight, it is difficult to uniformly disperse in the polyamide resin, and the strength tends to decrease.

  Examples of other types of polymers include other polyamides, polyethylenes, polypropylenes, polyesters, polycarbonates, polyphenylene ethers, polyphenylene sulfides, liquid crystal polymers, polysulfones, polyether sulfones, ABS resins, SAN resins, polystyrenes, and the like. In order to improve the impact resistance of the polyamide resin, a modified polyolefin such as a (co) polymer obtained by polymerizing an olefin compound and / or a conjugated diene compound is preferably used.

  Examples of the (co) polymer include an ethylene copolymer, a conjugated diene polymer, and a conjugated diene-aromatic vinyl hydrocarbon copolymer.

  Here, the ethylene-based copolymer means a copolymer of ethylene and another monomer and a multi-component copolymer, and the other monomer copolymerized with ethylene is an α having 3 or more carbon atoms. It can be selected from among olefins, non-conjugated dienes, vinyl acetate, vinyl alcohol, α, β-unsaturated carboxylic acids and derivatives thereof.

  Examples of the α-olefin having 3 or more carbon atoms include propylene, butene-1, pentene-1, 3-methylpentene-1, octacene-1, and the like, and propylene and butene-1 can be preferably used. Non-conjugated dienes include 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-crotyl Norbornene compounds such as 2-norbornene, 5- (2-methyl-2-butenyl) -2-norbornene, 5- (2-ethyl-2-butenyl) -2-norbornene, 5-methyl-5-vinylnorbornene, Dicyclopentadiene, methyltetrahydroindene, 4,7,8,9-tetrahydroindene, 1,5-cyclooctadiene 1,4-hexadiene, isoprene, 6-methyl-1,5-heptadiene, 11-tridecadiene, etc. Preferably, 5-methylidene-2-norbrunene, 5-ethylidene- - norbornene, dicyclopentadiene, 1,4-hexadiene, and the like. Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and butenedicarboxylic acid. Derivatives thereof include alkyl esters and aryls. Examples include esters, glycidyl esters, acid anhydrides, and imides.

  The conjugated diene polymer is a polymer containing at least one conjugated diene as a constituent component. For example, a homopolymer such as 1,3-butadiene, 1,3-butadiene, isoprene (2-methyl- 1,3-butadiene), 2,3-dimethyl-1,3-butadiene, a copolymer of one or more monomers selected from 1,3-pentadiene, and the like. Those in which some or all of the unsaturated bonds of these polymers are reduced by hydrogenation can also be preferably used.

  The conjugated diene-aromatic vinyl hydrocarbon-based copolymer is a block copolymer or a random copolymer composed of a conjugated diene and an aromatic vinyl hydrocarbon. And 1,3-butadiene and isoprene are particularly preferable. Examples of the aromatic vinyl hydrocarbon include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, 1,3-dimethyl styrene, vinyl naphthalene, and among them, styrene is preferably used. In addition, a conjugated diene-aromatic vinyl hydrocarbon copolymer in which some or all of unsaturated bonds other than double bonds other than aromatic rings are reduced by hydrogenation can be preferably used.

  Polyamide elastomers and polyester elastomers can also be used. Two or more of these impact resistance improving materials can be used in combination.

  Specific examples of such impact modifiers include ethylene / propylene copolymers, ethylene / butene-1 copolymers, ethylene / hexene-1 copolymers, ethylene / propylene / dicyclopentadiene copolymers, Ethylene / propylene / 5-ethylidene-2-norbornene copolymer, unhydrogenated or hydrogenated styrene / isoprene / styrene triblock copolymer, unhydrogenated or hydrogenated styrene / butadiene / styrene triblock copolymer, ethylene / Methacrylic acid copolymers and some or all of the carboxylic acid moieties in these copolymers as salts with sodium, lithium, potassium, zinc, calcium, ethylene / methyl acrylate copolymers, ethylene / acrylic Ethyl acid copolymer, ethylene / methyl methacrylate copolymer, ethylene / methacrylic acid Ethyl acid copolymer, ethylene / ethyl acrylate-g-maleic anhydride copolymer (“g” represents graft, the same applies hereinafter), ethylene / methyl methacrylate-g-maleic anhydride copolymer, ethylene / Ethyl acrylate-g-maleimide copolymer, ethylene / ethyl acrylate-g-N-phenylmaleimide copolymer and partially saponified products of these copolymers, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / Glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / vinyl acetate / glycidyl acrylate copolymer, ethylene / glycidyl ether copolymer, ethylene / propylene-g -Anhydrous Inic acid copolymer, ethylene / butene-1-g-maleic anhydride copolymer, ethylene / propylene / 1,4-hexadiene-g-maleic anhydride copolymer, ethylene / propylene / dicyclopentadiene-g- Maleic anhydride copolymer, ethylene / propylene / 2,5-norbornadiene-g-maleic anhydride copolymer, ethylene / propylene-gN-phenylmaleimide copolymer, ethylene / butene-1-gN- Phenylmaleimide copolymer, hydrogenated styrene / butadiene / styrene-g-maleic anhydride copolymer, hydrogenated styrene / isoprene / styrene-g-maleic anhydride copolymer, ethylene / propylene-g-glycidyl methacrylate copolymer Polymer, ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene / propylene / 1,4-hexadiene-g-glycidyl methacrylate copolymer, ethylene / propylene / dicyclopentadiene-g-glycidyl methacrylate copolymer, hydrogenated styrene / butadiene / styrene-g-glycidyl methacrylate copolymer, Examples include nylon 12 / polytetramethylene glycol copolymer, nylon 12 / polytrimethylene glycol copolymer, polybutylene terephthalate / polytetramethylene glycol copolymer, polybutylene terephthalate / polytrimethylene glycol copolymer. it can. Among them, ethylene / methacrylic acid copolymers and some or all of the carboxylic acid moieties in these copolymers as salts with sodium, lithium, potassium, zinc, calcium, ethylene / propylene-g-anhydrous Maleic acid copolymers, ethylene / butene-1-g-maleic anhydride copolymers, hydrogenated styrene / butadiene / styrene-g-maleic anhydride copolymers are more preferable, ethylene / methacrylic acid copolymers and these A part or all of the carboxylic acid moiety in the copolymer made into a salt with sodium, lithium, potassium, zinc, calcium, ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene-1-g -Maleic anhydride copolymers are particularly preferred.

  The method for preparing the polyamide resin composition of the present invention is not particularly limited, but as specific examples, a raw material polyamide resin, an inorganic filler, and / or another kind of polymer are used as a single or twin screw extruder, Banbury mixer, Examples thereof include a method of supplying to a known melt kneader such as a kneader and a mixing roll and performing melt kneading.

  When a melt kneader is used as a method for uniformly dispersing these inorganic fillers and other polymers in the polyamide resin, the kneader L / D (screw length / screw diameter), presence or absence of a vent, kneading temperature, residence time It is effective to control the time, the addition position of each component, and the addition amount. In general, it is preferable to increase the L / D of the melt-kneader and to increase the residence time in order to promote uniform dispersion of these inorganic fillers and other types of polymers.

  Furthermore, the polyamide resin of the present invention has various additives such as antioxidants and heat stabilizers (hindered phenols, hydroquinones, phosphites and their substitution products, halogenated compounds, etc. as long as the effects of the present invention are not impaired. Copper, iodine compounds, etc.), weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), mold release agents and lubricants (aliphatic alcohol, aliphatic amide, aliphatic bisamide, bisurea and polyethylene) Waxes, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, aniline black, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkyl sulfates) Type anionic antistatic agent, quaternary ammonia Salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, etc.), flame retardant (melamine cyanurate, magnesium hydroxide, aluminum hydroxide, etc.) Phosphorous flame retardants such as hydroxide, ammonium polyphosphate, melamine polyphosphate, phosphinic acid metal salt, brominated polystyrene, brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resin or these brominated flame retardants. A combination with antimony oxide, etc.) can be added at any time.

  When the polyamide resin of the present invention is crystalline, it has a high melting point that can be satisfactorily molded, and has a high glass transition temperature, so heat resistance, hydrolysis resistance, and solvent resistance are required. It can be used suitably for a certain application. On the other hand, in the case of amorphous, it is used for applications that require heat resistance that takes advantage of the high glass transition temperature, and for applications that require good dimensional stability and good surface appearance that take advantage of the characteristics of amorphous. It can be preferably used.

  The polyamide resin and the polyamide resin composition of the present invention can be molded into a desired shape by any molding method such as injection molding, extrusion molding, blow molding, vacuum molding, melt spinning, film molding, etc. It can be used for resin molded products such as, fibers, films, sheets and the like. Specific applications include automotive engine coolant systems, especially radiator tank components such as radiator tank tops and bases, coolant reserve tanks, water pipes, water pump housings, water pump impellers, water pump components such as valves, and other automobiles. Parts used in contact with cooling water in the engine room, switches, micro slide switches, DIP switches, switch housings, lamp sockets, cable ties, connectors, connector housings, connector shells, IC sockets , Coil bobbin, bobbin cover, relay, relay box, condenser case, motor internal parts, small motor case, gear cam, dancing pulley, spacer, insulator, fastener, back , Wire clip, bicycle wheel, caster, helmet, terminal block, power tool housing, starter insulation, spoiler, canister, radiator tank, chamber tank, reservoir tank, fuse box, air cleaner case, air conditioner fan, terminal housing , Wheel cover, intake / exhaust pipe, bearing retainer, cylinder head cover, intake manifold, water pipe impeller, clutch release, speaker diaphragm, heat-resistant container, microwave oven part, rice cooker part, printer ribbon guide, etc. Useful in related parts, automobile / vehicle-related parts, home appliance / office electrical product parts, computer-related parts, facsimile / copier-related parts, machine-related parts, and other various applications A.

[Relative viscosity (ηr)]
Measurement was performed using an Ostwald viscometer at a concentration of 0.01 g / ml in 25% sulfuric acid in 98% sulfuric acid.

[Melting point, glass transition temperature]
About 5 mg of a sample was collected using a Seiko Instruments robot DSC (RDC220) and measured under the following conditions in a nitrogen atmosphere. The temperature of the endothermic peak (melting point: Tm ₁ ) observed when the temperature of the polymerized polyamide resin is raised to the melting point + 40 ° C. is obtained, held at the melting point + 40 ° C. for 2 minutes, and then cooled at a rate of 20 ° C./min. The temperature was lowered to 30 ° C. and held at 30 ° C. for 3 minutes. Subsequently, the temperature of the endothermic peak (melting point: Tm ₂ ) observed when the temperature was raised to the melting point + 40 ° C. at a temperature rising rate of 20 ° C./min was determined. Also, from the temperature at the midpoint of the stepwise endothermic peak of the DSC curve observed when the sample was rapidly cooled with liquid nitrogen from the melting point of the polyamide resin melting point + 30 ° C. at a rate of temperature increase of 20 ° C./min. The glass transition temperature (Tg) was determined.

[Stay stability]
When a sample held at a temperature of Tm ₁ + 20 ° C. for 30 minutes in a nitrogen atmosphere is dissolved in 98% sulfuric acid at a concentration of 0.01 g / ml, ○ is found to be completely dissolved, and insoluble components are observed. Is indicated by x. In the case of complete dissolution, the sulfuric acid viscosity retention (Y / X) was determined by setting the relative viscosity of sulfuric acid after melt residence to Y and the relative viscosity of sulfuric acid before residence to X.

Reference example 1 (adjustment of lysine decarboxylase)
The E. coli JM109 strain was cultured as follows. First, this platinum strain was inoculated into 5 ml of LB medium, and precultured by shaking at 30 ° C. for 24 hours. Next, 50 ml of LB medium was placed in a 500 ml Erlenmeyer flask and preliminarily steam sterilized at 115 ° C. for 10 minutes. The strain was precultured in this medium, and cultured for 24 hours under the condition of 30 cm in amplitude and 180 rpm while adjusting the pH to 6.0 with 1N aqueous hydrochloric acid. The bacterial cells thus obtained were collected and a cell-free extract was prepared by ultrasonic disruption and centrifugation. These lysine decarboxylase activities were measured according to a standard method (Kenji Sokota, Haruo Misono, Biochemistry Experiment Course, vol.11, P.179-191 (1976)). When lysine is used as a substrate, conversion by lysine monooxygenase, lysine oxidase, and lysine mutase, which are considered to be the main main pathways, can occur. Therefore, for the purpose of blocking this reaction system, the E. coli JM109 strain was isolated at 75 ° C. for 5 minutes. The cell-free extract was heated. Furthermore, this cell-free extract was fractionated with 40% saturated and 55% saturated ammonium sulfate. Using the crude purified lysine decarboxylase solution thus obtained, pentamethylenediamine was produced from lysine.

Reference Example 2 (Production of pentamethylenediamine)
1000 ml of aqueous solution prepared to be 50 mM lysine hydrochloride (manufactured by Wako Pure Chemical Industries), 0.1 mM pyridoxal phosphate (manufactured by Wako Pure Chemical Industries), 40 mg / L-crudely purified lysine decarboxylase (prepared in Reference Example 1) Was reacted for 48 hours at 45 ° C. while maintaining the pH at 5.5 to 6.5 with 0.1N hydrochloric acid aqueous solution to obtain pentamethylenediamine hydrochloride. By adding sodium hydroxide to this aqueous solution, pentamethylenediamine hydrochloride was converted to pentamethylenediamine, extracted with chloroform, and distilled under reduced pressure (10 mmHg, 60 ° C.) to obtain pentamethylenediamine.

Examples 1-6, Comparative Examples 1-7
An equimolar salt of an aliphatic diamine and a dicarboxylic acid was weighed so as to have a weight ratio shown in Tables 1 and 2 (in Example 5, aminocaproic acid was further added). Here, a diamine which is a main component of 2.0 mol% with respect to the total aliphatic diamine was added (the main component indicates a diamine having the largest content among the aliphatic diamines). Furthermore, 30 parts by weight of water was added to and mixed with 70 parts by weight of the total raw materials. This was charged into a pressure vessel, sealed, and purged with nitrogen. Start the heating-can pressure After reaching 25 kg / cm ^2, the water can internal pressure 25 kg / cm ² while releasing to the outside of the system, and held for 2 hours at a temperature 240 ° C. can. Thereafter, the contents were discharged from the reaction vessel onto a cooling belt. The low-order condensate thus obtained was vacuum-dried at 120 ° C. for 24 hours, and then solid-phase polymerized at 240 ° C. and 0.3 torr to obtain a polyamide resin. The abbreviations shown in Tables 1 and 2 are as follows.
5T: equimolar salt of pentamethylenediamine and terephthalic acid 5I: equimolar salt of pentamethylenediamine and isophthalic acid 6T: equimolar salt of hexamethylenediamine and terephthalic acid 6I: equimolar salt of hexamethylenediamine and isophthalic acid 10I: Equimolar mixture of 1,10-decanediamine and isophthalic acid 56: equimolar salt of pentamethylenediamine and adipic acid M5T: equimolar salt of 2-methylpentamethylenediamine and terephthalic acid 6: aminocaproic acid

  From a comparison between Examples 2 and 3 and Comparative Examples 2 and 4, the crystalline polyamide resin 5T / 5I of the present invention using pentamethylenediamine as the aliphatic diamine is hexagonal when the blending ratio of terephthalic acid and isophthalic acid is the same. The melting point can be made lower than that of crystalline 6T / 6I using methylenediamine, and since it has a high glass transition temperature, it can be seen that the molding processability and heat resistance are excellent. Moreover, it is excellent in melt residence stability.

  From a comparison between Example 3 and Comparative Example 5, it can be seen that the glass transition temperature decreases when the 5I component is replaced with 56 components.

  In Comparative Examples 6 and 7 in which the 6I component of Comparative Example 4 is replaced with 5T and M5T components, the dicarboxylic acid derivative is composed only of terephthalic acid, the melting point is higher than that of the polyamide resin of Comparative Example 4, and the molding processability is inferior. I understand.

Examples 7-12, Comparative Examples 8-11
After obtaining a low-order condensate by the same method as in Example 1 and vacuum-drying, the residence time was 5 minutes in a 30 mmφ vented twin screw extruder (TEX30, manufactured by Nippon Steel), the cylinder temperature was 300 ° C., and the screw rotation speed was The degree of melt polymerization was increased at 200 rpm.

  From comparison between Examples 7 and 8 and Comparative Examples 8 and 9, the amorphous 5T / 5I of the present invention using pentamethylenediamine as the aliphatic diamine is more than the amorphous 6T / 6I using hexamethylenediamine. It can be seen that the glass transition temperature is high and the melt retention stability is excellent.

  From the comparison between Examples 7 and 12 and Comparative Example 10, it can be seen that the glass transition temperature decreases when the total amount of terephthalic acid and isophthalic acid in the carboxylic acid derivative is less than 65% by weight.

Example 13
100 parts by weight of the polyamide resin produced in Example 3 was supplied to the main feeder of a twin screw extruder (TEX30 type manufactured by Nippon Steel) set at a cylinder temperature of 320 ° C. and a screw rotation speed of 250 rpm. 42.9 parts by weight of T289) manufactured by Denki Glass Co., Ltd. was supplied and melt-kneaded to obtain a polyamide resin composition. The extruded gut was pelletized and then vacuum-dried at 120 ° C. for 24 hours, followed by injection molding, and mechanical properties were evaluated. The results are shown in Table 4. Further, 0.25 g of a sample obtained by melting and retaining the obtained polyamide resin composition at 310 ° C. for 30 minutes in a nitrogen atmosphere was dissolved in 25 ml of hexafluoroisopropanol (HFIP), and the polyamide resin was dissolved to form the composition. In the case where no disappearance occurred, the case where the polyamide resin did not dissolve and the case where the shape of the composition was maintained without being dissolved was indicated by x.

Comparative Example 12
A polyamide resin composition was obtained in the same manner as in Example 13 except that the polyamide resin produced in Comparative Example 4 was used and the cylinder temperature was changed to 330 ° C.

  From a comparison between Example 13 and Comparative Example 12, the polyamide resin composition containing pentamethylenediamine as a constituent component has higher tensile strength, flexural modulus, and melt residence stability than the polyamide resin containing hexamethylenediamine as a constituent component. Excellent.

Claims (9)

A diamine containing 25% by weight or more of pentamethylenediamine with respect to the total weight of the diamine, and terephthalic acid or a derivative thereof and isophthalic acid or a derivative thereof as essential components, and the total amount thereof is 65% by weight based on the total weight of the dicarboxylic acid or the derivative % Of a 98% sulfuric acid solution at 25 ° C. obtained by polycondensation of a dicarboxylic acid or derivative thereof containing at least 1%, having a chemical structure consisting of repeating amide group units derived from these compounds, and having a concentration of 0.01 g / ml A polyamide resin having a relative viscosity of 1.5 to 4.0. The polyamide resin according to claim 1, which has a melting point of 315 ° C or lower or is amorphous. The polyamide resin according to claim 1 or 2, having a glass transition temperature of 120 ° C or higher. The Y / X is 0.7 or more and 1.5 or less, where Y is the sulfuric acid solution viscosity when retained at melting point + 20 ° C for 30 minutes, and X is the relative viscosity of sulfuric acid before retention. The polyamide resin described in 1. The polyamide resin according to any one of claims 1 to 4, wherein the weight of the repeating unit derived from terephthalic acid or a derivative thereof is 20% by weight or more and 80% by weight or less based on the total weight of the repeating unit derived from the dicarboxylic acid or the derivative thereof. . The polyamide resin composition formed by mix | blending 0.1-200 weight part of inorganic fillers with respect to 100 weight part of polyamide resins in any one of Claims 1-5. The polyamide resin composition according to claim 6, comprising an inorganic filler having an organic functional group introduced therein. A polyamide resin composition obtained by blending 5 to 100 parts by weight of an impact modifier with 100 parts by weight of the polyamide resin according to any one of claims 1 to 5. A polyamide resin composition obtained by blending 0.1 to 200 parts by weight of an inorganic filler and 5 to 100 parts by weight of an impact resistance improver with 100 parts by weight of the polyamide resin according to any one of claims 1 to 5.