JP2010121113A - Polyamide resin and polyamide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide resin including pentamethylene diamine as a component, having a low melting point, excellent molding processability, and excellent melt retention stability while having a high glass transition temperature, and a composition thereof. <P>SOLUTION: The polyamide resin is obtained by a polycondensation of (A) pentamethylene diamine, (B) terephthalic acid and/or a derivative thereof, (C) at least one material selected from a lactam, an aminocarboxylic acid, and a 7C or more aliphatic dicarboxylic acid, the total of (A), (B), and (C) being 75 wt.% or more. The relative viscosity of a 98% sulfuric acid solution of the polyamide resin (polyamide resin: 0.01 g/mL) at 25°C is 1.5 to 4.0. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyamide resin containing pentamethylenediamine as a constituent component and a composition thereof. More specifically, the present invention relates to a polyamide resin containing pentamethylenediamine as a constituent component and a composition thereof having a high glass transition temperature, a low melting point, excellent moldability, and excellent melt retention stability.

  Polyamide resins are widely used as engineering plastics in automobile parts, electrical and electronic parts, etc., but in recent years, semi-aromatic polyamides with high heat resistance and high glass transition temperature are in response to demands such as high heat resistance and low water absorption. Has been proposed.

  Patent Documents 1 and 2 disclose semi-aromatic polyamide 6T / 6 composed of units derived from terephthalic acid and hexamethylenediamine (6T) and units derived from ε-caprolactam (6). . Patent Document 3 discloses a semi-aromatic polyamide (6T / N) composed of hexamethylene terephthalamide (6T) and an aliphatic polyamide (N) having 8 or more carbon atoms per amide group. Has been. These semi-aromatic polyamides can adjust the glass transition temperature by changing the composition of the copolymer component, but in order to achieve high heat resistance and low water absorption, it is necessary to increase the glass transition temperature. It is often designed with more. However, as the 6T component increases, the melting point also increases at the same time, and the temperature during the molding process must be increased, and the problem is that the resin is easily deteriorated and carbonized. Another problem is that if the material is melted and retained, it tends to cause thickening and gelation.

  Patent Document 4 discloses a semi-aromatic polyamide 5T / 6T mainly composed of an aliphatic diamine having pentamethylenediamine and hexamethylenediamine as main components and a terephthalic acid derivative as main components. Since this semi-aromatic polyamide mainly uses a terephthalic acid derivative as a dicarboxylic acid component, the glass transition temperature is high, but in any copolymer composition, the melting point is high, and the molding processability is inferior as described above. Was an issue.

Japanese Patent Laid-Open No. 2-41318 Japanese Patent Laid-Open No. 10-152555 Japanese Patent Laid-Open No. 11-181083 JP 2003-292613 A

  The present invention provides a polyamide resin comprising pentamethylenediamine as a constituent component and a composition thereof having a high glass transition temperature, a low melting point, excellent molding processability, and excellent melt retention stability. Let it be an issue.

  As a result of intensive studies to solve the above problems, the present inventors have found that (A) pentamethylenediamine, (B) terephthalic acid and / or its derivative, (C) lactam, aminocarboxylic acid, and 7 per molecule. The present inventors have found that a polyamide resin obtained by polycondensation of at least one selected from aliphatic dicarboxylic acids having the above carbon can solve the above problems, and has completed the present invention.

That is, the present invention
1. At least one selected from (A) pentamethylenediamine, (B) terephthalic acid and / or its derivative, (C) lactam, aminocarboxylic acid, and aliphatic dicarboxylic acid having 7 or more carbons per molecule is used. A polyamide resin obtained by condensation, wherein the sum of (A), (B) and (C) is 75% by weight or more, and the relative viscosity at 25 ° C. of a 98% sulfuric acid solution of 0.01 g / ml is 1. Polyamide resin which is 5-4.0.
2. 2. The polyamide resin according to 1, wherein the component (C) is 10% by weight or more and less than 50% by weight.
3. Y / X is 0.8 or more and 1.5 or less, where Y is the sulfuric acid solution viscosity when retained at melting point (Tm ₁ ) + 20 ° C. for 30 minutes and X is the relative viscosity of sulfuric acid before retention. The polyamide resin as described in 1 or 2.
4). 4. The polyamide resin according to any one of 1 to 3, which has a melting point (Tm ₂ ) of 310 ° C. or lower and a glass transition temperature of 100 ° C. or higher.
5). The polyamide resin according to any one of 1 to 4, wherein the lactam and aminocarboxylic acid in the component (C) have 6 or more carbons per molecule.
6). The lactam and aminocarboxylic acid in the component (C) are at least one selected from caprolactam, undecalactam, dodecalactam, 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. 5. The polyamide resin according to 5.
7). The aliphatic dicarboxylic acid in the component (C) is at least one selected from suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid, according to any one of 1 to 4, Polyamide resin.
8. The polyamide resin according to any one of 1 to 7, which has a water absorption rate of 3.50% or less after water absorption treatment for 135 hours under conditions of 8.35 ° C. and a relative humidity of 95%.
9. The polyamide resin according to any one of 1 to 8, wherein the lactam and aminocarboxylic acid in the component (C) have 10 or more carbons per molecule.
10. The polyamide resin according to 9, wherein the lactam and aminocarboxylic acid in the component (C) are at least one selected from undecalactam, dodecalactam, 11-aminoundecanoic acid, and 12-aminododecanoic acid. .
11. The polyamide resin according to any one of 1 to 8, wherein the aliphatic dicarboxylic acid in the component (C) has 10 or more carbons per molecule.
12 12. The polyamide resin according to 11, wherein the aliphatic dicarboxylic acid in the component (C) is at least one selected from sebacic acid, undecanedioic acid, and dodecanedioic acid.
A polyamide resin composition comprising 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 13.1 to 12.
14 14. The polyamide resin composition according to 13, comprising an inorganic filler having an organic functional group introduced therein.
15. A polyamide resin composition obtained by blending 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 15.1 to 12.
A polyamide resin composition obtained by blending 0.1 to 100 parts by weight of an inorganic filler and 5 to 100 parts by weight of an impact modifier with 100 parts by weight of the polyamide resin according to any one of 16.1 to 12. .
17. A molded article comprising the polyamide resin according to any one of 17.1 to 12 or the polyamide resin composition according to any one of 13 to 16.
Is to provide.

  The present invention provides a polyamide resin having pentamethylenediamine as a constituent component and a composition thereof having a high glass transition temperature, a low melting point, excellent moldability, and excellent melt retention stability. It becomes possible.

  The present invention provides at least one selected from (A) pentamethylenediamine, (B) terephthalic acid and / or a derivative thereof, (C) a lactam, an aminocarboxylic acid, and an aliphatic dicarboxylic acid having 7 or more carbons per molecule. It is a polyamide resin obtained by polycondensation of seeds, and the total of (A), (B) and (C) is 75% by weight or more with respect to all monomer components used as a raw material for the polyamide resin.

  Although there is no restriction | limiting in the manufacturing method of the pentamethylenediamine which comprises (A) component of this invention, For example, the method of synthesize | combining from lysine using vinyl ketones, such as 2-cyclohexen-1-one, and a lysine decarboxylase is used. A method for converting from lysine has 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 into pentamethylenediamine, and is known to exist not only in Escherichia microorganisms such as Escherichia coli K12 but also in many organisms. Yes.

  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 lysine decarboxylase include Bacillus halodurans, Bacillus subtilis, Escherichia coli, Selenomonas ruminumium, and Selenomonas ruminumium. Vibrio cholerae), Vibrio parahaemolyticus, Streptomyces coelicolor, Streptomyces pirosus, Streptomyces pirusus Cuterium acididaminofilm, Salmonella typhimurium, Hafnia albei, Neisseria meningitide Pyrococcus abyssi) or Corynebacterium glutamicum.

  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 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 and / or its derivatives constituting the component (B) of the present invention include terephthalic acid, terephthalic acid chloride, dimethyl terephthalate, diethyl terephthalate and the like.

  Specific examples of the lactam constituting the component (C) of the present invention include 2-pyrrolidone, methyl pyrrolidone, caprolactam, enantolactam, undecaractam, dodecaractam and the like. Among them, lactam having 6 or more carbons per molecule is preferable, and caprolactam, undecaractam, and dodecaractam are preferable. Furthermore, in order to reduce water absorption, lactams having 10 or more carbons per molecule are preferable, and undecaractam and dodecaractam are preferable.

  Specific examples of the aminocarboxylic acid constituting the component (C) of the present invention include 3-aminopropionic acid, 4-aminobutyric acid, 5-aminovaleric acid, 6-aminocaproic acid, 7-aminoheptanoic acid, and 8-amino. Examples include octanoic acid, 9-aminononanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid. Of these, aminocarboxylic acids having 6 or more carbon atoms per molecule are preferable, and 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid are preferable. Further, from the viewpoint of reducing the water absorption rate, aminocarboxylic acids having 10 or more carbons per molecule are preferable, and 11-aminoundecanoic acid and 12-aminododecanoic acid are preferable.

  Specific examples of the aliphatic dicarboxylic acid having 7 or more carbons per molecule constituting the component (C) of the present invention include suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and derivatives thereof. Can be mentioned. Among these, aliphatic dicarboxylic acids having 10 or more carbons per molecule are preferable, and sebacic acid, undecanedioic acid, and dodecanedioic acid are preferable from the viewpoint of water absorption reduction.

  Lactam, aminocarboxylic acid, and aliphatic dicarboxylic acid having 7 or more carbons per molecule may be used alone, or two or more kinds may be used in combination as appropriate.

  In the present invention, the total of components (A), (B) and (C) is 75% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and most preferably 95% by weight or more. Specific examples of components other than (A), (B) and (C) that can be added within a range of less than 25% by weight include ethylenediamine, propanediamine (1,3-diaminopropane), tetramethylenediamine ( 1,4-diaminobutane), hexamethylenediamine (1,6-diaminohexane), heptamethylenediamine (1,7-diaminoheptane), octamethylenediamine (1,8-diaminooctane), nonamethylenediamine (1, 9-diaminononane), decane methylenediamine (1,10-diaminodecane), undecane methylenediamine (1,11-diaminoundecane), dodecane methylenediamine (1,12-diaminododecane), tridecane methylenediamine (1,13- Diaminotridecane), tetradecane methyle Diamine (1,14-diaminotetradecane), pentadecanmethylenediamine (1,15-diaminopentadecane), hexadecanmethylenediamine (1,16-diaminohexadecane), heptadecanmethylenediamine (1,17-diaminoheptadecane), octadecanmethylene Diamine (1,18-diaminooctadecane), nonadecane methylenediamine (1,19-diaminononadecane), eicosamethylenediamine (1,20-diaminoeicosane), 2-methyl-1,5-pentamethylenediamine ( Aliphatic diamines such as 2-methyl-1,5-diaminopentane), cyclohexanediamine, alicyclic diamines such as bis- (4-aminocyclohexyl) methane, aromatic diamines such as xylylenediamine, and oxalic acid Examples include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and adipic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. It is done.

  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 heat polycondensation method in which a mixture of pentamethylenediamine, terephthalic acid, lactam and / or aminocarboxylic acid (and other copolymerization components) is heated at a high temperature to cause a dehydration reaction, and pentamethylenediamine and lactam and / or Dissolve aminocarboxylic acid (and other copolymerization components) in water, dissolve terephthalic acid chloride (and other copolymerization components) in an organic solvent that does not mix with water, and polycondensate at the interface between these aqueous and organic phases. For example, an interfacial polymerization method. 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 uses an organic solvent and requires the neutralization of hydrochloric acid, which is a by-product during polycondensation. Is preferably used.

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 preferable. 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 by a pressurization 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.

  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 polyamide resin of the present invention can also be increased in molecular weight by heating polycondensation and further by solid-phase polymerization or by melt residence in an extruder. Solid phase polymerization proceeds by heating in a vacuum or in an inert gas within a temperature range of 100 ° C. to a melting point. Further, the melt retention in the extruder proceeds by melting and retaining at a temperature equal to or higher than the melting point of the polyamide resin. 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.

  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. Most preferably, it is 2.0-3.0. If the relative viscosity is less than 1.5, the practical strength is insufficient, and if it is 4.0 or more, the fluidity is lowered and the molding processability is 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.

  The component (C) of the present invention is preferably 10% by weight or more and less than 50% by weight with respect to the entire charged raw material. More preferably, they are 15 weight% or more and less than 45 weight%, More preferably, they are 20 weight% or more and 40 weight% or less. When the component (C) is less than 10% by weight with respect to the entire charged raw material, the temperature at the time of melt molding must be increased, and the resin is deteriorated. On the other hand, if it exceeds 50% by weight, the glass transition temperature of the resulting polyamide resin is lowered, which is not preferable.

In the present invention, a polyamide resin excellent in melt residence stability is to be obtained. Therefore, Y is the sulfuric acid solution viscosity when retained for 30 minutes at the melting point (Tm ₁ ) + 20 ° C., and the relative viscosity of sulfuric acid before retention. When X is set, Y / X is preferably 0.8 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 is increased by melting, so that the processability tends to be inferior. The melting point (Tm ₁ ) referred to here is 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. Shows the temperature of the endothermic peak. In the case of a polyamide resin in which the melting point is not detected, the value is a value when melted and retained at a temperature of glass transition temperature + 170 ° C.

  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, in a polyamide resin composed of hexamethylene adipamide units and hexamethylene terephthalamide units, it is known that when melted and retained, the above reaction proceeds and a gel is easily formed and the melt and residence stability is poor. . 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.

The present invention seeks to obtain a polyamide resin having pentamethylenediamine as a constituent component and having a high glass transition temperature and a low melting point and excellent molding processability, and has a melting point (Tm ₂ ) of 310 ° C. Hereinafter, the glass transition temperature is preferably 100 ° C. or higher. When the melting point (Tm ₂ ) exceeds 310 ° C., the temperature at the time of melt molding must be increased, and the resin is deteriorated. Moreover, when the glass transition temperature is less than 100 ° C., the heat resistance becomes poor, which is not preferable. Here, the melting point (Tm ₂ ) used in the present invention is a 20 ° C./20° C. temperature after cooling from a molten state to 30 ° C. at a temperature lowering rate of 20 ° C./min in an inert gas atmosphere using a differential scanning calorimeter. It is defined as the temperature of the endothermic peak that appears when the temperature is raised at a rate of minutes. However, when two or more endothermic peaks are detected, the peak having the higher temperature is defined as the melting point (Tm ₂ ). In addition, the glass transition temperature used in the present invention appears when a differential scanning calorimeter is used and the temperature is increased at a rate of temperature increase of 20 ° C./min after quenching with liquid nitrogen from a molten state in an inert gas atmosphere. It is defined as the temperature at the midpoint of the stepped endothermic peak. When the polyamide resin of the present invention is composed only of the components (A), (B) and (C), the melting point and glass transition temperature can be obtained by adding the component (C) in an amount of 21% by weight to 39% by weight. Can be obtained.

Furthermore, the polyamide resin of the present invention preferably has a water absorption rate of 3.50% or less after being subjected to a water absorption treatment for 135 hours at 35 ° C. and a relative humidity of 95%. Specifically, the water absorption rate used here is an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries), the cylinder temperature is the melting point + 20 ° C., the mold temperature is 70 ° C., and the injection pressure is the molding lower limit pressure. Using ASTM No. 4 dumbbell produced as +5 kgf / cm ² , the sample was treated in a constant temperature and humidity chamber set at 35 ° C. and relative humidity 95% for 135 hours and calculated from the weight change rate before and after the treatment.

  In order to reduce the water absorption, it is effective to reduce the concentration of the amide group (amide bond) in the polyamide resin, and the lactam, aminocarboxylic acid and aliphatic dicarboxylic acid constituting the component (C) are one molecule. It is preferred to have 10 or more carbons per hit. For example, as lactam and aminocarboxylic acid, undecalactam, dodecanalactam, 11-aminoundecanoic acid, and 12-aminododecanoic acid are preferable. As aliphatic dicarboxylic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid are preferable. .

  In the present invention, an inorganic filler and other kinds of polymers can be further added. 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.

  Inorganic fillers preferably have an organic functional group introduced, and should be 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. Is preferable in terms of obtaining superior mechanical strength. 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-aminopropyltrimethoxysilane / 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 kinds of these impact resistance improvers 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 compounding amount of the impact modifier in the present invention is 5 to 100 parts by weight with respect to 100 parts by weight of the polyamide resin. More preferably, it is 5 to 50 parts by weight, further preferably 10 to 40 parts by weight, and most preferably 10 to 30 parts by weight. If the amount is less than 5 parts by weight, the effect of improving impact resistance is small, and if it exceeds 100 parts by weight, the melt viscosity tends to be high and the moldability tends to be inferior.

  It is also preferable to add to the polyamide resin of the present invention a combination of the above-described inorganic filler and impact resistance improver. The blending amount of the inorganic filler and impact modifier is preferably 0.1 to 100 parts by weight of inorganic filler and 5 to 100 parts by weight of impact modifier with respect to 100 parts by weight of the polyamide resin. More preferably, it is 1 to 80 parts by weight of an inorganic filler, 5 to 50 parts by weight of an impact modifier, and more preferably 1.1 to 60 parts by weight of an inorganic filler and 10 to 40 parts by weight of an impact modifier. Yes, most preferably 5 to 50 parts by weight of an inorganic filler and 10 to 30 parts by weight of an impact resistance improver.

  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.

  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. 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.

  The polyamide resins produced in the examples and comparative examples were evaluated by the following methods.

[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 (Tm ₁ ), Melting Point (Tm ₂ ) Glass Transition Temperature (Tg)]
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 polyamide resin after polymerization was heated to the melting point + 40 ° C. was determined, held at the melting point + 40 ° C. for 2 minutes, and then the temperature decreasing rate was 20 ° C./minute. The temperature was lowered to 30 ° C. and kept 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 rate of temperature rise of 20 ° C./min was determined. In addition, for a sample rapidly quenched with liquid nitrogen from the melting point of the melting point of the polyamide resin + 20 ° C., the glass from the temperature at the midpoint of the stepwise endothermic peak of the DSC curve observed when the temperature is raised at a rate of temperature rise of 20 ° C./min. The transition temperature (Tg) was determined.

[Water absorption rate]
Using an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.), produce ASTM No. 4 dumbbell-shaped test pieces with a cylinder temperature of melting point + 20 ° C., a mold temperature of 70 ° C., and an injection pressure of molding lower limit pressure + 5 kgf / cm ^2. did. This test piece was treated in a constant temperature and humidity chamber set at 35 ° C. and relative humidity 95% for 135 hours, and the water absorption rate was calculated from the rate of change in weight before and after the treatment.

[Stay stability]
Investigate whether or not a sample held at a temperature of Tm ₁ + 20 ° C. for 30 minutes in a nitrogen atmosphere dissolves in 98% sulfuric acid at a concentration of 0.01 g / ml. Indicated by ×. 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)
E. E. coli strain JM109 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. The cell-free extract of E. coli strain JM109 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 and 2
About 60 g of a test tube was prepared by mixing a 30% by weight aqueous solution of pentamethylenediamine and equimolar salt of terephthalic acid (5T salt) prepared in Reference Example 2 and aminocaproic acid so that the weight ratios shown in Table 1 were obtained. In addition, pentamethylenediamine produced in Reference Example 2 in an amount of 1.0 mol% based on 5T salt was charged into a test tube, sealed in an autoclave, and purged with nitrogen. The jacket temperature was set to 310 ° C. and heating was started. After the internal pressure reached 17.5 kg / cm ² , the internal pressure was maintained at 17.5 kg / cm ² for 3 hours. Thereafter, the internal pressure of the can was released to normal pressure over 1 hour. Thereafter, the flow of nitrogen was stopped, and the heating was stopped when the temperature inside the can reached 270 ° C. After cooling to room temperature, the test tube was removed from the autoclave to obtain a polyamide oligomer. This polyamide oligomer was pulverized and subjected to solid phase polymerization at 240 ° C. and 0.3 torr for 8 hours to obtain a polyamide resin. Various evaluation results are shown in Table 1.

Example 3
A polyamide resin was obtained in the same manner as in Example 1 except that the solid state polymerization conditions were changed to 220 ° C. and 0.3 Torr for 8 hours. Various evaluation results are shown in Table 1.

Examples 4 and 5
A polyamide resin was obtained in the same manner as in Examples 1 and 2 except that aminocaproic acid was changed to aminoundecanoic acid. Various evaluation results are shown in Table 1.

Example 6
A polyamide resin was obtained in the same manner as in Example 3 except that aminocaproic acid was changed to aminoundecanoic acid. Various evaluation results are shown in Table 1.

Examples 7 and 8
A polyamide resin was obtained in the same manner as in Examples 1 and 2 except that aminocaproic acid was changed to aminododecanoic acid. Various evaluation results are shown in Table 1.

Example 9
A polyamide resin was obtained in the same manner as in Example 3 except that aminocaproic acid was changed to aminododecanoic acid. Various evaluation results are shown in Table 1.

Example 10
A polyamide resin was obtained in the same manner as in Example 2 except that aminocaproic acid was changed to a combination of aminoundecanoic acid and aminododecanoic acid. Various evaluation results are shown in Table 1.

Example 11, Comparative Example 7
A polyamide resin was obtained in the same manner as in Example 3 except that aminocaproic acid was changed to a combined use of aminododecanoic acid, and an equimolar salt (66 salt) of hexamethylenediamine and adipic acid. Various evaluation results are shown in Table 1.

Examples 12 and 13
The equimolar salt of pentamethylenediamine and terephthalic acid (5T salt) produced in Reference Example 2 and the equimolar salt of pentamethylenediamine and sebacic acid (510 salt) were blended so as to have the weight ratio shown in Table 1, and An excess of 1.0 mol% of pentamethylenediamine with respect to pentamethylenediamine was added. 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 20 kg / cm ^2, the water can internal pressure 20 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, and this was vacuum dried at 100 ° C. for 24 hours to obtain a polyamide oligomer. The obtained polyamide oligomer was pulverized and dried, and solid phase polymerized at 50 Pa and 240 ° C. to obtain a polyamide resin. Various evaluation results are shown in Table 1.

Comparative Examples 1 and 2
About 60 g of a solution prepared by mixing a 30% by weight aqueous solution of hexamethylenediamine and an equimolar salt of terephthalic acid (6T salt) and aminocaproic acid in a weight ratio shown in Table 2, was added to a 6T salt. 1.0 mol% of hexamethylenediamine was charged into a test tube, sealed in an autoclave, and purged with nitrogen. The jacket temperature was set to 310 ° C. and heating was started. After the internal pressure reached 17.5 kg / cm ² , the internal pressure was maintained at 17.5 kg / cm ² for 3 hours. Thereafter, the internal pressure of the can was released to normal pressure over 1 hour. Thereafter, the flow of nitrogen was stopped, and the heating was stopped when the temperature inside the can reached 270 ° C. After cooling to room temperature, the test tube was removed from the autoclave to obtain a polyamide resin. Various evaluation results are shown in Table 2.

Comparative Example 3
About 60 g of a solution prepared by mixing a 30% by weight aqueous solution of hexamethylenediamine and an equimolar salt of terephthalic acid (6T salt) and aminocaproic acid in a weight ratio shown in Table 2, was added to a 6T salt. 1.0 mol% of hexamethylenediamine was charged into a test tube, sealed in an autoclave, and purged with nitrogen. The jacket temperature was set to 310 ° C. and heating was started. After the internal pressure reached 17.5 kg / cm ² , the internal pressure was maintained at 17.5 kg / cm ² for 3 hours. Thereafter, the internal pressure of the can was released to normal pressure over 1 hour. Thereafter, the flow of nitrogen was stopped, and the heating was stopped when the temperature inside the can reached 270 ° C. After cooling to room temperature, the test tube was removed from the autoclave to obtain a polyamide oligomer. This polyamide oligomer was pulverized and subjected to solid phase polymerization at 220 ° C. and 0.3 torr for 8 hours to obtain a polyamide resin. Various evaluation results are shown in Table 2.

Comparative Examples 4 and 5
A polyamide resin was obtained in the same manner as in Comparative Examples 1 and 2 except that aminocaproic acid was changed to aminododecanoic acid. Various evaluation results are shown in Table 2.

Comparative Example 6
A polyamide resin was obtained in the same manner as in Comparative Example 3 except that aminocaproic acid was changed to aminododecanoic acid. Various evaluation results are shown in Table 2.

Comparative Examples 8 and 9
A 30% by weight aqueous solution of an equimolar salt of pentamethylenediamine and terephthalic acid (5T salt) produced in Reference Example 2 and a 30% by weight aqueous solution of an equimolar salt of hexamethylenediamine and terephthalic acid (6T salt) were prepared. About 60 g of the solution mixed so as to have a weight ratio shown in FIG. 2 is charged into a test tube, and further, 2.24 mol% of pentamethylenediamine produced in Reference Example 2 with respect to 5T salt is charged into the test tube and placed in an autoclave. Sealed and purged with nitrogen. The jacket temperature was set to 310 ° C. and heating was started. After the internal pressure reached 17.5 kg / cm ² , the internal pressure was maintained at 17.5 kg / cm ² for 3 hours. Thereafter, the jacket temperature was set to 320 ° C., and the internal pressure of the can was released to normal pressure over 1 hour. Thereafter, the flow of nitrogen was stopped, and the heating was stopped when the temperature inside the can reached 280 ° C. After cooling to room temperature, the test tube was removed from the autoclave to obtain a polyamide oligomer. The polyamide oligomer was pulverized and subjected to solid phase polymerization at 240 ° C. and 0.3 torr for 10 hours to obtain a polyamide resin. Various evaluation results are shown in Table 2.

Comparative Examples 10 and 11
An equimolar salt of hexamethylene diamine and terephthalic acid (6T salt) and an equimolar salt of hexamethylene diamine and sebacic acid (610 salt) were blended so as to have a weight ratio shown in Table 2, and further with respect to hexamethylene diamine. 1.0 mol% excess of hexamethylenediamine was added. 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 20 kg / cm ^2, the water can internal pressure 20 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, and this was vacuum dried at 100 ° C. for 24 hours to obtain a polyamide oligomer. The obtained polyamide oligomer was pulverized and dried, and solid phase polymerized at 50 Pa and 240 ° C. to obtain a polyamide resin. Various evaluation results are shown in Table 2.

  From the comparison of Examples 1-3 and Comparative Examples 1-3, the comparison of Examples 7-9 and Comparative Examples 4-6, the comparison of Examples 12, 13 and Comparative Examples 10, 11, pentamethylenediamine as an aliphatic diamine was obtained. The polyamide resins 5T / 6, 5T / 12, and 5T / 510 of the present invention having a higher glass transition temperature than the polyamide resins 6T / 6, 6T / 12, and 6T / 610 using hexamethylenediamine. However, it has a low melting point and is found to have excellent heat resistance and molding processability. It can also be seen that the retention stability is excellent.

  Furthermore, 5T / 11, 5T / 12, 5T / 11/12, 5T / 12/66 described in Examples 4 to 13 using an aminocarboxylic acid having 10 or more carbons per molecule and an aliphatic dicarboxylic acid, It can be seen that 5T / 510 has a low water absorption rate.

  From the comparison between Example 11 and Comparative Example 7, when other components than (A), (B), and (C) are copolymerized, if the copolymerization amount is less than 25% by weight, it is a feature of the present invention. A polyamide resin having a low melting point while having a high glass transition temperature can be obtained.

  In Comparative Examples 8 and 9, it can be seen that the dicarboxylic acid derivative is composed only of terephthalic acid, has a higher melting point than the polyamide resin of the example, and is inferior in molding processability.

Claims (17)

At least one selected from (A) pentamethylenediamine, (B) terephthalic acid and / or its derivative, (C) lactam, aminocarboxylic acid, and aliphatic dicarboxylic acid having 7 or more carbons per molecule is used. A polyamide resin obtained by condensation, wherein the sum of (A), (B) and (C) is 75% by weight or more, and the relative viscosity at 25 ° C. of a 98% sulfuric acid solution of 0.01 g / ml is 1. Polyamide resin which is 5-4.0. The polyamide resin according to claim 1, wherein the component (C) is 10% by weight or more and less than 50% by weight. Y / X is 0.8 or more and 1.5 or less, where Y is the sulfuric acid solution viscosity when retained at melting point (Tm ₁ ) + 20 ° C. for 30 minutes and X is the relative viscosity of sulfuric acid before retention. The polyamide resin according to claim 1 or 2. 4. The polyamide resin according to claim 1, having a melting point (Tm ₂ ) of 310 ° C. or lower and a glass transition temperature of 100 ° C. or higher. The polyamide resin according to any one of claims 1 to 4, wherein the lactam and aminocarboxylic acid in the component (C) have 6 or more carbons per molecule. The lactam and aminocarboxylic acid in the component (C) are at least one selected from caprolactam, undecalactam, dodecalactam, 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. The polyamide resin according to claim 5. The aliphatic dicarboxylic acid in the component (C) is at least one selected from suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid. The polyamide resin described. The polyamide resin according to any one of claims 1 to 7, which has a water absorption rate of 3.50% or less after 135 hours of water absorption under conditions of 35 ° C and a relative humidity of 95%. The polyamide resin according to any one of claims 1 to 8, wherein the lactam and aminocarboxylic acid in the component (C) have 10 or more carbons per molecule. The lactam and aminocarboxylic acid in the component (C) are at least one selected from undecalactam, dodecalactam, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Polyamide resin. The polyamide resin according to any one of claims 1 to 8, wherein the aliphatic dicarboxylic acid in the component (C) has 10 or more carbons per molecule. The polyamide resin according to claim 11, wherein the aliphatic dicarboxylic acid in the component (C) is at least one selected from sebacic acid, undecanedioic acid, and dodecanedioic acid. 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 1-12. The polyamide resin composition according to claim 13, wherein an inorganic filler having an organic functional group introduced therein is blended. A polyamide resin composition obtained by blending 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 12. A polyamide resin composition comprising 0.1 to 100 parts by weight of an inorganic filler and 5 to 100 parts by weight of an impact modifier with respect to 100 parts by weight of the polyamide resin according to any one of claims 1 to 12. . A molded article comprising the polyamide resin according to any one of claims 1 to 12 or the polyamide resin composition according to any one of claims 13 to 16.