JP2013127059A - Polyamide resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin excellent in moldability, heat resistance, crystallinity, and residence stability.SOLUTION: This polyamide resin includes pentamethylenediamine and a 6C or more linear aliphatic diamine, which is obtained by polycondensing a diamine, whose proportion of pentamethylenediamine to total amount of diamine is 10-80 mol%, and a dicarboxylic acid component whose proportion of cyclohexanedicarboxylic acid and derivatives thereof to total amount of dicarboxylic acid component is 81-100 mol%. The polyamide resin has relative viscosity at 25°C of 1.5-4.5 in a 98% sulfuric acid solution containing 0.01 g/mL of the polyamide.

Description

  The present invention relates to a molding process obtained by polycondensing an aliphatic diamine containing pentamethylene diamine and a linear aliphatic diamine having 6 or more carbon atoms and a dicarboxylic acid component containing cyclohexanedicarboxylic acid and / or a derivative thereof. The present invention relates to a polyamide resin having excellent properties, heat resistance, crystallinity, and retention stability.

  Polyamide resins are widely used as engineering plastics in automobile parts, electrical and electronic parts, and recently, polyamides containing alicyclic dicarboxylic acids having excellent heat resistance and weather resistance have been proposed.

  Patent Document 1 discloses a polyamide resin obtained by polymerizing a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid and a diamine containing a diamine having a substituent branched from the main chain of at least 50 mol%. . However, the polyamide resin disclosed in Patent Document 1 has a problem of poor crystallinity.

  On the other hand, Patent Document 2 discloses a polyamide resin in which 85 to 100 mol% of dicarboxylic acid units are composed of 1,4-cyclohexanedicarboxylic acid units and 60 to 100 mol% of diamine units are composed of aliphatic diamine units having 6 to 18 carbon atoms. However, since the melting point was high, the moldability was poor. Moreover, the subject that it was inferior to residence stability occurred.

  Patent Document 3 includes a polyamide resin containing 5 mol% or more and 25 mol% or less of an alicyclic monomer, and Patent Document 4 includes 10 to 80 mol% of 1,4-cyclohexanedicarboxylic acid in all dicarboxylic acid components. Polyamide resins have been disclosed, but all have the problem of poor retention stability.

  Further, Patent Document 5 discloses a polyamide obtained by polymerizing a dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid and a diamine having a pentamethylenediamine skeleton of at least 50 mol%. Example 8 of Patent Document 5 describes a polyamide resin having a structural unit composed of pentamethylenediamine and cyclohexanedicarboxylic acid and a structural unit composed of pentamethylenediamine and adipic acid, but has the problem of poor crystallinity. there were.

  On the other hand, Non-Patent Document 1 describes a copolymerized polyamide using terephthalic acid and adipic acid as raw materials as dicarboxylic acids. Since terephthalic acid and adipic acid have almost the same molecular size, they become isomorphous substitution, and this copolyamide has a feature of high crystallinity in all compositions.

JP 2010-1111843 A JP 9-012868 A JP2011-68876A International Publication No. 2002/048239 International Publication No. 2011/030742

“Journal of Polymer Science”, 1960, Vol. 42, p. 249-257

  Unlike terephthalic acid, which has no isomer, cyclohexanedicarboxylic acid has a complicated molecular conformation due to the presence of cis / trans isomers. In addition, since cyclohexanedicarboxylic acid and adipic acid have different molecular sizes, the polyamide resin shown in Example 8 of Patent Document 5 is different from the polyamide resin of Non-Patent Document 1 in that it does not undergo Isomorphrous substitution and is obtained by copolymerization. Crystallinity decreases. An object of the present invention is to provide a polyamide resin excellent in molding processability, heat resistance, crystallinity, and retention stability using pentamethylenediamine and cyclohexanedicarboxylic acid as raw materials.

  In order to obtain a polyamide resin excellent in moldability, crystallinity, and retention stability, the present inventors use pentamethylenediamine and a linear aliphatic diamine having 6 or more carbon atoms, heat resistance, The inventors have found that it is effective to use cyclohexanedicarboxylic acid and / or a derivative thereof in order to impart crystallinity and residence stability, and have reached the present invention.

That is, the present invention
(I) a diamine containing pentamethylenediamine and a linear aliphatic diamine having 6 or more carbon atoms, wherein the proportion of pentamethylenediamine with respect to the total amount of diamine is 10 mol% or more and 80 mol% or less, cyclohexanedicarboxylic acid with respect to the total amount of dicarboxylic acid components, and The relative viscosity at 25 ° C. of a 98% sulfuric acid solution obtained by polycondensation of a dicarboxylic acid component having a derivative ratio of 81 mol% or more and 100 mol% or less and 0.01 g / ml is 1.5 to 4.5. A polyamide resin,
(Ii) Using a differential scanning calorimeter, the melting point is 260 ° C. or higher and 325 ° C. when the temperature is increased from the molten state to 30 ° C. at a temperature decreasing rate of 20 ° C./min and then heated at a temperature increasing rate of 20 ° C./min. The polyamide resin described in (i),
(Iii) The polyamide resin according to (i) or (ii), wherein the ratio of pentamethylenediamine to the total amount of diamine is 20 mol% or more and 65 mol% or less,
(Iv) The polyamide resin according to any one of (i) to (iii), wherein the ratio of cyclohexanedicarboxylic acid and its derivative to the total amount of dicarboxylic acid and its derivative is 90 mol% or more and 100 mol% or less,
(V) straight chain aliphatic diamine having 6 or more carbon atoms is 1,6-diaminohexane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane and 1 Polyamide resin according to any one of (i) to (iv), which is at least one selected from the group consisting of 1,12-diaminododecane,
(Vi) A molded article obtained by molding the polyamide resin according to any one of (i) to (v).

  According to the present invention, it is possible to provide a polyamide resin excellent in molding processability, heat resistance, crystallinity, and retention stability.

  The polyamide resin of the present invention is obtained by polycondensation of a diamine and a dicarboxylic acid component composed of dicarboxylic acid and / or a derivative thereof. Of the total amount of diamine and dicarboxylic acid components constituting the polyamide resin, the total weight of pentamethylenediamine, straight chain aliphatic diamine having 6 or more carbon atoms, cyclohexanedicarboxylic acid and derivatives thereof is preferably 80% by weight or more, 90 More preferably, it is at least wt%.

  The polyamide resin of the present invention is characterized by using pentamethylene diamine and a straight-chain aliphatic diamine having 6 or more carbon atoms as the diamine as a constituent component. By using pentamethylenediamine, a polyamide resin having excellent retention stability can be obtained. Moreover, by using a linear aliphatic diamine having 6 or more carbon atoms, it is possible to obtain a polyamide resin having a melting point capable of being molded and suppressing thermal decomposition while maintaining crystallinity.

  In the present invention, the ratio of pentamethylenediamine to the total amount of diamine constituting the polyamide resin is from 10 mol% to 80 mol%, preferably from 20 mol% to 65 mol%. More preferably, it is less than 50 mol%, More preferably, it is 45 mol% or less. When the proportion of pentamethylenediamine is less than 10 mol% or more than 80 mol%, the melting point of the polyamide resin is remarkably increased and is thermally decomposed during the molding process, and the residence stability tends to be lowered.

  Specific examples of the straight chain aliphatic diamine having 6 or more carbon atoms include 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-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane and the like. Two or more of these may be used. By using 1,6-diaminohexane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, heat during molding processing Since decomposition can be suppressed, 1,10-diaminodecane and 1,12-diaminododecane are more preferable. The linear aliphatic diamine having 6 or more carbon atoms is preferably 20 mol% or more and 90 mol% or less in the total amount of diamine. 35 mol% or more and 80 mol% or less is more preferable, and 25 mol% or more and 50 mol% or less is more preferable.

  The polyamide resin of the present invention is characterized in that cyclohexanedicarboxylic acid and / or a derivative thereof is used as a dicarboxylic acid component which is a constituent component. By using cyclohexanedicarboxylic acid, a polyamide resin excellent in heat resistance, crystallinity, and retention stability can be obtained.

  In the present invention, the ratio of cyclohexanedicarboxylic acid and its derivative to the total amount of dicarboxylic acid components constituting the polyamide resin is 81 mol% or more and 100 mol% or less, preferably 90 mol% or more and 100 mol% or less. When the ratio of cyclohexanedicarboxylic acid and its derivative is less than 81 mol%, the heat resistance, residence stability, and crystallinity of the polyamide resin are impaired.

  Specific examples of cyclohexanedicarboxylic acid include 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Specific examples of the cyclohexanedicarboxylic acid derivative include dimethyl 1,3-cyclohexanedicarboxylate, dimethyl 1,4-cyclohexanedicarboxylate, diethyl 1,3-cyclohexanedicarboxylate, diethyl 1,4-cyclohexanedicarboxylate and the like. It is done. Two or more of these may be used. 1,4-cyclohexane is more preferred.

  The polyamide resin of the present invention has, as its constituent dicarboxylic acid component, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid. Dicarboxylic acids such as aliphatic dicarboxylic acids such as acid, brassic acid, tetradecanedioic acid, pentadecanedioic acid and octadecanedioic acid, aromatic dicarboxylic acids such as terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid and their derivatives, etc. 19 mol% or less can be used with respect to the total amount.

  The polyamide resin of the present invention can be copolymerized with other components in an amount of preferably 20% by weight or less, more preferably 10% by weight or less, and in an amount that does not impair the effects of the present invention. Examples of other components include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, ethylenediamine, 1,3 -Aliphatic diamines such as aliphatic diamines such as diaminopropane and 1,4-diaminobutane, cyclohexanediamine, bis- (4-aminocyclohexyl) methane, and aromatic diamines such as xylylenediamine.

  The relative viscosity of the polyamide resin of the present invention is 1.5 to 4.5. When the relative viscosity is less than 1.5, the degree of polymerization is low, and the practical strength is insufficient. 1.8 or more is preferable. On the other hand, when the relative viscosity exceeds 4.5, the fluidity at the time of melting is lowered and the moldability is impaired. 3.5 or less is preferable. Here, the relative viscosity of the polyamide resin in the present invention refers to the relative viscosity at 25 ° C. of a 98% sulfuric acid solution of 0.01 g / ml. A polyamide resin having such a relative viscosity can be obtained, for example, by adjusting the raw material charging amount so as to maintain the equimolarity of the total amino group amount and the total carboxyl group amount in the polymerization system, as described later.

  The polyamide resin of the present invention preferably has a melting point of 260 ° C. or higher and 325 ° C. or lower. When the melting point is 260 ° C. or higher, the melting point is equal to or higher than that of aliphatic polyamide resins such as polyhexamethylene adipamide resin (nylon 66) and polypentamethylene adipamide resin (nylon 56), and heat resistance is improved. . 270 ° C or higher is more preferable, and 285 ° C or higher is more preferable. On the other hand, if the melting point is 325 ° C. or lower, thermal decomposition during molding can be suppressed. 310 ° C. or lower is more preferable, and 305 ° C. or lower is further preferable. Here, the melting point of the polyamide resin in the present invention is 20 ° C. after the polyamide resin is cooled from the molten state to 30 ° C. at a temperature decreasing 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 increased at a rate of temperature increase per minute. However, when two or more endothermic peaks are detected, the endothermic peak having the highest peak intensity is taken as the melting point. Examples of a method for obtaining a polyamide resin having a melting point in the above range and having excellent moldability include, for example, containing pentamethylenediamine in the above-mentioned range with respect to the total amount of diamine, and a linear aliphatic having 6 or more carbon atoms Examples of the diamine include 1,6-diaminohexane, 1,10-diaminodecane, and 1,12-diaminododecane.

  Although there is no restriction | limiting in the manufacturing method of the pentamethylenediamine which comprises the polyamide resin 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, and lysine A method of converting from 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. In the present invention, lysine decarboxylase present in these organisms can be preferably used, and those derived from recombinant cells in which the intracellular activity of lysine decarboxylase is also preferably 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, ordinary methods are 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 to 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.

  Either a stationary method or a stirring method can 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.

  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 heating polycondensation method in which a mixture of pentamethylenediamine, straight chain aliphatic diamine having 6 or more carbon atoms, cyclohexanedicarboxylic acid and / or a derivative thereof, and, if necessary, other copolymerization components is heated at a high temperature to advance a dehydration reaction. Etc. 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.

  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. If water is 10 weight% or more, the uniform melt | dissolution of a nylon salt can be advanced efficiently, and an excessive heat history can be suppressed. On the contrary, if water is 70 weight% or less, the heat energy required for water removal is suppressed, and a prepolymer can be efficiently generated. Furthermore, it is preferable that the pressure hold | maintained in a pressurized state shall be 0.8-3.5 MPa. If it is 0.8 MPa or more, volatilization of pentamethylenediamine outside the polymerization system can be suppressed. Moreover, if it is 3.5 MPa or less, the production | generation of the piperidine (polymerization terminator) by the side reaction of pentamethylenediamine can be suppressed.

  As the heat polycondensation method, a salt of pentamethylenediamine and cyclohexanedicarboxylic acid, a straight chain aliphatic diamine having 6 or more carbon atoms and a salt of cyclohexanedicarboxylic acid are prepared, mixed in the presence of water, and heated. A method for proceeding with the dehydration reaction is generally used. However, since a salt of a straight-chain aliphatic diamine having 6 or more carbon atoms and cyclohexanedicarboxylic acid is inferior in water solubility, a method of charging raw materials may be used without preparing a salt.

  When preparing the salt in advance, by changing the mixing ratio of the salt of pentamethylenediamine and cyclohexanedicarboxylic acid, the straight chain aliphatic diamine having 6 or more carbon atoms and the salt of cyclohexanedicarboxylic acid, By changing the charging ratio of each raw material, the copolymer composition ratio of the polyamide resin can be changed.

  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. 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.

  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 deammonification 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, in order to synthesize a high molecular weight polyamide resin, it is preferable to previously add an excessive amount of a specific amount of pentamethylenediamine and control the amount of amino groups in the polymerization system at the stage of charging the raw materials. The raw material composition ratio is adjusted so that the ratio a / b is 1.003 to 1.10, where a is the number of moles of aliphatic diamine used as a raw material and b is the number of moles of dicarboxylic acid and its derivatives. The raw material composition ratio is more preferably adjusted to be 1.008 to 1.05. More preferably, it is 1.010-1.04. If a / b is 1.003 or more, the total amino group amount in the polymerization system is sufficiently present with respect to the total carboxyl group amount, so that a sufficiently high molecular weight polymer is easily obtained. On the other hand, if a / b is 1.10 or less, the total amount of carboxyl groups in the polymerization system is sufficiently large with respect to the total amount of amino groups, so that a sufficiently high molecular weight polymer is easily obtained. Furthermore, since the volatilization amount of the diamine component is also reduced, it is preferable from the viewpoint of productivity and environment.

  In the present invention, a polymerization accelerator can be added as necessary. As the polymerization accelerator, for example, inorganic phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, alkali metal salts thereof, and alkaline earth metal salts thereof are preferable. Sodium phosphite and sodium hypophosphite are 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 constituting the polyamide resin. If the amount of the polymerization accelerator used is 0.001 part by weight or more, the effect of addition is remarkably exhibited, and if it is 1 part by weight or less, the melt moldability of the resulting polyamide resin can be kept high. .

  A polyamide resin composition can be obtained by blending the polyamide resin of the present invention with a filler, other polymers, and the like. As the filler, known materials generally used as fillers for resins are used, and the strength, rigidity, heat resistance, dimensional stability and the like of the polyamide resin composition can be improved. 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, selenium Site, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, asbestos, aluminosilicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate , Barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide, silica and the like. These may be hollow, and two or more of these fillers may be used. These fillers may be used after being treated 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. As for montmorillonite, 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.

  Other types of polymers include other polyamides, polyethylene, polypropylene, polyester, polycarbonate, polyphenylene ether, polyphenylene sulfide, liquid crystal polymer, polysulfone, polyether sulfone, ABS resin, SAN resin, polystyrene, and the like. In order to improve the impact resistance of the polyamide resin composition, 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 refers to a copolymer of ethylene and another monomer and a multi-component copolymer, and the other monomer copolymerized with ethylene has 3 or more carbon atoms. Examples include α-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- Norbornene compounds such as crotyl-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-norbornene, 5-ethylidene 2-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, butenedicarboxylic acid, and derivatives thereof include alkyl esters. And aryl 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), and the like. -1,3-butadiene), 2,3-dimethyl-1,3-butadiene, and a copolymer of one or more monomers selected from 1,3-pentadiene. 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. The body is mentioned. In particular, 1,3-butadiene and isoprene are preferred. 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 part 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, ethyne / 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 male 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, nylon 12 / polytetramethylene glycol copolymer, nylon 12 / polytrimethylene glycol copolymer, polybutylene terephthalate / polytetramethylene glycol copolymer, polybutylene terephthalate / polytrimethylene glycol copolymer, and the like. . 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.

  Furthermore, various additives such as antioxidants and heat stabilizers (hindered phenols, hydroquinones, phosphites and their substitutes, and copper are added to the polyamide resin of the present invention as long as the effects of the present invention are not impaired. Compounds), mold release agents and lubricants (aliphatic alcohols, aliphatic amides, aliphatic bisamides, bisureas, polyethylene waxes, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, aniline black, etc.) , Plasticizer (octyloxyoxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agent (alkyl sulfate type anionic antistatic agent, quaternary ammonium salt type cationic antistatic agent, polyoxyethylene sorbitan monosteare Nonionic antistatic agent such as rate, betaine amphoteric band Inhibitors, etc.), flame retardants (melamine cyanurate, mono (β-cyanoethyl) isocyanurate, bis (β-cyanoethyl) isocyanurate, tris (β-cyanoethyl) isocyanurate, etc., magnesium hydroxide, water Metal hydroxide flame retardants such as aluminum oxide, red phosphorus, ammonium polyphosphate, melamine polyphosphate, (di) phosphinic acid metal salt, phosphazene compound, aromatic phosphate ester, aromatic condensed phosphate ester, phosphorus halide Phosphorus flame retardants such as acid esters, brominated polystyrenes, brominated polyphenylene oxides, brominated polycarbonates, brominated flame retardants such as brominated epoxy resins, or combinations of these brominated flame retardants with antimony trioxide) Thus, a polyamide resin composition can be obtained.

  Examples of the antioxidant include phenol-based, sulfur-based, and phosphorus-based compounds.

  Examples of phenolic antioxidants include 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,6-di- t-butyl-4-ethylphenol, 4,4′-butylidenebis (6-t-butyl-3-methylphenol), 2,2′-methylene-bis (4-methyl-6-t-butylphenol), 2, 2′-methylene-bis (4-ethyl-6-tert-butylphenol), octadecyl-3 (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, tetrakis [methylene-3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl-4-hydroxy-5-di-t-butylphenyl) butane, (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6 -Hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5- Di-t-butylanilino) -1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), N, N′- Hexamethylene-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate-diethyl ester 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,4-bis [(octylthio) methyl] -o-cresol And isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate.

  Sulfuric antioxidants include dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, ditridecyl thiodipropionate, pentaerythrityl (3-lauryl thiopropionate), 2 -Mercaptobenzimidazole etc. are mentioned.

  Phosphorus antioxidants include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di -Phosphite, bis (2,4-di-cumylphenyl) pentaerythritol-di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) ) -4,4′-bisphenylene phosphite, di-stearyl pentaerythritol-di-phosphite, triphenyl phosphite, 3,5-dibutyl-4-hydroxybenzyl phosphonate diethyl ester and the like.

  These antioxidants may be used singly or in combination of two or more, since a synergistic effect may be obtained.

  Copper compounds used as heat stabilizers include cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cupric sulfate. , Cupric nitrate, copper phosphate, cuprous acetate, cupric acetate, cupric salicylate, cupric stearate, cupric benzoate and the inorganic copper halide and xylylenediamine, 2-mercapto Examples thereof include complex compounds such as benzimidazole and benzimidazole. Of these, monovalent copper compounds, particularly monovalent copper halide compounds are preferred, and cuprous acetate and cuprous iodide are more preferred. It is preferable that the addition amount of a copper compound is 0.01-1 weight part normally with respect to 100 weight part of polyamide resins. More preferably, it is 0.013-0.5 weight part, More preferably, it is 0.015-0.3 weight part. As a copper atom, it is preferable that it is 30-6500 ppm with respect to 100 weight part of polyamide resins. More preferably, it is 40-1600 ppm, More preferably, it is 50-1000 ppm. In the present invention, an alkali halide can be added in combination with a copper compound. Examples of the alkali halide compound include lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide, sodium bromide and sodium iodide. Sodium chloride is particularly preferred.

  The polyamide resin produced by the present invention, or a polyamide resin composition blended with an inorganic filler and other types of polymers can be formed by any molding method such as injection molding, extrusion molding, blow molding, vacuum molding, melt spinning, film molding, etc. Can be molded. These molded products can be molded into a desired shape, and can be used for resin molded products such as automobile parts and machine parts. 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, LED reflectors, cable ties, connectors, connector housings, connector shells, IC sockets, coil bobbins, bobbin covers, relays, relay boxes, condenser cases, motor internal parts, small motor cases, gears / cams, dancing pulleys, spacers, insulators, Fastener, buckle, 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, Representative of 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. Electrical / electronic related parts, automobile / vehicle related parts, home appliance / office electrical product parts, computer related parts, facsimile / copier related parts, machine related parts, It is useful in other various applications.

  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, heat of fusion]
Using a DSC RDC220 manufactured by Seiko Instruments Inc., about 5 mg of a sample that was pulverized and vacuum-dried as described in the Examples was precisely weighed and measured under the following conditions in a nitrogen atmosphere. Endothermic peak temperature (Tm1) observed when the temperature is increased from 30 ° C. at a rate of temperature increase of 20 ° C./min. After raising the temperature to 40 ° C. to a molten state, 30 ° C. at a rate of temperature decrease of 20 ° C./min. The temperature of the endothermic peak (melting point: Tm2) and the heat of fusion ΔHm observed when the temperature was raised to Tm1 + 40 ° C. at a rate of temperature increase of 20 ° C./min was determined. .

[Stay stability]
The relative viscosity ηr1 of the sample held at a temperature of Tm1 + 20 ° C. for 30 minutes in a nitrogen atmosphere was measured, and the ratio (ηr1 / ηr) to the relative viscosity ηr of the sample before being held at a temperature of Tm1 + 20 ° C. for 30 minutes was determined. If ηr1 / ηr was 1.00 or more, it was judged that the retention stability was excellent.

Reference Example 1 (Preparation 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 (1.33 kPa, 60 ° C.) to obtain pentamethylenediamine. .

Examples 1-6, Comparative Examples 1-9
A total of 10 g of aliphatic diamine and dicarboxylic acid are mixed in a molar ratio as shown in Tables 1 and 2 and charged into a test tube. An excess of 3.0 mol% of pentane with respect to an equimolar salt composed of diamine and dicarboxylic acid. Methylenediamine or the main component diamine was added. Furthermore, water was added so that water might be 15 weight% with respect to all the raw materials. This was charged in a pressure vessel, sealed, and purged with nitrogen. After starting the heating, reaching the can internal pressure of 1.0 MPa and the can internal temperature of 200 ° C., controlling the internal pressure of the can to 1.0 MPa while releasing the moisture out of the system, and reaching the can internal temperature of 275 ° C., The temperature was maintained for 2 hours and heating was stopped. After allowing to cool to room temperature, the test tube was taken out of the pressurized container, and the resulting solid was pulverized. This was vacuum-dried at 100 ° C. for 24 hours to obtain a polyamide resin.

Examples 7 and 8 and Comparative Example 10
A total of 10 g of aliphatic diamine and dicarboxylic acid were blended in a molar ratio as shown in Tables 1 and 2 and charged into a test tube. In Example 7, for an equimolar salt composed of diamine and dicarboxylic acid, 1,10-decanediamine was added in an excess of 1.0 mol%. In Example 8 and Comparative Example 10, penmethylenediamine was further added in excess of 3.0 mol% with respect to an equimolar salt composed of diamine and dicarboxylic acid. Then, water was added so that water might be 20 weight% with respect to all the raw materials in Examples 7, 8 and Comparative Example 10. This was charged in a pressure vessel, sealed, and purged with nitrogen. After heating was started and the internal pressure of the can reached 1.0 MPa and the internal temperature of the can reached 200 ° C., the internal pressure was maintained for 90 minutes at an internal pressure of 1.0 MPa while releasing moisture out of the system. At this time, the inside temperature of the can reached 272 ° C. Thereafter, over 50 minutes, the internal pressure of the can was made normal (the internal temperature reached 300 ° C.) and held for 2 hours in a nitrogen atmosphere (the internal temperature reached 310 ° C.). After stopping the heating and allowing to cool to room temperature, the test tube was taken out of the pressurized container, and the resulting solid was pulverized. This was vacuum-dried at 120 ° C. for 24 hours to obtain a polyamide resin.

The raw materials used are as follows.
Pentamethylenediamine: Reference Example 2
Hexamethylenediamine: manufactured by Tokyo Chemical Industry Co., Ltd. 1,10-decanediamine: manufactured by Ogura Gosei Kogyo Co., Ltd. 1,12-dodecanediamine: manufactured by Ogura Gosei Kogyo Co., Ltd. 2-methylpentamethylenediamine: Tokyo Kasei Co., Ltd. 1,4-cyclohexanedicarboxylic acid manufactured (cis / trans = 3/7): adipic acid manufactured by Tokyo Chemical Industry Co., Ltd .: manufactured by Tokyo Chemical Industry Co., Ltd. The abbreviations shown in Tables 1 and 2 are as follows.
5C: equimolar mixture of pentamethylenediamine and 1,4-cyclohexanedicarboxylic acid 6C: equimolar mixture of hexamethylenediamine and 1,4-cyclohexanedicarboxylic acid 10C: 1,10-decanediamine and 1,4-cyclohexanedicarboxylic acid 12C: equimolar mixture of 1,12-dodecanediamine and 1,4-cyclohexanedicarboxylic acid M5C: equimolar mixture of 2-methylpentamethylenediamine and 1,4-cyclohexanedicarboxylic acid 56: pentamethylenediamine Equimolar mixture of adipic acid

  By comparing Examples 1 to 8 and Comparative Examples 1 and 2, a polyamide resin having excellent molding processability can be obtained by using a linear aliphatic diamine having 6 or more carbon atoms and pentamethylene diamine in combination.

  Comparison between Examples 1 and 2 and Comparative Examples 4 and 5 makes it possible to obtain a polyamide resin having a high melting point and excellent crystallinity by using in combination with pentamethylenediamine having no branching.

  By comparison between Example 2 and Comparative Example 6, it is possible to obtain a polyamide resin having excellent residence stability by using pentamethylenediamine together.

  By comparing Examples 1 to 3 and Comparative Example 7 with the ratio of pentamethylenediamine to the total amount of diamine being 80 mol% or less, a polyamide resin having excellent residence stability and molding processability can be obtained.

  By comparing Examples 1 to 3 and Comparative Example 8 with the ratio of pentamethylenediamine to the total amount of diamine being 10 mol% or more, a polyamide resin having excellent residence stability and molding processability can be obtained.

  By comparing Examples 1 to 6 and Comparative Example 9 with the ratio of cyclohexanedicarboxylic acid to the total amount of the dicarboxylic acid component being 81 mol% or more, a polyamide resin having excellent residence stability can be obtained.

  From Comparative Example 10, when the amount of the cyclohexanedicarboxylic acid component in the dicarboxylic acid component is small, the crystallinity is low.

  The polyamide resin of the present invention can be molded by any known method such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning, etc., and is processed into various molded products and used. be able to. As molded products, it can be used as injection molded products, extrusion molded products, blow molded products, various films such as uniaxially stretched and biaxially stretched, sheets, various fibers such as unstretched yarn, stretched yarn, and superstretched yarn. . In particular, in the present invention, it is possible to process various electric / electronic parts, automobile parts and the like by taking advantage of excellent molding processability, heat resistance, crystallinity, and retention stability.

Claims (6)

A diamine containing pentamethylenediamine and a linear aliphatic diamine having 6 or more carbon atoms, wherein the ratio of pentamethylenediamine to the total amount of diamine is 10 mol% to 80 mol%, and cyclohexanedicarboxylic acid and its derivatives to the total amount of dicarboxylic acid components Polyamide resin having a relative viscosity of 1.5 to 4.5 at 25 ° C. in a 98% sulfuric acid solution obtained by polycondensation of a dicarboxylic acid component having a ratio of 81 mol% to 100 mol% in 0.01 g / ml. . Using a differential scanning calorimeter, the melting point is 260 ° C. or higher and 325 ° C. or lower when the temperature is lowered from the molten state to 30 ° C. at a temperature lowering rate of 20 ° C./min and then heated at a temperature rising rate of 20 ° C./min. The polyamide resin according to claim 1. The polyamide resin according to claim 1 or 2, wherein the ratio of pentamethylenediamine to the total amount of diamine is 20 mol% or more and 65 mol% or less. The polyamide resin according to any one of claims 1 to 3, wherein a ratio of cyclohexanedicarboxylic acid and a derivative thereof to a total amount of the dicarboxylic acid component is 90 mol% or more and 100 mol% or less. Straight chain aliphatic diamines having 6 or more carbon atoms are 1,6-diaminohexane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane and 1,12- The polyamide resin according to claim 1, which is at least one selected from the group consisting of diaminododecane. A molded product formed by molding the polyamide resin according to claim 1.