JP2010150445A - Polyamide resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide resin which comprises pentamethylene diamine, a long-chain diamine, and a terephthalic acid derivative as the main constituents, and is excellent in moldability, heat resistance, low water-absorption, and residence stability. <P>SOLUTION: The polyamide resin can be obtained by condensation polymerization of an aliphatic diamine and a dicarboxylic acid derivative, wherein: the aliphatic diamine comprises pentamethylene diamine and an diamine having 7 or more carbon atoms as the main constituents; and the dicarboxylic acid derivative comprises a terephthalic acid derivative as the main constituent. The polyamide resin has a relative viscosity of 1.5-4.5 in a 98% sulfuric acid solution at 0.01 g/mL at 25°C. The polyamide resin composition contains the polyamide resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention provides molding processability and heat resistance obtained by polycondensation of an aliphatic diamine containing pentamethylene diamine and a diamine having 7 or more carbon atoms as main components and a dicarboxylic acid derivative containing a terephthalic acid derivative as a main component. The present invention relates to a polyamide resin excellent in low water absorption and melt residence stability, and a composition thereof.

  Pentamethylenediamine is expected as a non-petroleum raw material, a synthetic raw material for pharmaceutical intermediates and the like, and a polymer raw material, and the demand is increasing in recent years. Patent Document 1 discloses a polypentamethylene adipamide resin.

  On the other hand, Patent Document 2 discloses a polyamide resin mainly containing an aliphatic diamine and terephthalic acid derivatives mainly containing pentamethylenediamine and hexamethylenediamine. This polyamide resin is composed of a bond unit of pentamethylenediamine and terephthalic acid (5T) and a bond unit of hexamethylenediamine and terephthalic acid (6T), and the melting point is controlled by a specific copolymerization ratio. However, the melting point still remained high and the molding processability was poor.

Furthermore, Patent Document 3 discloses a polyamide resin composed of a bond unit (10T) of diaminodecane and terephthalic acid, but has poor molding processability due to its high melting point. Moreover, the subject that it was inferior to melt residence stability occurred.
JP 2003-292612 A JP 2003-292613 A JP 60-158220 A

  An object of the present invention is to provide a polyamide resin having pentamethylenediamine, a long-chain diamine, and a terephthalic acid derivative as main components and excellent in moldability, heat resistance, low water absorption, and retention stability.

  The present inventors use a long-chain diamine to obtain a polyamide resin composition excellent in moldability and low water absorption, and use an aromatic dicarboxylic acid to impart heat resistance. In order to further improve the retention stability, it has been found that it is effective to contain pentamethylenediamine as a diamine component, and the present invention has been achieved.

That is, the present invention
(I) 0.01 g / ml obtained by polycondensing an aliphatic diamine containing pentamethylenediamine and a diamine having 7 or more carbon atoms as main components and a dicarboxylic acid derivative containing terephthalic acid derivatives as main components; A polyamide resin having a relative viscosity at 25 ° C. of the 98% sulfuric acid solution of 1.5 to 4.5,
(Ii) Using a differential scanning calorimeter, the melting point is 255 ° C. or higher and 314 ° 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 glass transition temperature is 100 ° C. or higher and 160 ° C. or lower,
(Iv) The polyamide resin according to any one of (i) to (iii), wherein the pentamethylenediamine component is 5% by weight or more and 80% by weight or less based on the total amount of the aliphatic diamine;
(V) The terephthalic acid derivative component is 70% by weight or more based on the total amount of the dicarboxylic acid derivative, The polyamide resin according to any one of claims (i) to (iv),
(Vi) The diamine having 7 or more carbon atoms is at least one selected from 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane (i) to ( v) the polyamide resin according to any one of
(Vii) A polyamide resin composition obtained by blending 0.1 to 100 parts by weight of an inorganic filler with respect to 100 parts by weight of the polyamide resin according to any one of (i) to (vi),
(Viii) The polyamide resin composition (ix) according to any one of (vii) to (vi), which is formed by blending an inorganic filler having an organic functional group introduced therein. A polyamide resin composition comprising 5 to 100 parts by weight of an impact resistance improver.
(X) A molded article comprising the polyamide resin according to any one of (i) to (vi) or the polyamide resin composition according to any one of (vi) to (ix).

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

  A polyamide resin obtained by polycondensation of an aliphatic diamine containing pentamethylenediamine and a diamine having 7 or more carbon atoms as main components and a dicarboxylic acid derivative containing a terephthalic acid derivative as a main component is, among the constituent components, It is a polyamide resin in which the total weight of pentamethylenediamine, diamine having 7 or more carbon atoms, and terephthalic acid derivative is 80% by weight or more. More preferably, it is 90 weight% or more, More preferably, it is 95 weight% or more. Here, among the constituent components of the polyamide resin, when the aliphatic diamine is 100% by weight and the total of pentamethylene diamine and diamine having 7 or more carbon atoms is 80% by weight or more, pentamethylene diamine and 7 or more carbon atoms are used. An aliphatic diamine containing diamine as a main component is used. Further, when the dicarboxylic acid derivative is 100% by weight and the total of the terephthalic acid derivatives is 80% by weight or more, the dicarboxylic acid derivative containing the terephthalic acid derivative as a main component is used.

  Specific examples of the diamine having 7 or more carbon atoms include 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, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane, and other aliphatic diamines. Since the diamine having a substituent in the side chain inhibits the crystallinity of the polyamide resin, a diamine having no substituent in the side chain is used as the aliphatic diamine, or a diamine having a substituent in the side chain is all aliphatic. It is preferable to set it as 30 weight% or less with respect to diamine.

  Specific examples of the terephthalic acid derivative that is a dicarboxylic acid component include terephthalic acid, terephthalic acid chloride, dimethyl terephthalate, and diethyl terephthalate.

  The copolymer unit of less than 20% by weight contained in the constituent component of the polyamide resin of the present invention includes amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, ε- Examples include caprolactam and lactam such as ω-laurolactam. Further, the copolymer units of less than 20% by weight contained in the dicarboxylic acid derivative include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid. , Dodecanedioic acid, brassic acid, tetradecanedioic acid, pentadecanedioic acid, aliphatic dicarboxylic acid such as octadecanedioic acid, alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid And aromatic dicarboxylic acids. Further, the copolymer unit of less than 20% by weight contained in the aliphatic diamine includes ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane and other aliphatic diamines, cyclohexanediamine. And alicyclic diamines such as bis- (4-aminocyclohexyl) methane and aromatic diamines such as xylylenediamine.

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

  The lysine decarboxylase used in the latter method is an enzyme that converts lysine 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 activity of lysine decarboxylase is cultured in an appropriate medium. It is possible to collect the grown cells and use them as resting cells, or to crush the cells and prepare a cell-free extract for use, and purify as necessary. It is also possible to use it.

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

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

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

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

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

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

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

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

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

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

  The lysine decarboxylase may be immobilized.

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

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

  In the present invention, the aliphatic diamine is used in combination with a diamine having 7 or more carbon atoms and pentamethylenediamine because it has a unique effect of improving the retention stability of the polyamide resin. As described in Encyclopedia of Polymer Science and Technology, Vol.10, p546, the polyamide resin composed of diamine and dicarboxylic acid is a gelling point due to the triamine generated by the deammonification reaction between terminal amino groups. It is known to do. A diamine having 7 or more carbon atoms does not cyclize itself, but pentamethylenediamine has a property of causing an intramolecular cyclization reaction. As a reason why the residence stability of the polyamide resin of the present invention is excellent, it is considered that the cyclization reaction of pentamethylenediamine suppresses the deammonification reaction between terminal diamines and delays the generation of triamine.

  Since the present invention is intended to obtain a polyamide resin excellent in molding processability, the temperature of the polyamide resin is lowered from the molten state by 20 ° C./min in an inert gas atmosphere using a differential scanning calorimeter. The temperature of the endothermic peak that appears when the temperature is lowered to 30 ° C. and then raised at a rate of temperature increase of 20 ° C./min is preferably 255 ° C. or higher and 314 ° C. or lower. More preferably, it is 270 degreeC or more and 310 degrees C or less. In the present invention, the temperature of this endothermic peak is defined as the melting point. However, when two or more endothermic peaks are detected, the endothermic peak having the highest peak intensity is taken as the melting point. When the melting point is lower than 255 ° C., the melting point is equal to or lower than the melting point of aliphatic polyamide resins such as polyhexamethylene adipamide resin (nylon 66) and polypentamethylene adipamide resin (nylon 56). The effect of improving heat resistance cannot be obtained. Moreover, when melting | fusing point is higher than 314 degreeC, there exists a tendency for melt molding to become difficult.

  Furthermore, in the present invention, in addition to the melting point, the glass transition temperature of the polyamide resin is preferably 100 ° C. or higher and 160 ° C. or lower. When the glass transition temperature is less than 100 ° C, the effect of improving heat resistance is small, and when it is higher than 160 ° C, melt molding tends to be difficult.

  In order to obtain a polyamide resin having excellent residence stability and moldability, it is preferable to blend the pentamethylenediamine component with respect to the total amount of the aliphatic diamine so as to be 5% by weight or more and 80% by weight or less. More preferably, they are 10 weight% or more and 75 weight% or less, More preferably, they are 15 weight% or more and 60 weight% or less.

  Moreover, in order to obtain a polyamide resin excellent in moldability and heat resistance, it is preferable to blend the terephthalic acid derivative component with respect to the total amount of the dicarboxylic acid derivative so as to be 70% by weight or more. More preferably, it is 75 weight% or more, More preferably, it is 80 weight% or more.

  As a method for producing the polyamide resin of the present invention, a known method can be applied. For example, a method disclosed in “Polyamide Resin Handbook” (Fukumoto Shushu) or the like can be used. A mixture of pentamethylenediamine, a diamine having 7 or more carbon atoms and terephthalic acid is heated at a high temperature to cause a dehydration reaction, and pentamethylenediamine and a diamine having 7 or more carbon atoms are dispersed in water. And a method of dissolving terephthalic acid chloride in an organic solvent that is not mixed with water and polycondensing at the interface between the aqueous phase and the organic phase (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 is complicated by using an organic solvent and neutralizing hydrochloric acid, which is a by-product during polycondensation. It is preferable to use it.

In the heat polycondensation of polyamide resin, it is necessary to go through a step of maintaining the polymerization system in a pressurized state and generating a prepolymer, which is usually required in melt polymerization, and is performed in the presence of water. It is necessary. The amount of water charged is preferably 10 to 70% by weight with respect to the total amount of raw material and water combined. When the water content is less than 10% by weight, it takes a long time to uniformly dissolve the nylon salt, and an excessive heat history tends to be applied. On the other hand, when the amount of water is more than 70% by weight, a great amount of heat energy is consumed for removing the water, and it takes time to produce the prepolymer. Furthermore, it is preferable that the pressure hold | maintained in a pressurized state shall be 10-25 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. Further, when the temperature is kept higher than 25 kg / cm ^2, it is necessary to increase the temperature in the polymerization system, and as a result, pentamethylenediamine is liable to volatilize out of the system, which is not preferable.

  As the heat polymerization method, there is a method of preparing a salt of pentamethylenediamine and terephthalic acid, a salt of diamine and terephthalic acid having 7 or more carbon atoms, mixing them in the presence of water, and heating to proceed the dehydration reaction. Used. However, since the salt of diamine and terephthalic acid having 7 or more carbon atoms is inferior in water solubility, a method of preparing raw materials without preparing a salt may be used.

  When preparing the salt in advance, changing the mixing ratio of the salt of pentamethylenediamine and terephthalic acid, the diamine having 7 or more carbon atoms and the salt of terephthalic acid. By changing, 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 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 1.003 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 1.008 to 1.05. More preferably, it is 1.010-1.04. When a / b is less than 1.003, the total amount of amino groups in the polymerization system is extremely smaller than the total amount of carboxyl groups, making it difficult to obtain a sufficiently high molecular weight polymer. On the other hand, when a / b is larger than 1.10, the total amount of carboxyl groups in the polymerization system is extremely smaller than the total amount of amino groups, and it becomes difficult to obtain a sufficiently high molecular weight polymer. Furthermore, the volatilization amount of the diamine component increases, which is not preferable from the viewpoint of productivity and environment.

  The degree of polymerization of the polyamide resin of the present invention requires that the relative viscosity at 25 ° C. of a 98% sulfuric acid solution of 0.01 g / ml be 1.5 to 4.5. Most preferably, it is 2.0-3.5. If the relative viscosity is less than 1.5, the practical strength is insufficient, and if it is 4.5 or more, the fluidity is lowered and the molding processability is impaired.

  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.

  In addition, when the inorganic filler is pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound, it can obtain better mechanical strength. Preferred in meaning. Particularly preferred are organosilane compounds, and specific examples thereof include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyl. Epoxy group-containing alkoxysilane compounds such as trimethoxysilane, γ-mercaptopropyltrimethoxysilane, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxy Silane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane and other ureido group-containing alkoxysilane compounds, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyana Isocyanato group-containing alkoxysilane compounds such as topropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane Amino group-containing alkoxysilane compounds such as γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxypropyltri Hydroxyl-containing alkoxysilane compounds such as methoxysilane and γ-hydroxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N-β- (N-bi Nylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrocarbon salt-containing alkoxysilane compounds such as hydrochloride, and acid anhydride group-containing alkoxysilane compounds such as 3-trimethoxysilylpropylsuccinic acid. 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 0.1-100 weight part with respect to 100 weight part of polyamide resins. More preferably, it is 1 to 80 parts by weight, further preferably 1.1 to 60 parts by weight, and most preferably 5 to 50 parts by weight. If the amount is less than 0.1 parts by weight, the effect of improving rigidity and strength is small. If the amount exceeds 100 parts by weight, it is difficult to uniformly disperse in the polyamide resin, and the strength tends to decrease.

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

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

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

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

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

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

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

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

  The compounding amount of the impact resistance improving material 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.

  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.

  Further, 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 within the range not impairing the effects of the present invention. 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.) (E.g., hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resin, or a combination of these brominated flame retardants and antimony trioxide) at any time. Can do.

  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), glass transition temperature (Tg)]
About 5 mg of a sample was sampled using a Seiko Instruments robot DSC RDC220 and measured under the following conditions in a nitrogen atmosphere. After the temperature was raised to the melting point of the polyamide resin + 40 ° C. to obtain a molten state, the temperature was lowered to 30 ° C. at a temperature lowering rate of 20 ° C./min. The temperature of the endothermic peak (melting point: Tm) observed when the temperature was raised to the melting point + 40 ° C. at the rate of temperature rise was determined. Also, from the temperature at the midpoint of the stepwise endothermic peak of the DSC curve observed when the sample was rapidly cooled with liquid nitrogen from the melting point of the polyamide resin melting point + 30 ° C. at a rate of temperature increase of 20 ° C./min. The glass transition temperature (Tg) was determined.

[Water absorption rate]
A film having a thickness of about 150 μm prepared by hot pressing was treated in a hot air oven at 150 ° C. for 10 minutes. This film was immersed in water and treated in a hot air oven at 50 ° C. for 100 hours, and the water absorption was determined from the weight change rate before and after the treatment.

[Stay stability]
A sample held at a temperature of melting point + 20 ° C. in a nitrogen atmosphere for 1 hour was examined to see if it dissolved in 98% sulfuric acid at a concentration of 0.01 g / ml. It showed in.

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 1-11, Comparative Examples 1-4, 6-11
Aliphatic diamine and dicarboxylic acid equimolar salts or raw materials were directly weighed and blended so that the weight ratios shown in Tables 1, 2 and 3 were obtained. Except for the case where the diamine having the highest content among all aliphatic diamines is a diamine having 7 or more carbon atoms, an excessive amount of 1.0 mol% of the diamine as the main component is added to the total aliphatic diamine. . 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 resin oligomer. The obtained polyamide resin oligomer was pulverized, dried, and solid-phase polymerized at 50 Pa and 240 ° C. (Comparative Examples 3 and 4 were solid-phase polymerized at 180 ° C.) to obtain a polyamide resin.

The abbreviations shown in Table 1, Table 2, and Table 3 are as follows.
5T: equimolar salt of pentamethylenediamine and terephthalic acid 10T: equimolar mixture of 1,10-decanediamine and terephthalic acid 9T: equimolar mixture of 1,9-nonanediamine and terephthalic acid 56: of pentamethylenediamine and adipic acid Equimolar salt 106: equimolar mixture of 1,10-decanediamine and adipic acid 66: equimolar salt of hexamethylenediamine and adipic acid 6T: equimolar salt of hexamethylenediamine and terephthalic acid 1010: 1,10-decanediamine And equimolar mixture of sebacic acid 6: aminocaproic acid

Comparative Example 5
To an equimolar salt of pentamethylenediamine and adipic acid, an excess of 1.0 mol% of pentamethylenediamine was added to the pentamethylenediamine in the salt. 30 parts by weight of water was added to and mixed with 70 parts by weight of all raw materials. This was charged into a pressure vessel, sealed, and purged with nitrogen. Start the heating, after the can internal pressure reaches 17.5 kg / cm ^2, while releasing moisture out of the system can internal pressure 17.5 kg / cm ^2, at a temperature 240 ° C. cans 1.5 hour hold did. Thereafter, the internal pressure of the can was returned to normal pressure over 1 hour, and further maintained at 270 ° C. for 30 minutes under a reduced pressure of −160 mmHg to complete the polymerization. The polymer was discharged from the polymerization can in a gut shape and pelletized to obtain a polypentamethylene adipamide resin.

  By comparing Examples 1 to 7 and Comparative Example 1 together with a diamine having 7 or more carbon atoms and pentamethylene diamine, a polyamide resin having excellent residence stability can be obtained.

  By comparing Examples 8 to 10 and Comparative Examples 2 to 4, among the constituent components, the total weight of pentamethylene diamine, diamine having 7 or more carbon atoms, and terephthalic acid derivative is set to 80% by weight or more. Thus, a polyamide resin excellent in low water absorption can be obtained.

  A comparison between Example 4 and Comparative Examples 7 and 11 improves the molding processability by using a diamine having 7 or more carbon atoms, and further makes it a polyamide resin having excellent retention stability by using it together with pentamethylenediamine. be able to.

Example 12
After dry blending 100 parts by weight of the polyamide resin obtained in Example 5 and 35 parts by weight of glass fiber (T-747GH manufactured by Nippon Electric Glass Co., Ltd.), the mixture was supplied to the hopper of a 40 mmφ single screw extruder, and the cylinder temperature was 310 ° C. Melt kneading was performed under the condition of a screw rotation speed of 100 rpm to obtain a glass fiber reinforced composition. This composition has a melting point of 290 ° C. and a water absorption rate of 2.91%, and can further reduce water absorption as compared with the polyamide resin of Example 5.

Example 13
100 parts by weight of a polyphenylene ether resin (Mitsubishi Engineering Plastics Iupiace PX-100F), 1.2 parts by weight of maleic anhydride and 0.1 parts by weight of a radical generator (Perhexine 25B: manufactured by NOF Corporation) are dry blended and cylinder A modified polyphenylene ether resin was prepared by melt-kneading at a temperature of 320 ° C. After 100 parts by weight of the polyamide resin obtained in Example 5 and 30 parts by weight of the modified polyphenylene ether resin were dry blended, they were supplied to a hopper of a 40 mmφ single screw extruder, under conditions of a cylinder temperature of 310 ° C. and a screw rotation speed of 100 rpm. Melt kneading was performed to obtain a polyamide resin composition. This composition has a melting point of 289 ° C. and a water absorption rate of 2.78%, and can further reduce water absorption as compared with the polyamide resin of Example 5.

Claims (10)

98% of 0.01 g / ml obtained by polycondensation of an aliphatic diamine containing pentamethylenediamine and a diamine having 7 or more carbon atoms as main components and a dicarboxylic acid derivative containing terephthalic acid derivatives as main components A polyamide resin having a relative viscosity of 1.5 to 4.5 at 25 ° C. of the sulfuric acid solution. Using a differential scanning calorimeter, the melting point is 255 ° C. or higher and 314 ° C. or lower when the temperature is lowered from a 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 glass transition temperature is 100 ° C or higher and 160 ° C or lower. The polyamide resin according to any one of claims 1 to 3, wherein the pentamethylenediamine component is 5% by weight or more and 80% by weight or less based on the total amount of the aliphatic diamine. The polyamide resin according to any one of claims 1 to 4, wherein the terephthalic acid derivative component is 70% by weight or more based on the total amount of the dicarboxylic acid derivative. The diamine having 7 or more carbon atoms is at least one selected from 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane. The polyamide resin described. The polyamide resin composition formed by mix | blending 0.1-100 weight part of inorganic fillers with respect to 100 weight part of polyamide resins in any one of Claims 1-6. The polyamide resin composition according to claim 7, comprising an inorganic filler having an organic functional group introduced therein. A polyamide resin composition obtained by blending 5 to 100 parts by weight of an impact resistance improver with 100 parts by weight of the polyamide resin according to any one of claims 1 to 6. A molded article comprising the polyamide resin according to any one of claims 1 to 6 or the polyamide resin composition according to any one of claims 7 to 9.