JP4158399B2 - Polyamide resin - Google Patents

Description

【００６３】
実施例１〜３と比較例１〜３の比較により、側鎖に置換基がない特定の脂肪族ジアミンと、テレフタル酸を特定の組成比で重縮合することによって、溶融成形可能な、結晶化速度、結晶化度が高いポリアミド樹脂が得られることを確認した。
【００６４】
【発明の効果】
本発明により、ペンタメチレンジアミンとヘキサメチレンジアミンを主要成分として含有する脂肪族ジアミンと、テレフタル酸誘導体を主要成分として含有するテレフタル酸誘導体を特定の組成比で重縮合することにより、溶融成形可能な、耐熱性、結晶性に優れたポリアミド樹脂を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aliphatic diamine containing pentamethylenediamine and hexamethylenediamine as main components and a dicarboxylic acid containing a terephthalic acid derivative as a main component, the melting point of which is controlled to be lower than the decomposition temperature of the polymer. The present invention relates to a polyamide resin having a high crystallization temperature and a high crystallinity.
[0002]
[Prior art]
Conventionally, semi-aromatic polyamides have been proposed as polyamides having excellent heat resistance, dimensional stability, and mechanical properties. For example, a semi-aromatic polyamide homopolymer composed of a short-chain aliphatic diamine such as tetramethylene diamine, pentamethylene diamine, and hexamethylene diamine and terephthalic acid has a melting point higher than the decomposition temperature of the polymer and is difficult to melt-mold. . Therefore, as a semi-aromatic polyamide, for example, a polyamide composed of a mixture of hexamethylene diamine and 2-methylpentamethylene diamine and terephthalic acid is disclosed in JP-T-6-50359. In this semi-aromatic polyamide, it is considered that 2-methylpentamethylenediamine is copolymerized as a third component to control the melting point of the polymer so that it can be melt-molded.
[0003]
[Problems to be solved by the invention]
However, since the aliphatic diamine having a methyl group introduced into the side chain is more sterically hindered than the aliphatic diamine having no substituent in the side chain, the copolymerization of such a third component is not possible with the polymer. Although effective as a technique for lowering the melting point, there has been a problem of causing a decrease in crystallization speed and crystallinity.
[0004]
Therefore, the present inventors polycondensate a mixture of a specific aliphatic diamine having no substituent in the side chain with terephthalic acid, thereby changing the melting point of the polyamide resin to 290 ° C. or higher and 330 ° C., which is lower than the decomposition temperature. The inventors have found that a polyamide resin can be obtained that is controlled at a temperature of ℃ or less, can be melt-molded, and has a high crystallization speed and high crystallinity.
[0005]
[Means for Solving the Problems]
  That is, the present invention
  (1) A polyamide resin obtained by polycondensation of an aliphatic diamine containing pentamethylenediamine and hexamethylenediamine as main components and a dicarboxylic acid derivative containing terephthalic acid derivatives as main components,The hexamethylenediamine component in the aliphatic diamine is 30 mol% or more and 68 mol% or less with respect to the total aliphatic diamine,Using a differential scanning calorimeter, the polyamide resin is cooled from a molten state to 30 ° C. at a temperature decrease rate of 20 ° C./min, and then has a melting point of 290 ° C. or higher when heated at a temperature increase rate of 20 ° C./min. A polyamide resin having a temperature of ℃ or less.
[0006]
(2) The temperature-falling crystallization temperature that appears when the temperature is lowered from the molten state to 30 ° C. at a rate of temperature reduction of 20 ° C./min using a differential scanning calorimeter is 250 ° C. or higher. Polyamide resin.
[0007]
(3) The polyamide resin according to (1) or (2), wherein an absolute value of the temperature-falling crystallization in the temperature-falling crystallization temperature ± 40 ° C range is 40 J / g or more.
[0008]
(4) It is obtained by heat polycondensation of an aliphatic diamine containing pentamethylenediamine and hexamethylenediamine as main components and a dicarboxylic acid containing terephthalic acid as main components (1) to (3 ) Any of the polyamide resins.
[0009]
(5) It is obtained by heat polycondensation of a mixture of an aliphatic diamine containing pentamethylenediamine and hexamethylenediamine as main components and a dicarboxylic acid salt containing terephthalic acid as main components, and water. The polyamide resin according to (4).
[0010]
(6) The pentamethylenediamine is produced from lysine using a microorganism having lysine decarboxylase, a recombinant microorganism having improved lysine carbonase activity, or an extract thereof (1) -Polyamide resin as described in (5).
Consists of.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
[0012]
The present invention is a copolymerized polyamide derived from an aliphatic diamine containing pentamethylenediamine and hexamethylenediamine as main components and a dicarboxylic acid derivative containing terephthalic acid derivatives as main components. Further, since it is intended to obtain a polyamide resin having excellent heat resistance and capable of being melt-molded, using a differential scanning calorimeter, the polyamide resin is removed from the molten state at 20 ° C./min under an inert gas atmosphere. It is necessary that the temperature of the endothermic peak that appears when the temperature is decreased to 30 ° C. at a temperature decreasing rate and then increased at a temperature increasing rate of 20 ° C./min is 290 ° C. to 330 ° C. 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 290 ° C., the heat resistance is lowered, so the melting point needs to be controlled to 290 ° C. or higher. Further, when the melting point is higher than 330 ° C, the decomposition of the polyamide is promoted and it becomes difficult to perform melt molding. Therefore, it is necessary to control the melting point to 330 ° C or lower. Here, examples of the terephthalic acid derivative include terephthalic acid, terephthalic acid chloride, and dimethyl terephthalate.
[0013]
In the present invention, the main component means that the total number of moles of pentamethylene diamine, hexamethylene diamine and terephthalic acid among the constituent components is at least 90.mol% Or more, preferably 95molPolyamide containing at least%.
[0014]
  Further, the hexamethylene diamine component in the aliphatic diamine is mixed and used so that it is 30 mol% or more and 68 mol% or less with respect to the total aliphatic diamine.The
[0015]
Hexamethylenediamine component in the aliphatic diamine is 30mol%, 68molWhen it is more than%, the melting point of the polyamide resin is higher than 330 ° C., and melt molding becomes difficult.
[0016]
Further, in the present invention, when the temperature is lowered from the molten state, a polyamide resin that is quickly crystallized is to be obtained. Therefore, using a differential scanning calorimeter, the temperature is lowered from the molten state by 20 ° C./min. The temperature of the exothermic peak that appears when the temperature is lowered to 30 ° C is preferably 250 ° C or higher. In the present invention, the temperature of this exothermic peak is defined as the temperature-falling crystallization temperature. However, when two or more exothermic peaks are detected, the exothermic peak having the highest peak intensity is set as the temperature-falling crystallization temperature. A temperature lowering crystallization temperature lower than 250 ° C. is not preferable because crystallization from a molten state is slow.
[0017]
In the present invention, since a polyamide resin having a high degree of crystallinity is to be obtained, the temperature drop that appears in the differential scanning calorimetric curve when the temperature is lowered to 30 ° C. at a temperature drop rate of 20 ° C./min from the molten state. It is preferable that the absolute value of the cooling crystallization heat amount obtained when the crystallization temperature + 40 ° C. and the cooling crystallization temperature −40 ° C. are used as a baseline is 40 J / g or more. As the absolute value of the temperature drop crystallization heat quantity is larger, it is considered that the degree of crystallization when the temperature is lowered from the molten state is increased. Therefore, the temperature drop crystallization heat quantity is more preferably 45 J / g or more.
[0018]
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 and hexamethylenediamine and terephthalic acid are heated at a high temperature to cause a dehydration reaction. A mixture of pentamethylenediamine and hexamethylenediamine is dissolved in water, and terephthalic acid chloride is dissolved in water. And a method of dissolving them in an organic solvent that is not mixed with them and polycondensing them 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.
[0019]
As the heat polymerization method, a method of preparing a salt of pentamethylene diamine and terephthalic acid, a salt of hexamethylene diamine and terephthalic acid, mixing them in the presence of water, and heating to proceed the dehydration reaction is preferably used. . Further, the copolymer composition ratio in the polyamide can be changed by changing the mixing ratio of the salt of pentamethylenediamine and terephthalic acid or the salt of hexamethylenediamine and terephthalic acid. When the salt of hexamethylene diamine and terephthalic acid is 70 wt% or more or 29 wt% or less with respect to the total salt amount, the melting point of the resulting polyamide is higher than 330 ° C. The acid salt is preferably 30 wt% or more and 69 wt% or less with respect to the total salt amount. Furthermore, the polyamide resin of the present invention can also be increased in molecular weight by further solid-phase polymerization after heat polycondensation. 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.
[0020]
There is no restriction | limiting in particular in the polymerization degree of the polyamide resin of this invention, It is preferable that the relative viscosity in 25 degreeC of the 98% sulfuric acid solution made 0.01 g / ml is 1.5-8.0, and 1.8- More preferably, it is 5.0. If the relative viscosity is less than 1.5, the practical strength is insufficient, and if it is 8.0 or more, the fluidity is lowered and the molding processability is impaired.
[0021]
The polyamide resin of the present invention contains 10 of the constituent components.mol%, Preferably 5molIt is possible to copolymerize other components in an amount of less than% and do not impair the effects of the present invention. Typical copolymerization 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, oxalic acid, malon Aliphatic acids such as 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, octadecanedioic acid Dicarboxylic acid, cycloaliphatic dicarboxylic acid such as cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, aromatic dicarboxylic acid such as naphthalenedicarboxylic acid, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane 1,7-diaminoheptane, 1,8-di Aminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diamino Pentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 2-methyl-1,5-diaminopentane And aliphatic diamines such as cyclohexanediamine, alicyclic diamines such as bis- (4-aminohexyl) methane, and aromatic diamines such as xylylenediamine.
[0022]
The production method of pentamethylenediamine constituting the present invention is not limited. For example, a method of synthesizing from lysine using vinyl ketones such as 2-cyclohexen-1-one as a catalyst (Chemistry Letters, 893 (1986), JP 4-B) 10452) and a method for converting from lysine using lysine decarboxylase have already been proposed. As the reaction temperature increases, the amount of 2,3,4,5-tetrahydropyridine and piperidine produced by the deammonification reaction increases as the reaction temperature increases, and these cyclic amines may decompose the polyamide resin. Therefore, it is preferable to obtain pentamethylenediamine by a production method having a low reaction temperature because the amount of cyclic amine as a by-product can be reduced. In the former method, the reaction temperature is as high as about 150 ° C., whereas the latter method is less than 100 ° C., so it is preferable to use pentamethylenediamine obtained by the latter method as a raw material.
[0023]
The lysine decarboxylase used in the latter method is an enzyme that converts lysine to pentamethylenediamine, and is known to exist not only in Escherichia coli microorganisms such as Escherichia coli K12 but also in many organisms. Yes.
[0024]
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. .
[0025]
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.
[0026]
Further, a plurality of lysine decarboxylases may be used in combination.
[0027]
Microorganisms having such lysine decarboxylase include Bacillus halodurans, Bacillus subtilis, Escherichia coli, Selenomonas ruminantium, Vibrio cholera ( Vibrio cholerae), Vibrio parahaemolyticus, Streptomyces coelicolor, Streptomyces pilosus, Eikenella corrodens, E. bacterium u acidaminophilum, Salmonella typhimurium, Hafnia alvei, Neisseria meningitidis, Thermoplasma acidophilum Pyrococcus abyssi or Corynebacterium glutamicum.
[0028]
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.
[0029]
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, 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, or yeast extract. In addition to these, a small amount of calcium phosphate, calcium sulfate, iron ion, manganese ion or the like is added as necessary.
[0030]
The culture conditions are not particularly limited. For example, in the case of E. coli, the culture is preferably performed for about 16 to 72 hours under aerobic conditions, and the culture temperature is 30 ° C to 45 ° C, particularly preferably 37 ° C. The pH should be controlled to 5-8, particularly preferably pH 7. For adjusting the pH, inorganic or organic acidic or alkaline substances, ammonia gas and the like can be used.
[0031]
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.
[0032]
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.
[0033]
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.
[0034]
There is no particular limitation on the concentration of lysine in the reaction solution.
[0035]
The amount of lysine decarboxylase may be sufficient to catalyze the reaction of converting lysine to pentamethylenediamine.
[0036]
The reaction temperature is usually 28 to 55 ° C, preferably around 40 ° C.
[0037]
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.
[0038]
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.
[0039]
A filler, another kind polymer, etc. can be added to the polyamide resin of the present invention. 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 of the present invention 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.
[0040]
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.
[0041]
Examples of the (co) polymer include an ethylene copolymer, a conjugated diene polymer, and a conjugated diene-aromatic vinyl hydrocarbon copolymer.
[0042]
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.
[0043]
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, and 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 aryl. Examples include esters, glycidyl esters, acid anhydrides, and imides.
[0044]
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.
[0045]
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 part or all of unsaturated bonds other than double bonds other than aromatic rings are reduced by hydrogenation can be preferably used.
[0046]
Polyamide elastomers and polyester elastomers can also be used. Two or more of these impact resistance improving materials can be used in combination.
[0047]
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 these, 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 preferred, 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.
[0048]
Furthermore, the polyamide resin of the present invention has various additives such as antioxidants and heat stabilizers (hindered phenols, hydroquinones, phosphites and their substitution products, halogenated compounds, etc. as long as the effects of the present invention are not impaired. Copper, iodine compounds, etc.), weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), mold release agents and lubricants (aliphatic alcohol, aliphatic amide, aliphatic bisamide, bisurea and polyethylene) Waxes, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, aniline black, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkyl sulfates) Type anionic antistatic agent, quaternary ammonia Salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, etc.), flame retardant (melamine cyanurate, magnesium hydroxide, aluminum hydroxide, etc.) (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.
[0049]
The polyamide resin 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., and can be molded into resin molded products such as machine parts, clothing / industrial It can be used as a fiber for materials, packaging and magnetic recording films.
[0050]
【Example】
Examples Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of these examples.
[0051]
[DSC (Differential Scanning Calorimetry)]
Using a robot DSC RDC220 manufactured by Seiko Denshi Kogyo, approximately 5 mg of a sample was collected under a nitrogen atmosphere and measured under the following conditions.
After the sample is completely melted and held for 3 minutes, the temperature of the exothermic peak (temperature-decreasing crystallization temperature Tc) that appears when the temperature is lowered to 30 ° C. at a rate of temperature decrease of 20 ° C./min, and the temperature of the exothermic peak ± 40 ° C. The amount of heat in this range (temperature-falling crystallization heat amount ΔHc) was determined. Subsequently, after maintaining at 30 ° C. for 3 minutes, the temperature of the endothermic peak (melting point Tm) observed when the temperature was increased from 30 ° C. at a rate of temperature increase of 20 ° C./min was determined.
[0052]
[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.
[0053]
Reference example 1 (adjustment of lysine decarboxylase)
The E. coli JM109 strain was cultured as follows. First, this platinum strain was inoculated into 5 ml of LB medium, and precultured by shaking at 30 ° C. for 24 hours.
[0054]
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)).
[0055]
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, may occur. The cell-free extract was heated. Furthermore, this cell-free extract was fractionated with 40% saturated and 55% saturated ammonium sulfate. Using the crude purified lysine decarboxylase solution thus obtained, pentamethylenediamine was produced from lysine.
[0056]
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.
[0057]
Reference Example 3 (Preparation of salt of pentamethylenediamine and terephthalic acid)
An aqueous solution obtained by dissolving 20.0 g of pentamethylenediamine of Reference Example 2 in 122.6 g of water is immersed in a water bath at 60 ° C. and stirred, and about 1 g of terephthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) is added. In the vicinity of the neutralization point, about 0.2 g was added, and the pH change of the aqueous solution with respect to the addition amount of terephthalic acid was examined. The neutralization point was determined to be pH 7.24. The amount of adipic acid added at the neutralization point was 32.5 g. A 30 wt% aqueous solution of an equimolar salt of pentamethylenediamine and terephthalic acid was prepared so that the pH was 7.24.
[0058]
Reference Example 4 (Preparation of 2-methylpentamethylenediamine and terephthalic acid salt)
An aqueous solution obtained by dissolving 20.0 g of 2-methylpentamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) in 113.4 g of water is immersed in a 60 ° C. water bath and stirred, and about 1 g of terephthalic acid is added. About 0.2 g was added in the vicinity of the neutralization point, and the pH change of the aqueous solution with respect to the addition amount of terephthalic acid was examined to obtain a neutralization point of pH 7.02. The amount of terephthalic acid added at the neutralization point was 28.6 g. A 30 wt% aqueous solution of an equimolar salt of 2-methylpentamethylenediamine and terephthalic acid was prepared so that the pH was 7.02.
[0059]
Reference Example 5 (Preparation of a salt of hexamethylenediamine and terephthalic acid)
An aqueous solution prepared by dissolving 20.0 g of hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) in 194.4 g of water is immersed in a 60 ° C. water bath and stirred, and about 1 g of terephthalic acid is added at a neutralization point. About 0.2 g was added in the vicinity, and the pH change of the aqueous solution with respect to the addition amount of terephthalic acid was examined to obtain a neutralization point of pH 7.14. The amount of terephthalic acid added at the neutralization point was 28.6 g. A 20 wt% aqueous solution of an equimolar salt of pentamethylenediamine and terephthalic acid was prepared so that the pH was 7.14.
[0060]
  Example 13Comparative Example 1
  A 30 wt% aqueous solution of an equimolar salt of pentamethylene diamine and terephthalic acid prepared in Reference Example 3 and a 20 wt% aqueous solution of hexamethylene diamine and terephthalic acid prepared in Reference Example 5 were used. About 60 g of the mixed solution was charged into a test tube, placed in an autoclave, sealed, and purged with nitrogen. The jacket temperature was set to 310 ° C. and heating was started. The pressure inside the can is 17.5 kg / cm²The pressure inside the can is 17.5 kg / cm²For 3 hours. Thereafter, the jacket temperature was set to 320 ° C., and the internal pressure of the can was released to normal pressure over 1 hour. Thereafter, when the internal temperature reached 280 ° C., heating was stopped. After cooling to room temperature, the test tube was removed from the autoclave to obtain a polyamide resin. The polyamide resin thus obtained was pulverized and subjected to solid phase polymerization at 240 ° C. and 0.3 torr for 10 hours to obtain a polyamide resin.
[0061]
Comparative Examples 2 and 3
Using a 30 wt% aqueous solution of an equimolar salt of 2-methylpentamethylenediamine and terephthalic acid prepared in Reference Example 4 and hexamethylenediamine and terephthalic acid prepared in Reference Example 5, a polyamide resin was prepared in the same manner as in Example 1. Got.
[0062]
[Table 1]

[0063]
  Example 13Comparison of Comparative Examples 1 to 3 shows that a specific aliphatic diamine having no substituent in the side chain and terephthalic acid are polycondensed at a specific composition ratio, and can be melt-molded. It was confirmed that a high polyamide resin was obtained.
[0064]
【The invention's effect】
According to the present invention, melt molding is possible by polycondensing an aliphatic diamine containing pentamethylenediamine and hexamethylenediamine as main components and a terephthalic acid derivative containing terephthalic acid derivatives as main components at a specific composition ratio. A polyamide resin excellent in heat resistance and crystallinity can be obtained.

Claims (6)

And aliphatic diamines containing pentamethylenediamine and hexamethylenediamine as the main component, a dicarboxylic acid derivative containing a terephthalic acid derivative as the main component a polycondensation polyamide resin obtained by, hexa in the aliphatic diamine The methylenediamine component was 30 mol% or more and 68 mol% or less with respect to the total aliphatic diamine, and the polyamide resin was cooled to 30 ° C. from the molten state at a temperature decreasing rate of 20 ° C./min using a differential scanning calorimeter. Thereafter, a polyamide resin having a melting point of 290 ° C. or higher and 330 ° C. or lower when the temperature is raised at a rate of 20 ° C./min. The polyamide resin according to claim 1, wherein a temperature-falling crystallization temperature that appears when the temperature is lowered from a molten state to 30 ° C at a rate of temperature reduction of 20 ° C / min using a differential scanning calorimeter is 250 ° C or higher. 3. The polyamide resin according to claim 1, wherein an absolute value of a temperature-falling crystallization heat amount in a range of ± 40 ° C. of the temperature-falling crystallization temperature is 40 J / g or more. It is obtained by heat polycondensation of an aliphatic diamine containing pentamethylenediamine and hexamethylenediamine as main components, and a dicarboxylic acid containing terephthalic acid as a main component. Polyamide resin. A dicarboxylic acid salt containing pentamethylenediamine and hexamethylenediamine as main components and a dicarboxylic acid salt containing terephthalic acid as main components and a mixture of water are obtained by heat polycondensation. 4. The polyamide resin according to 4. 6. The pentamethylene diamine is produced from lysine using a microorganism having lysine decarboxylase, a recombinant microorganism having improved lysine carbonase activity, or an extract thereof. Polyamide resin.