JP2016069644A - Polyamide resin, manufacturing method therefor and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin having high melting point excellent in long time molten retention stability.SOLUTION: There is provided a polyamide resin containing a dicarboxylic acid unit of which 50 to 100 mol% consists of an oxalic acid unit and a diamine unit, nonionic organic iodine compound in the polyamide resin and the content of iodine atom derived from the nonionic organic iodine compound is 20 ppm to 6000 ppm based on the weight of the polyamide resin.SELECTED DRAWING: None

Description

  The present invention relates to a polyamide resin containing a nonionic organic iodine compound and having excellent long-term melt retention stability.

  Nylon 6 and nylon 66, which are representative of crystalline polyamides, are widely used as clothing, industrial fibers, or general engineering plastics because of their excellent characteristics and ease of melt molding. However, on the other hand, there are problems such as changes in physical properties caused by water absorption, deterioration in acid, high-temperature alcohol, and hot water, and there is an increasing demand for polyamide resins with excellent dimensional stability, chemical resistance, and heat resistance. ing. In the field of electrical and electronic parts, with the development of surface mounting (SMT) technology, there is an increasing demand for polyamide resins having high heat resistance including reflow heat resistance. Thus, there is a need to develop high quality polyamides that have good heat resistance, good dimensional stability, and good chemical resistance.

  On the other hand, a polyamide resin called a polyoxamide having an oxalic acid unit as a dicarboxylic acid unit is known. Compared to other polyamide resins having the same amide group concentration, it has a low water absorption, so that it can solve the problem of deterioration of physical properties due to water absorption and can be expected to be used in a region where it is difficult to use the current polyamide.

  For example, polyoxamide having 1,6-diaminohexane as a diamine unit shown in Non-Patent Document 1 (J. Polym. Sci., 11, 1 (1973)) has a high melting point (320 ° C. or higher) and is melt-processed. Sometimes significant degradation occurs. In addition, among the polyoxamide PA62 / 2-M52 resins described in Patent Document 1 (WO2011 / 136263), the polyoxamide resin having a melting point of 280 ° C. or higher does not increase in relative viscosity (relative viscosity less than 2.05), In addition, the viscosity of the resin is greatly reduced during melt processing. Furthermore, in the polyoxamide PA52 resin described in Patent Document 2 (Japanese Patent Application Laid-Open No. 2011-236387), the viscosity is increased by a specific solid phase polymerization method, but the melt retention stability is poor, and the polyoxamide resin at the time of melt processing is poor. The viscosity is greatly reduced. Thus, the polyamide resin containing an oxalic acid unit has a problem of poor melt residence stability.

  Patent Document 3 (Japanese Translation of PCT International Publication No. 2002-527558) shows that the addition of an organic halogen compound is effective for thermal stabilization of a polyamide resin. However, there was no specific description of the organic iodine compound. Further, Patent Document 4 (Japanese Patent Application Laid-Open No. 63-275627) describes a halogen organic compound as a polymerization catalyst for polyamide resin, but there is no description for improving the melt residence stability. Furthermore, Patent Document 5 (CN1038665058A) shows that the addition of a metal halide compound is effective in order to improve the melt residence stability of a polyamide resin containing an oxalic acid unit. However, there has been a demand for improvement in long-term melt residence stability.

International Publication No. 2011-136263 JP 2011-236387 A JP-T-2002-527558 JP-A 63-275627 Chinese Patent Application No. 103865058

J. et al. Polym. Sci. , 11, 1 (1973)

  An object of the present invention is to provide a polyamide resin having a high melting point that is excellent in long-term melt residence stability.

In order to solve the above problems, the present invention has the following configuration.
(1) A polyamide resin in which 50 to 100 mol% of the dicarboxylic acid unit includes a dicarboxylic acid unit composed of an oxalic acid unit and a diamine unit, the polyamide resin includes a nonionic organic iodine compound, A polyamide resin, wherein the content of iodine atoms derived from a nonionic organic iodine compound is 20 ppm or more and 6000 ppm or less based on weight.
(2) A 96% sulfuric acid solution was used as a solvent to prepare a sulfuric acid solution having a polyamide resin concentration of 0.01 g / ml, and the relative viscosity A measured at 25 ° C. of the sulfuric acid solution was 1.8. It is the range of -6.0, The polyamide resin as described in (1) characterized by the above-mentioned.
(3) When the polyamide resin is cooled from the molten state to 30 ° C. at a temperature lowering rate of 20 ° C./min using a differential scanning calorimeter under an inert gas, and then measured at a temperature rising rate of 20 ° C./min. The polyamide resin according to either (1) or (2), wherein the melting point appearing in the temperature raising process is 280 to 320 ° C.
(4) The ratio (B / A) of the relative viscosity B after melting and staying at a temperature of the melting point of the polyamide resin + 20 ° C. for 2 hours in a nitrogen atmosphere and the relative viscosity A of the polyamide resin is 0.60 or more and 1.8. The polyamide resin according to any one of (2) and (3), wherein:
(5) The polyamide resin according to any one of (1) to (4), wherein the diamine unit is at least one selected from a tetramethylenediamine unit, a pentamethylenediamine unit, and a hexamethylenediamine unit.
(6) Any of (1) to (5), wherein the nonionic organic iodine compound is at least one selected from a saturated alkyl iodine compound, an unsaturated alkyl iodine compound, an aromatic iodine compound, and a heterocyclic iodine compound The polyamide resin described in 1.
(7) The polyamide resin according to any one of (1) to (6), wherein the nonionic organic iodine compound is 1,10-diiododecane and / or 2-amino-6-iodopurine.
(8) A step of synthesizing a prepolymer having a relative viscosity of 1.02 to 1.75, and post-polymerizing the prepolymer in a temperature range of 200 ° C. to 335 ° C. until the relative viscosity is 1.80 to 6.0 The method for producing a polyamide resin according to any one of (1) to (7), wherein a nonionic organic iodine compound is added during the post-polymerization step or after the post-polymerization step.
(9) The method for producing a polyamide resin as described in (8), wherein the post-polymerization step time is less than 5 hours.
(10) A molded product obtained by molding the polyamide resin according to any one of (1) to (7).

  According to the present invention, a polyamide resin having excellent melting stability for a long time and a high melting point can be obtained.

Hereinafter, the present invention will be described in detail.
In the present invention, the polyamide resin includes those containing a small amount of additives as long as the original performance of the polyamide resin is not impaired.

  In the present invention, the diamine unit is -NH-R-NH- (R is an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group), and the dicarboxylic acid unit is -CO-CO. — Or —CO—R′—CO— (R ′ represents an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group). These aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group may have a substituent.

  It is preferable that 10 to 100 mol% of the total amount of diamine units contained in the polyamide resin of the present invention is a diamine unit having 3 to 18 carbon atoms. More preferably, the diamine unit is at least one selected from a tetramethylenediamine unit, a pentamethylenediamine unit, and a hexamethylenediamine unit.

  Specific examples of the diamine used as a raw material for the diamine unit having 3 to 18 carbon atoms include 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7 -Heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14- Linear alkyl diamine such as tetradecane diamine, 1,15-pentadecane diamine, 1,16-hexadecane diamine, 1,17-heptadecane diamine, 1,18-octadecane diamine, 2-methyl-1,5-pentane diamine, 2 -Branched alkyl diamines such as methyl-1,8-octanediamine, cyclohexane diamine Alicyclic diamines such as, aromatic diamines such as diaminobenzene, and aromatic alkyl diamines such as xylylenediamine. By using a diamine having 3 to 18 carbon atoms as a raw material for the polyamide resin, a polyamide resin excellent in heat resistance and melt processability can be obtained. As for content of a C3-C18 diamine unit in a diamine unit, 50 mol% or more is preferable. More preferably, it is 80 mol% or more, more preferably 90 mol% or more, and most preferably 100 mol%. In order to improve the crystallinity of the polyamide resin, it is preferable to use a linear alkyldiamine as a raw material for the diamine unit. Further, in order to obtain a polyamide resin having a melting point of 280 ° C. or higher, at least one selected from 1,4-butanediamine, 1,5-pentanediamine, and 1,6-hexanediamine is used as a raw material for the diamine unit. It is preferable to include. As a raw material for the diamine unit of the homopolymer, 1,5-pentanediamine is preferable.

  In this invention, 50-100 mol% with respect to all the dicarboxylic acid units is an oxalic acid unit. By setting it in this range, a polyamide resin excellent in low water absorption can be obtained. In order to achieve both low water absorption and crystallinity, 80 mol% or more is preferable. 90 mol% or more is more preferable, and 100 mol% is the most preferable.

  As raw materials of the oxalic acid unit, oxalic acid, dimethyl oxalate, diethyl oxalate, di-n-propyl oxalate, diisopropyl oxalate, di-n-butyl oxalate, isobutyl oxalate, or di-t-oxalate One or more selected from butyl, diphenyl oxalate and the like can be mentioned. Particularly preferred are dimethyl oxalate, diethyl oxalate, di-n-propyl oxalate, di-n-butyl oxalate, and diphenyl oxalate, which are highly reactive with diamines.

  Examples of raw materials for dicarboxylic acid units other than oxalic acid units include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,11-undecylniic acid, and 1,12-dodecyl dicarboxylic acid. Aliphatic dicarboxylic acids such as acid, 1,13-tridecyl diacid, 1,14-tetradecyl niic acid, 1,15-pentadecyl niic acid, 1,16-cetyl niic acid, 1,18-octadecyl niic acid, 1,19-nonadecyl niic acid Acids, dialkyl esters of these aliphatic dicarboxylic acids, alicyclic dicarboxylic acids such as 1,4- / 1,3-cyclohexanedicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, dimethyl terephthalate, diethyl terephthalate , Dialkyl aromatic dicarboxylates such as dimethyl isophthalate and diethyl isophthalate Tel and the like.

  The raw material for the polyamide resin of the present invention may further contain lactam and aminocarboxylic acid. Examples of the lactam include caprolactam and laurolactam. Examples of aminocarboxylic acids include 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. The addition amount of the lactam component and / or aminocarboxylic acid component is preferably 20 mol% or less with respect to 100 mol% of the polyamide resin raw material. More preferably, it is 10 mol% or less.

  In order to improve the heat resistance and melt processability of the polyamide resin, the content of amide groups (the number of moles of amide groups in 1 g of polyamide) of the polyamide resin of the present invention is 7.8 mmol / g or more. preferable. The polyamide resin excellent in heat resistance can be obtained by setting it as 7.8 mmol / g or more. 9.0 mmol / g or more is more preferable, and 11.0 mmol / g or more is more preferable. On the other hand, the polyamide resin excellent in melt processability can be obtained by setting it as 14.0 mmol / g or less. 13.0 mmol / g or less is more preferable.

  Since the polyamide resin containing an oxalic acid unit of the present invention is inferior in melt retention stability as compared to a general-purpose polyamide resin such as nylon 66, it is essential to add a heat-resistant agent. However, it was impossible to improve the long-term melt residence stability only by adding a metal halide known as a representative example of the heat resistance agent of nylon 66. The present application has found that an organic iodine compound is effective in order to improve long-term melt residence stability, which is a problem peculiar to polyamide resins containing oxalic acid units. It is considered that the organic iodine compound is superior in dispersibility in the polyamide resin as compared with the metal halide and the organic bromine compound, and thus contributes to the improvement of the melt residence stability.

  Although it does not specifically limit as a nonionic organic iodine compound of this invention, In order to improve the dispersibility in a polyamide resin, it is preferable that a molecular weight is 1000 or less. More preferably, the molecular weight is 500 or less. Specific examples thereof include iodomethane, diiodomethane, triiodomethane, iodoethane, 1-iodopropane, 2-iodopropane, iodoisopropyl, 1-iodobutane, 2-iodobutane, 1-iodoisobutane, 2-iodoisobutane and 1-iodo. Pentane, 2-iodopentane, 3-iodopentane, 1-iodoisopentane, 2-iodoisopentane, 3-iodoisopentane, 1-iodohexane, 2-iodohexane, 3-iodohexane, 1-iodoisohexane, 2- Iodoisohexane, 3-iodoisohexane, 1-iodooctane, 1-iodononane, 1-iododecane, 1-iodododecane, 1-iodocyclopropane, 1-iodocyclobutane, 1-iodocyclopentane, 1-iodocyclohexane, 1, -Diiodoethane, 1,2-diiodoethane, 1,3-diiodopropane, 1,4-diiodobutane, 1,5-diiodopentane, 1,6-diiodohexane, 1,8-diiodooctane, 1,10 -Saturated alkyl iodine compounds such as diiododecane, 1,12-diiodododecane, unsaturated alkyl iodine compounds such as iodoallyl, iodobenzene, 1,4-diiodo-2,3,5,6-tetrahydrobenzene, 1 , 3-Dimethyl-2-iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 4,4′-diiododiphenyl, 1-iodo-4-butyl Benzene, 1-iodo-4- (trifluoromethoxy) benzene, 1-iodonaphthalene, 4-iodoanisole, 4-iodo Trobenzene, 3,5-diiodo-4-hydroxybenzonitrile, 2-iodofluorene, 4,4 "-diiodo-p-terphenyl, 4-iodo-2-nitrotoluene, 4-iodo-3-nitrotoluene, 3- Aromatic iodine compounds such as iodo-o-xylene, 3-iodoanisole and 2-iodo-5-nitroanisole, heterocyclic iodine compounds such as 2-amino-6-iodopurine and 4-iodopyridine, benzyl iodide ( Aromatic alkyl iodine compounds such as Benzyl iodide etc. Among these, nonionic organic iodine compounds having a boiling point of 200 ° C. or more that are less likely to volatilize during polyamide resin production or polyamide resin molding are preferred. Specific examples include 1,10-iododecane and / or 2-amino-6-iodopurine. That.

  The iodine content of the nonionic organic iodine compound in the polyamide resin is 20 to 6000 ppm. By making it 20 ppm or more, the melt residence stability of the polyamide resin can be improved. Preferably it is 100 ppm or more, More preferably, it is 200 ppm or more. On the other hand, by setting it to 6000 ppm or less, gelation when the polyamide resin is melted can be suppressed. Preferably, it is 3000 ppm or less, More preferably, it is 2000 ppm or less, More preferably, it is 1000 ppm or less.

  The polyamide resin undergoes thermal decomposition as described in Polymer Degradation and Stability 49 (1995), pages 127 to 133 during a high temperature processing step or when used in a high temperature environment. The methylene group adjacent to the nitrogen atom of the amide group tends to form free radicals easily. The free radical is stabilized by a resonance structure formed by a π bond between a lone pair on nitrogen and a carbonyl group. For example, in a polyamide resin such as polyamide 66, free radicals are generated in a methylene group adjacent to nitrogen in the amide group, and are easily thermally oxidized and decomposed. The polyamide resin of the present invention includes an oxamide unit as a structural unit, and the oxamide unit is adjacent to two amide groups, and can form a more stable resonance structure than a general single amide group. Therefore, free radicals are generated in the methylene group adjacent to nitrogen in the amide group, and are easily thermally oxidized and decomposed. The nonionic organic iodine compound found in the present invention can effectively suppress the thermal oxidative degradation of the polyamide resin, and in particular, the thermal oxidation of a polyamide resin having a high melting point (polyamide resin having a melting point of 280 ° C. or higher). The effect of suppressing decomposition is great.

  The 96% concentrated sulfuric acid solution as the solvent, the concentration of the polyamide resin is 0.01 g / ml, and the relative viscosity (A) ηr measured at 25 ° C. is preferably in the range of 1.8 to 6.0. By setting it to 1.8 or more, a polyamide resin excellent in toughness and strength can be obtained. More preferably, it is 2.0 or more, More preferably, it is 2.35 or more, Most preferably, it is 2.5 or more. On the other hand, by setting it to 6.0 or less, a polyamide resin having excellent melt processability can be obtained. More preferably, it is 4.5 or less, More preferably, it is 4.0 or less.

  In the present invention, using a differential scanning calorimeter, the polyamide resin is cooled from the molten state to 30 ° C. at a temperature decreasing rate of 20 ° C./min under an inert gas atmosphere, and then the temperature is increased by 20 ° C./min. The temperature of the endothermic peak that appears in the temperature rising process measured by the speed is defined as the melting point (Tm) of the polyamide resin. The melting point of the polyamide resin obtained by the present invention is preferably 280 ° C. or higher. More preferably, it is 290 degreeC or more. By setting the temperature to 280 ° C. or higher, a polyamide resin having excellent heat resistance can be obtained. The melting point of the polyamide resin is preferably 320 ° C. or less. More preferably, it is 315 degrees C or less. By setting it to 320 ° C. or lower, decomposition during melting can be suppressed.

  In the present invention, the ratio (B / A) of the relative viscosity B when the polyamide resin is melt-retained for 2 hours in a nitrogen atmosphere at a melting point of the polyamide resin + 20 ° C. and the relative viscosity A of the polyamide resin (B / A) Is preferably 0.60 to 1.8. By setting B / A to 0.60 or more, decomposition during melt processing can be suppressed. More preferably, it is 0.70 or more, and further preferably 0.80 or more. On the other hand, by setting B / A to 1.8 or less, significant thickening during melt processing can be suppressed. More preferably, it is 1.7 or less, More preferably, it is 1.6 or less. By setting the iodine atom content derived from the nonionic organic iodine compound to 20 ppm or more and 6000 ppm or less with respect to the weight of the polyamide resin, B / A can be controlled to 0.6 or more and 1.8 or less.

  The method for producing the polyamide resin of the present invention includes a step of synthesizing a polyamide prepolymer having a relative viscosity of 1.02 to 1.75, and a post-polymerization step for increasing the degree of polymerization in a temperature range of 200 ° C. to 335 ° C. And a method of adding a nonionic organic iodine compound at at least one time selected from the prepolymer synthesis step, the postpolymerization step, and the postpolymerization step. By this method, a polyamide resin having a relative viscosity of 1.8 to 6.0 and excellent melt stability can be obtained.

  Here, it is preferable to synthesize the prepolymer with the ratio (E / F) of the supply molar amount (E) of diamine to the supply molar amount (F) of dicarboxylic acid being 0.90 to 1.15. 0.95 or more is more preferable. Moreover, 1.10 or less is more preferable and 1.06 or less is further more preferable. By controlling E / F within the above range, the equimolarity of the diamine and the dicarboxylic acid is maintained, and the prepolymer can be easily increased in degree of polymerization.

  The time for the post-polymerization step when increasing the degree of polymerization of the prepolymer is preferably less than 5 hours. By setting it to less than 5 hours, the heat history at the time of superposition | polymerization reduces and deterioration of the obtained polyamide resin can be suppressed. The post-polymerization step time is more preferably less than 4 hours.

The following method is mentioned as a specific example of the manufacturing method of the polyamide resin of this invention.
Production method 1 (Prepolymer synthesis)
A raw material of an organic solvent and a diamine unit is added to a reactor equipped with a cooler, and nitrogen substitution is performed. Then, a raw material of a dicarboxylic acid unit is added and mixed. Next, stirring is started, and the mixture is heated to the reflux temperature of the solvent and reacted for 0.5 to 5 hours, and then the precipitated components are collected and dried to obtain a prepolymer. Although it does not specifically limit as an organic solvent, Toluene, xylene, chlorobenzene, phenol, or trifluoroethanol etc. are mentioned.

Production method 2 (post-polymerization: melt polymerization)
The prepolymer obtained by the production method 1 or a mixture of the prepolymer and the nonionic organic iodine compound was added into the reactor and replaced with an inert gas. This reactor is put in a heater, and then heating is started, and a temperature not lower than the melting point of the polymer is reached to carry out melt polymerization. The melt polymerization may be performed under reduced pressure or normal pressure. In the case of melt polymerization under reduced pressure, the pressure is preferably 500 Pa or less. By setting it as this range, deterioration of the polyamide resin can be suppressed and the post-polymerization time can be shortened. In addition, when melt polymerization is performed under normal pressure, it is preferably performed under an inert gas stream. By performing the process under an inert gas stream, deterioration of the polyamide resin can be suppressed. The post-polymerization time is preferably 0.1 to 5 hours. When the nonionic organic iodine compound is not added during the melt polymerization step, the organic iodine compound is added to the polymer after the melt polymerization step.

Production method 3 (post-polymerization: solid-phase polymerization)
The prepolymer obtained by the production method 1 or a mixture of the prepolymer and the nonionic organic iodine compound was added to the reactor and replaced with an inert gas. Thereafter, solid phase polymerization is performed at 200 ° C. or higher and a melting point or lower. Solid phase polymerization may be performed under reduced pressure or normal pressure. When solid phase polymerization is performed under reduced pressure, the pressure is preferably 500 Pa or less. By setting it as this range, deterioration of the polyamide resin can be suppressed and the post-polymerization time can be shortened. In addition, when solid phase polymerization is performed under normal pressure, it is preferably performed under an inert gas stream. By performing the process under an inert gas stream, deterioration of the polyamide resin can be suppressed. When the nonionic organic iodine compound is not added during the solid phase polymerization step, the organic iodine compound is added to the polymer after the solid phase polymerization step.

  The polyamide resin of the present invention may contain various fillers as necessary, and specific fillers are as follows.

  For example, as non-fibrous inorganic filler, graphite, barium sulfate, calcium carbonate, antimony oxide, titanium oxide, aluminum oxide, nickel, aluminum, iron, steel, talc, bentonite, montmorillonite, mica, titanium dioxide, silica, silicic acid Examples thereof include a filler such as salt. As the layered silicate, montmorillonite obtained by exchanging organic cations between layers with organic ammonium ions can also be used. In order to obtain a polyamide resin having an excellent surface appearance, the average particle diameter of the inorganic filler is preferably 0.001 μm to 10 μm. By setting the average particle size to 0.001 μm or more, the melt processability of the polyamide resin can be improved. On the other hand, when the average particle diameter is 10 μm or less, the appearance of the molded product can be improved.

  Moreover, an organic fibrous filler and an inorganic fibrous filler are also mentioned as another filler. Examples of the organic fibrous filler include aromatic polyamide fibers such as wholly aromatic polyamide fibers, and cellulose fibers. Examples of the inorganic fibrous filler include glass fiber, carbon fiber, and boron fiber. Moreover, 1 or more types, such as whisker or needle-like crystals, such as metal fiber, potassium titanate, aluminum borate, gypsum, calcium carbonate, magnesium sulfate, sepiolite, zonolite, wollastonite, are mentioned. Furthermore, a long fiber having a length of 5 to 50 mm can be used, and a fiber having a length of 0.05 to 5 mm can be used.

  When producing the polyamide resin of the present invention, various additives such as a weathering agent, a release agent, a lubricant, a pigment, a dye, a plasticizer, an antistatic agent, a flame retardant, or one as necessary. Other polymers as described above can be added. Specifically, resorcinol-based, salicylic acid-based, benzotriazole-based, benzophenone-based, hindered amine-based weathering agents, or release agents such as aliphatic alcohols, aliphatic amides, aliphatic bisamides, bisureas, polyethylene waxes, Lubricants, pigments such as cadmium sulfide, phthalocyanine and carbon black, dyes such as nigrosine and aniline black, plasticizers such as hydroxybenzoic acid octyl ester and N-butylbenzenesulfonamide, alkylsulfate anionic antistatic agents, Antistatic agent such as quaternary ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate alcohol or betaine amphoteric antistatic agent, melamine cyanurate, magnesium hydroxide or aluminum hydroxide Hydroxides such as nium, ammonium polyphosphate, brominated polyethylene, brominated polyphenylene sulfide, polybrominated polycarbonate, brominated epoxy or combinations of these bromide flame retardants and antimony trioxide, polyamide, polyethylene, polypropylene, polyester, Other polymers such as polycarbonate, polyphenylene ether, polyphenylene sulfide, liquid crystal polymer, ABS resin, SAN resin and polystyrene can be added.

  In order to improve the impact resistance of the polyamide resin of the present invention, 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 copolymer refers to a copolymer and a multi-component copolymer of ethylene and another monomer, and the other monomer copolymerized with ethylene is an α- having 3 or more carbon atoms. It can be selected from olefins, non-conjugated dienes, vinyl acetate, vinyl alcohol, α, β-unsaturated carboxylic acids and derivatives thereof.

  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 and film formation, such as automobile parts and machine parts. It can be used for resin molded products, fibers, films and the like. Specifically, automotive engine cooling system parts, radiator tank parts such as radiator tank top and base, coolant reserve tank, water pipe, water pump housing, water pump impeller, water pump parts such as valves, etc. And parts used in contact with cooling water. Small switches, switch housings, lamp sockets, connectors, connector housings, connector shells, IC sockets, bobbins, bobbin covers, relays, relay boxes, condenser cases, motor internal parts, small motor cases, gears, cams, Dancing pulley, spacer, insulator, fastener, buckle, clip, caster, helmet, terminal block, starter insulation, fuse box, terminal housing, wheel cover, intake / exhaust pipe, bearing retainer, wire / cable sheathing, fiber optic cable It is useful for electrical and electronic parts such as cases, automobile-related parts, computer-related parts, machine-related parts, and other various applications.

The following examples illustrate the invention, but the invention is not limited to these embodiments. Various characteristics in Examples and Comparative Examples were measured by the following methods.

(1) A sulfuric acid solution of polyamide resin having a concentration of 0.01 g / ml was prepared using 96% sulfuric acid as a relative viscosity solvent. The relative viscosity of this solution was measured at 25 ° C.

(2) Thermal characteristics
Using a TA DSC-Q100 analyzer, approximately 5 mg of a sample was accurately weighed and measured under the following test conditions. In a nitrogen atmosphere, the obtained polyamide resin was heated to a temperature 30 ° C. higher than the endothermic peak temperature (T0) that appeared when the temperature was raised to 20 ° C./min, and held at that temperature for 2 minutes. The solution was cooled to 30 ° C. at a temperature decrease rate of ° C./min, and held at 30 ° C. for 2 minutes. Next, an endothermic peak temperature (Tm: melting point) and a heat of fusion (ΔHm) observed when the temperature was raised to 30 ° C. higher than T 0 at a rate of temperature increase of 20 ° C./min were obtained.

(3) Melt retention stability Under a nitrogen atmosphere, heated to a temperature 20 ° C. higher than the melting point, the relative viscosity (B) of the polyamide resin subjected to the melt residence treatment for 2 hours, the relative viscosity of the polyamide resin before the melt residence treatment (A) From this, the relative viscosity retention (B / A) was determined.
(Abbreviation explanation)
DN5: 1,5-pentanediamine (manufactured by Sigma-Aldrich)
DPO: Diphenyl oxalate (manufactured by TCI)
DN6: 1,6-hexamethylenediamine (manufactured by Sigma-Aldrich)
M5: 2-methylpentanediamine (manufactured by Sigma-Aldrich)
DEA: Adipic acid diethyl ester (Sigma-Aldrich)
DMT: Dimethyl terephthalate (Sigma-Aldrich)
AA: Adipic acid (manufactured by Sigma Aldrich)
CuI (Sigma-Aldrich)
KI (Sigma-Aldrich)
1,10-diiododecane (manufactured by TCI)
2-Amino-6-iodopurine (manufactured by TCI)
Example 1
Initially, a three-necked flask (500 ml) was purged with nitrogen for 15 minutes to maintain a stream of nitrogen. Toluene (300 ml) and DPO (24.22 g, 0.100 mol) were added to the three-necked flask, and then stirring was started, and the temperature was raised to 70 ° C. DPO was completely dissolved in toluene at 70 ° C., then DN5 (10,218 g, 0.100 mol) was added thereto, heated to 130 ° C., and refluxed for 1 hour. After filtration and washing, it was dried in a vacuum oven at 100 ° C. for 12 hours. The relative viscosity of the obtained prepolymer was 1.63.

  2.00 g of the obtained prepolymer was supplied to a glass tube having a diameter of 19 mm and repeatedly purged with nitrogen five times. The pressure of the system was lowered to 300 Pa or less, and then placed in a metal bath at 280 ° C. After 25 hours, the polymerization reaction was carried out. To 2 g of the blend prepared by adding 1000 ppm of 1,10-diiododecane to the polymer powder, 15 ml of toluene was added, stirred for 4 hours, and toluene was removed under reduced pressure to obtain a polyamide resin. Table 1 shows the properties of the polyamide resin.

Comparative Example 1
A polyamide resin was obtained in the same manner as in Example 1 except that 1,10-diiododecane was not added.

Comparative Example 2
A polyamide resin was obtained in the same manner as in Example 1 except that KI / CuI was added instead of diiododecane, and the addition amount of KI was 471 ppm and the addition amount of CuI was 202 ppm. KI and CuI were added during the solid phase polymerization of the prepolymer.

Example 2
A polyamide resin was obtained in the same manner as in Example 1 except that the amount of 1,10-diiododecane added was 310 ppm.

Example 3
A polyamide resin was obtained in the same manner as in Example 1 except that the amount of 1,10-diiododecane added was 500 ppm.

Example 4
A polyamide resin was obtained in the same manner as in Example 1 except that the amount of 1,10-diiododecane added was 2000 ppm.

Example 5
A polyamide resin was obtained in the same manner as in Example 1 except that the amount of 1,10-diiododecane added was 4000 ppm.
Example 6
A polyamide resin was obtained in the same manner as in Example 1 except that 2-amino-6-iodopurine was changed to 1000 ppm instead of 1,10-diiododecane.

Example 7
Instead of DN5, DN6 and M5 are added, DN6 is added at 9.300 g (0.08 mol), M5 is added at 2.320 g (0.02 mol), and DN6 and M5 are added at 80:20 A polyamide resin was obtained in the same manner as in Example 1 except that post-polymerization was performed under the conditions shown in Table 3.

Comparative Example 3
A polyamide resin was obtained in the same manner as in Example 1, except that the amount of 1,10-diiododecane added was 11000 ppm.

Comparative Example 4
A polyamide resin was obtained in the same manner as in Example 1 except that the amount of 1,10-diiododecane added was 26 ppm.

Example 8
A polyamide resin was obtained in the same manner as in Example 1, except that the amount of DN5 added was 10.13 g (0.098 mol), the molar ratio of DN5 to DPO was 0.98, and the post-polymerization was carried out under the conditions shown in Table 4. It was.

Example 9
A polyamide resin was obtained in the same manner as in Example 1 except that the amount of DN5 added was 10.422 g (0.102 mol), the molar ratio of DN5 to DPO was 1.02, and the post-polymerization was carried out under the conditions shown in Table 4. It was.

Example 10
A polyamide resin was obtained in the same manner as in Example 1 except that the amount of DN5 added was 10.729 g (0.105 mol), the molar ratio of DN5 to DPO was 1.05, and the post-polymerization was carried out under the conditions shown in Table 4. It was.

Comparative Example 5
As the dicarboxylic acid unit, the addition amount of DPO and DEA, DPO is 7.267 g (0.030 mol), the addition amount of DEA is 14.16 g (0.070 mol), and the addition molar ratio of DPO and DMT is 30:70. A polyamide resin was obtained in the same manner as in Example 1 except that the polymerization was performed under the conditions shown in Table 4.

Comparative Example 6
As the dicarboxylic acid unit, the addition amount of DPO and DMT, DPO was 6.056 g (0.025 mol), the addition amount of DMT was 14.56 g (0.075 mol), and the addition molar ratio of DPO and DMT was 25:75. A polyamide resin was obtained in the same manner as in Example 1 except that the polymerization conditions were as shown in Table 4.

Example 11
A polyamide resin was obtained in the same manner as in Example 1 except that the post-polymerization time was 0.06 hr.

Example 12
A polyamide resin was obtained in the same manner as in Example 1 except that the post-polymerization time was 0.16 hr.

Example 13
A polyamide resin was obtained in the same manner as in Example 1 except that DBO was used instead of DPO, the molar ratio of DN5 to DPO was 1.05, and the post-polymerization was performed under the conditions shown in Table 5.

Example 14
A polyamide resin was obtained in the same manner as in Example 1 except that DN10 was used instead of DN5, the post-polymerization was performed under the conditions shown in Table 5, and the amount of 1,10-diiododecane added was 500 ppm.

Comparative Example 7
A polyamide resin was obtained in the same manner as in Example 13 except that 1,10-diiododecane was not added.

Comparative Example 8
A polyamide resin was obtained in the same manner as in Example 14 except that 1,10-diiododecane was not added.

Comparative Example 9
A test tube was charged with 20 g of a 50 wt% aqueous solution of DN6 and AA equimolar salts, placed in an autoclave, sealed, and purged with nitrogen. The jacket temperature was set to 310 ° C. and heating was started. After the internal pressure of the can reached 1.7 MPa, the internal pressure of the can was maintained at 1.7 MPa for 3 hours (the internal temperature of the can increased to 243 ° C.). Thereafter, the jacket temperature was set to 320 ° C., and the internal pressure of the can was released to normal pressure over 1 hour. Thereafter, the heating was stopped when the temperature inside the can reached 285 ° C. After allowing to cool to room temperature, the test tube was taken out of the autoclave and freeze-pulverized to obtain a polyamide resin.

Comparative Example 10
By adding 15 ml of toluene to a blend of 2 g prepared by adding 1000 ppm of 1,10-diiododecane to the polyamide resin obtained in Comparative Example 9, stirring for 4 hours, and removing the toluene under reduced pressure, A polyamide resin was obtained.

  The polyamide resin composition of the present invention can be used for resin molded products such as automobile parts and machine parts, fibers, films and the like.

Claims (10)

  A polyamide resin in which 50 to 100 mol% of the dicarboxylic acid unit includes a dicarboxylic acid unit composed of an oxalic acid unit and a diamine unit, the polyamide resin includes a nonionic organic iodine compound, and is based on the weight of the polyamide resin. And a polyamide resin, wherein the content of iodine atoms derived from the nonionic organic iodine compound is 20 ppm or more and 6000 ppm or less.   A 96% sulfuric acid solution was used as a solvent to prepare a sulfuric acid solution having a polyamide resin concentration of 0.01 g / ml, and the relative viscosity A measured at 25 ° C. of the sulfuric acid solution was 1.8 to 6. The polyamide resin according to claim 1, wherein the polyamide resin is in the range of 0.   Using a differential scanning calorimeter under an inert gas, the polyamide resin is cooled from the molten state to 30 ° C. at a temperature lowering rate of 20 ° C./min, and then heated up when measured at a temperature rising rate of 20 ° C./min. 3. The polyamide resin according to claim 1, which has a melting point of 280 to 320 ° C.   In a nitrogen atmosphere, the ratio (B / A) of the relative viscosity B after melting and residence for 2 hours at a temperature of the melting point of the polyamide resin + 20 ° C. and the relative viscosity A of the polyamide resin is 0.60 or more and 1.8 or less. The polyamide resin according to any one of claims 2 and 3, wherein   The polyamide resin according to any one of claims 1 to 4, wherein the diamine unit is at least one selected from a tetramethylenediamine unit, a pentamethylenediamine unit, and a hexamethylenediamine unit.   The polyamide resin according to any one of claims 1 to 5, wherein the nonionic organic iodine compound is at least one selected from a saturated alkyl iodine compound, an unsaturated alkyl iodine compound, an aromatic iodine compound, and a heterocyclic iodine compound. .   The polyamide resin according to any one of claims 1 to 6, wherein the nonionic organic iodine compound is 1,10-diiododecane and / or 2-amino-6-iodopurine.   Synthesizing a prepolymer having a relative viscosity of 1.02-1.75, and post-polymerizing the prepolymer in a temperature range of 200 ° C. to 335 ° C. until the relative viscosity becomes 1.80 or more and 6.0 or less. A method for producing a polyamide resin according to claim 1, wherein a nonionic organic iodine compound is added during or after the post-polymerization step.   The method for producing a polyamide resin according to claim 8, wherein the post-polymerization step time is less than 5 hours. A molded product formed by molding the polyamide resin according to claim 1.