Polyamide resin composition, method for producing polyamide resin composition and molded body

Abstract

To provide a polyamide resin composition which has improved glass transition temperature and has improved tensile strength under high temperature, and enables shortening of the molding time of the polyamide resin composition, and to provide a molded body of the polyamide resin composition.SOLUTION: A composition is provided, including: crystalline polyamine (A1) which includes a component unit derived from a dicarboxylic acid and a component unit derived from norbornane diamine; and crystalline polyamide (A2). Each of the polyamides (A1) and (A2) has a component unit derived from the same aromatic or alicyclic dicarboxylic acid, and has a component unit derived from the same linear or branched diamine. The crystalline polyamide (A2) has a mole fraction of the diamine higher than the that of crystalline polyamide (A1). The content of the crystalline polyamide resin (A2) is 5 mass% or more and 60 mass% or less, in the polyamide resin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyamide resin composition, a method for producing the polyamide resin composition, and a molded article. [Background technology]

[0002] Polyamide resin compositions have been known as molding materials. Polyamide resin compositions are widely used as materials for various parts, such as automotive parts and electrical and electronic parts, and are known to have excellent mechanical strength in molded articles. In particular, polyamide resin compositions containing polyamide resins containing component units derived from norbornanediamine are known to have high glass transition temperatures and excellent heat resistance.

[0003] For example, Patent Documents 1 to 3 disclose polyamide resin compositions using crystalline polyamides containing component units derived from diamines having specific structures such as norbornanediamine. According to Patent Documents 1 to 3, by using the polyamide resin compositions, the tensile strength of molded articles at high temperatures was good. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2022 / 014390 [Patent Document 2] International Publication No. 2023 / 136205 [Patent Document 3] International Publication No. 2023 / 136207 Summary of the Invention [Problem to be solved by the invention]

[0005] However, for polyamide resins containing component units derived from norbornanediamine as described in Patent Documents 1 to 3, further improvement in molding time when molding a polyamide resin composition to produce a molded article has been desired.

[0006] An object of the present invention is to provide a polyamide resin composition containing a polyamide resin containing component units derived from norbornanediamine, which has an increased glass transition temperature and increased tensile strength at high temperatures and can shorten the molding time, and a molded product thereof. [Means for solving the problem]

[0007] In order to solve the above problems, one aspect of the present invention relates to the following polyamide resin compositions [1] to [8]. [1] A crystalline polyamide resin (A1) containing a component unit (A1a) derived from a dicarboxylic acid and a component unit (A1b) derived from a diamine; A polyamide resin composition comprising a crystalline polyamide resin (A2) containing component units (A2a) derived from a dicarboxylic acid and component units (A2b) derived from a diamine, the diamine-derived component units (A1b) comprise component units (A1b1) derived from norbornanediamine, which account for at least 10 mol % and less than 50 mol % of the total number of moles of the diamine-derived component units (A1b), and component units (A1b2) derived from a linear or branched aliphatic diamine having from 4 to 18 carbon atoms, which account for at least 50 mol % and less than 90 mol % of the total number of moles of the diamine-derived component units (A1b); the diamine-derived component unit (A2b) includes a linear or branched aliphatic diamine-derived component unit (A2b2) having from 4 to 18 carbon atoms, the molar fraction of the aliphatic diamine-derived component unit (A1b2) in the diamine-derived component unit (A2b) is higher than the molar fraction of the aliphatic diamine-derived component unit (A2b2) in the diamine-derived component unit (A1b); the dicarboxylic acid-derived unit (A1a) and the dicarboxylic acid-derived unit (A2a) comprise unit(s) derived from the same aromatic dicarboxylic acid or the same alicyclic dicarboxylic acid, the diamine-derived unit (A1b2) and the diamine-derived unit (A2b2) comprise unit(s) derived from the same diamine, the content of the crystalline polyamide resin (A2) is 5% by mass or more and 60% by mass or less based on the total mass of the polyamide resins contained in the polyamide resin composition; Polyamide resin composition. [2] In the crystalline polyamide resin (A2), the diamine-derived component units (A2b) contain only the aliphatic diamine-derived component units (A1b1). [1] The polyamide resin composition according to [1]. [3] The crystalline polyamide resin (A2) contains only component units having a structure in which amide bond sites contained in the component units are arranged in a straight line on either side of the main skeleton of the component units. [1] or [2]. The polyamide resin composition. [4] The content of the crystalline polyamide resin (A2) is 5% by mass or more and 30% by mass or less based on the total mass of the polyamide resins contained in the polyamide resin composition. [3] The polyamide resin composition according to [3]. [5] The aromatic dicarboxylic acid is terephthalic acid or naphthalenedicarboxylic acid. The polyamide resin composition according to any one of [1] to [4]. [6] The aliphatic diamine is at least one diamine selected from the group consisting of 1,4-diaminobutane, 1,6-diaminohexane, 1,9-diaminononane, 1,10-diaminodecane, 2-methyl-1,5-diaminopentane, and 2-methyl-1,8-diaminooctane; The polyamide resin composition according to any one of [1] to [5]. [7] The crystalline polyamide resin (A2) is a polyamide resin selected from the group consisting of polyamide 6T66, polyamide 6TDT, and polyamide 6T6I. The polyamide resin composition according to any one of [1] to [6]. [8] The crystalline polyamide resin (A2) is polyamide 6T66. [7] The polyamide resin composition according to [7].

[0008] In order to solve the above problems, another aspect of the present invention relates to the following method for producing a polyamide resin composition [9]. [9] A method for producing a crystalline polyamide resin (A1) comprising a dicarboxylic acid-derived unit (A1a) and a diamine-derived unit (A1b), and a crystalline polyamide resin (A2) comprising a dicarboxylic acid-derived unit (A2a) and a diamine-derived unit (A2b), comprising: the diamine-derived component units (A1b) comprise component units (A1b1) derived from norbornanediamine, which account for at least 10 mol % and less than 50 mol % of the total number of moles of the diamine-derived component units (A1b), and component units (A1b2) derived from a linear or branched aliphatic diamine having from 4 to 18 carbon atoms, which account for at least 50 mol % and less than 90 mol % of the total number of moles of the diamine-derived component units (A1b); the diamine-derived component unit (A2b) includes a linear or branched aliphatic diamine-derived component unit (A2b2) having from 4 to 18 carbon atoms, the molar fraction of the aliphatic diamine-derived component unit (A2b1) in the diamine-derived component unit (A2b) is higher than the molar fraction of the aliphatic diamine-derived component unit (A2b2) in the diamine-derived component unit (A1b); the dicarboxylic acid-derived unit (A1a) and the dicarboxylic acid-derived unit (A2a) comprise unit(s) derived from the same aromatic dicarboxylic acid or the same alicyclic dicarboxylic acid, the diamine-derived unit (A1b2) and the diamine-derived unit (A2b2) comprise unit(s) derived from the same aliphatic diamine, The blending amount of the crystalline polyamide resin (A2) is 5% by mass or more and 60% by mass or less based on the total mass of the polyamide resins. A method for producing a polyamide resin composition.

[0009] Another aspect of the present invention for solving the above problems relates to the following molded article

[10] .

[10] A molded article obtained by molding the polyamide resin composition according to any one of [1] to [8]. [Effects of the Invention]

[0010] According to the present invention, there are provided a polyamide resin composition and a molded article thereof which have an increased glass transition temperature and increased tensile strength at high temperatures and can shorten the molding time. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0012] 1. Polyamide resin composition The polyamide resin composition according to this embodiment contains two types of crystalline polyamide resins, (A1) and (A2), each of which contains a dicarboxylic acid-derived unit and a diamine-derived unit. The dicarboxylic acid-derived unit and diamine-derived unit contained in the crystalline polyamide resin (A1) are referred to as the dicarboxylic acid-derived unit (A1a) and the diamine-derived unit (A1b), respectively. The dicarboxylic acid-derived unit and diamine-derived unit contained in the crystalline polyamide resin (A2) are referred to as the dicarboxylic acid-derived unit (A2a) and the diamine-derived unit (A2b), respectively.

[0013] The crystalline polyamide resin (A1) contains, as diamine-derived component units (A1b), component units (A1b1) derived from norbornanediamine and component units (A1b2) derived from a linear or branched aliphatic diamine having from 4 to 18 carbon atoms. The molar fractions of these component units (A1b1) and (A1b2), relative to the total number of moles of component units (A1b), are such that component units (A1b1) are from 10 mol % to less than 50 mol %, and component units (A1b2) are from 50 mol % to 90 mol %, respectively.

[0014] The crystalline polyamide resin (A2) contains, as diamine-derived component units (A2b), component units (A2b2) derived from a linear or branched aliphatic diamine having from 4 to 18 carbon atoms. However, the molar fraction of the component units (A2b2) contained in the crystalline polyamide resin (A2) is higher than the molar fraction of the component units (A2b2) contained in the crystalline polyamide resin (A1). In other words, the crystalline polyamide resin (A2) has a higher proportion of linear or branched aliphatic diamine than the crystalline polyamide resin (A1).

[0015] The crystalline polyamide resin (A1) and the crystalline polyamide resin (A2) contain, as the dicarboxylic acid-derived component units (A1a) and (A2a), component units derived from the same aromatic dicarboxylic acid or the same alicyclic dicarboxylic acid, and also contain, as the diamine-derived component units (A1b) and (A2b), component units derived from diamine.

[0016] The content of the crystalline polyamide resin (A2) is 10% by mass or more and 60% by mass or less based on the total mass of the polyamide resins contained in the polyamide resin composition.

[0017] As described above, there is room for improvement in molding time for polyamide resin compositions using polyamide resins containing component units derived from norbornanediamine. Norbornanediamine has a bicyclo skeleton, which is a bulky and rigid cyclic structure in its molecular structure, thereby reducing molecular mobility and increasing the glass transition temperature of the polyamide resin. On the other hand, the amount of crystallization sites contained in the molecular structure is reduced, which is thought to slow down the crystallization rate of the polyamide resin and increase the time it takes for the polyamide resin to crystallize. This is thought to increase the molding time of the polyamide resin composition.

[0018] In response to this, the present inventors have found that the molding time can be shortened by using a crystalline polyamide resin (A2) containing a large amount of component units derived from a linear or branched aliphatic diamine in addition to a crystalline polyamide resin (A1) containing component units derived from norbornanediamine.

[0019] The crystalline polyamide resin (A2) has a higher molar fraction of component units derived from linear or branched aliphatic diamines than the crystalline polyamide resin (A1). The component units derived from the aliphatic diamines can serve as crystallization sites for the polyamide resin, so a crystalline polyamide resin (A2) containing a higher amount of these components has a higher crystallization rate than the crystalline polyamide resin (A1). Therefore, the addition of the crystalline polyamide resin (A2) can increase the crystallization rate of the polyamide resin as a whole. This is thought to shorten the molding time for the polyamide resin composition.

[0020] Furthermore, the crystalline polyamide resin (A1) and the crystalline polyamide resin (A2) contain component units derived from the same monomer in both the component units derived from dicarboxylic acid and the component units derived from diamine. This makes the crystalline polyamide resin (A1) and the crystalline polyamide resin (A2) more compatible. This compatibility facilitates interaction between the component units derived from the same monomer. As a result, when the crystalline polyamide resin (A2) crystallizes, the crystallization of the crystalline polyamide resin (A1) is more likely to be accelerated. This can increase the crystallization rate of the crystalline polyamide resin (A1), thereby increasing the tensile strength of the molded article at high temperatures.

[0021] As a result of investigations by the present inventors, it was found that the above effect can be achieved by setting the content of the crystalline polyamide resin (A2) to 10% by mass or more relative to the total mass of the polyamide resins contained in the polyamide resin composition.

[0022] Furthermore, by setting the content of crystalline polyamide resin (A2) to 60% by mass or less, based on the total mass of polyamide resins contained in the polyamide resin composition, the glass transition temperature or tensile strength at high temperatures of the polyamide resin composition can be increased. Specifically, when the molecular structure of crystalline polyamide resin (A2) contains a bent structure (e.g., a component unit derived from isophthalic acid), setting the content of crystalline polyamide resin (A2) to 60% by mass or less can suppress a decrease in compatibility between the two crystalline polyamide resins and suppress a decrease in tensile strength at high temperatures. Furthermore, when the molecular structure of crystalline polyamide resin (A2) does not contain a bent structure, the molecular mobility of crystalline polyamide resin (A2) is high and the glass transition temperature is likely to be low. Therefore, by setting the content to 60% by mass or less, the content of crystalline polyamide resin (A1) can be increased, thereby increasing the glass transition temperature of the polyamide resin composition.

[0023] For these reasons, the polyamide resin composition according to this embodiment has an increased glass transition temperature and tensile strength at high temperatures, and can shorten the molding time.

[0024] 1-1. Crystalline polyamide resin (A1) In this specification, "crystalline polyamide resin" means a polyamide resin whose melting point can be observed by a differential scanning calorimeter (DSC), and more specifically, a polyamide resin whose endothermic peak has a half-width of 15°C or less when heated at a rate of 10°C / min by a differential scanning calorimeter (DSC). Crystalline polyamide resins form crystals in molded articles, which can increase the mechanical strength (such as tensile strength) of the molded articles.

[0025] The crystalline polyamide resin (A1) contains a component unit (A1a) derived from a dicarboxylic acid and a component unit (A1b) derived from a diamine.

[0026] (Constituent unit (A1a) derived from dicarboxylic acid) The dicarboxylic acid-derived component units (A1a) include component units derived from aromatic dicarboxylic acids or alicyclic dicarboxylic acids. Of these, the dicarboxylic acid-derived component units (A1a) preferably include component units derived from aromatic dicarboxylic acids.

[0027] Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2-methylterephthalic acid, and naphthalenedicarboxylic acid. Of these, the aromatic dicarboxylic acid is preferably terephthalic acid or naphthalenedicarboxylic acid, and more preferably terephthalic acid.

[0028] The content of the component units derived from terephthalic acid is preferably 40 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, and even more preferably 75 mol% or more and 100 mol% or less, based on the total number of moles of the component units (Aa) derived from dicarboxylic acids.

[0029] Examples of alicyclic dicarboxylic acids include cyclohexanedicarboxylic acid and its esters.

[0030] The content of the component units derived from the alicyclic dicarboxylic acid is preferably from 20 mol % to 80 mol % and more preferably from 25 mol % to 75 mol % relative to the total number of moles of the component units (A1a) derived from the dicarboxylic acid.

[0031] The dicarboxylic acid-derived component unit (A1a) may contain other dicarboxylic acid-derived component units. Examples of other dicarboxylic acids include aliphatic dicarboxylic acids.

[0032] Examples of the aliphatic dicarboxylic acid include aliphatic dicarboxylic acids having 4 to 20 carbon atoms. The number of carbon atoms is preferably 6 to 12. Examples of such aliphatic dicarboxylic acids include adipic acid, azelaic acid, and sebacic acid. Among these, adipic acid and sebacic acid are preferred, and adipic acid is more preferred.

[0033] The content of the component units derived from other dicarboxylic acids is preferably 0 mol % or more and 5 mol % or less, more preferably 0 mol % or more and less than 2 mol %, even more preferably 0 mol % or more and less than 1 mol %, and particularly preferably 0 mol %, relative to the total number of moles of the component units (A1a) derived from dicarboxylic acids.

[0034] (Diamine-derived component unit (A1b)) In this embodiment, the diamine-derived component unit (A1b) includes a norbornanediamine-derived component unit (A1b1) and an aliphatic diamine-derived component unit (A1b2) having 4 or more and 18 or less carbon atoms.

[0035] Norbornanediamine, the raw material for the unit (A1b1), has a rigid cyclic structure containing a bicyclo skeleton. Therefore, the unit (A1b1) reduces the mobility of the molecular chains of the polyamide resin. Therefore, diamines containing the unit (A1b1) can increase the glass transition temperature (Tg) of the crystalline polyamide resin (A1) compared to diamines without the unit (A1b1). Thus, the inclusion of the unit (A1b1) in the crystalline polyamide resin (A1) can increase the glass transition temperature of the polyamide resin composition and the tensile strength of molded articles in high-temperature environments.

[0036] The number of carbon atoms in the aliphatic diamine used as a raw material for the component unit (A1b1) is preferably from 4 to 12, and more preferably from 6 to 12. The aliphatic diamine may be a linear alkylenediamine or a branched alkylenediamine.

[0037] Examples of the linear alkylenediamine include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane. Among these, 1,6-diaminohexane, 1,9-nonanediamine, and 1,10-diaminodecane are preferred, with 1,6-diaminohexane being more preferred. The linear alkylenediamine may be used alone or in combination of two or more.

[0038] Examples of the branched alkylenediamine include 2,2-dimethyldiaminopropane, 1,1-dimethyl-1,4-diaminobutane, 1-ethyl-1,4-diaminobutane, 1,2-dimethyl-1,4-diaminobutane, 1,3-dimethyl-1,4-diaminobutane, 1,4-dimethyl-1,4-diaminobutane, 2,3-dimethyl-1,4-diaminobutane, 2-methyl-1,5-diaminopentane, 2,5-dimethyl-1,6-diaminohexane, 2,4 -Dimethyl-1,6-diaminohexane, 3,3-dimethyl-1,6-diaminohexane, 2,2-dimethyl-1,6-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, 2,4,4-trimethyl-1,6-diaminohexane, 2,4-diethyl-1,6-diaminohexane, 2,3-dimethyl-1,7-diaminoheptane, 2,4-dimethyl-1,7-diaminoheptane, 2,5-dimethyl-1,7-diaminoheptane, 2,2- Dimethyl-1,7-diaminoheptane, 2-methyl-4-ethyl-1,7-diaminoheptane, 2-ethyl-4-methyl-1,7-diaminoheptane, 2,2,5,5-tetramethyl-1,7-diaminoheptane, 3-isopropyl-1,7-diaminoheptane, 3-isooctyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 1,3-dimethyl-1,8-diaminooctane, 1,4-dimethyl-1,8-diaminooctane, 2, Examples of branched alkylene diamines include 4-dimethyl-1,8-diaminooctane, 3,4-dimethyl-1,8-diaminooctane, 4,5-dimethyl-1,8-diaminooctane, 2,2-dimethyl-1,8-diaminooctane, 3,3-dimethyl-1,8-diaminooctane, 4,4-dimethyl-1,8-diaminooctane, 3,3,5-trimethyl-1,8-diaminooctane, 2,4-diethyl-1,8-diaminooctane, and 5-methyl-1,9-diaminononane. Among these, 2-methyl-1,5-diaminopentane is preferred. Branched alkylene diamines may be used alone or in combination of two or more.

[0039] Of these linear and branched alkylenediamines, the aliphatic diamine is preferably at least one diamine selected from the group consisting of 1,4-diaminobutane, 1,6-diaminohexane, 1,9-diaminononane, 1,10-diaminodecane, 2-methyl-1,5-diaminopentane, and 2-methyl-1,8-diaminooctane.

[0040] The diamine-derived component units (A1b) comprise, relative to the total number of moles of the diamine-derived component units (A1b), 10 mol % to less than 50 mol % of norbornanediamine-derived component units (A1b1) and 50 mol % to 90 mol % of the aliphatic diamine-derived component units (A1b2); preferably, 10 mol % to 40 mol % of norbornanediamine-derived component units (A1b1) and 60 mol % to 90 mol % of the aliphatic diamine-derived component units (A1b2); and more preferably, 10 mol % to 35 mol % of norbornanediamine-derived component units (A1b1) and 65 mol % to 90 mol % of the aliphatic diamine-derived component units (A1b2).

[0041] The diamine-derived unit (A1b) may contain other diamine-derived units. Examples of other diamines include alicyclic diamines having from 4 to 20 carbon atoms and aromatic diamines.

[0042] Examples of the alicyclic diamine having 4 to 20 carbon atoms include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 2,5-bisaminomethylnorbornane, and 2,6-bisaminomethylnorbornane. Examples of the aromatic diamine include metaxylylenediamine.

[0043] The constituent units of the crystalline polyamide resin (A1) and their ratios can be calculated from the charge ratios when the crystalline polyamide resin (A1) is prepared, or can be measured by the NMR method.

[0044] 1 In the case of H-NMR measurement, for example, a nuclear magnetic resonance apparatus (ECX400 model manufactured by JEOL Ltd.) is used, the solvent is deuterated orthodichlorobenzene, the sample concentration is 20 mg / 0.6 mL, the measurement temperature is 120 °C, and the observation nucleus is 1 The conditions are H (400 MHz), sequence is single pulse, pulse width is 5.12 μsec (45° pulse), repetition time is 7.0 sec, and the number of accumulations is 500 or more. The reference chemical shift is set to 0 ppm for hydrogen in tetramethylsilane, but similar results can also be obtained by setting the peak derived from residual hydrogen in deuterated orthodichlorobenzene at 7.10 ppm as the reference value for the chemical shift. 1 Peaks such as H can be assigned by conventional methods.

[0045] 13 In the case of C-NMR measurement, for example, a nuclear magnetic resonance apparatus (ECP500 model manufactured by JEOL Ltd.) is used as the measurement apparatus, a mixed solvent of ortho-dichlorobenzene / heavy benzene (80 / 20% by volume) is used as the solvent, the measurement temperature is 120°C, and the observation nucleus is 13 The conditions were: C (125 MHz), single pulse proton decoupling, 45° pulse, repetition time 5.5 seconds, accumulation number 10,000 or more, and chemical shift reference value 27.50 ppm. Assignment of various signals was performed based on the standard method, and quantification could be performed based on the accumulated value of signal intensity.

[0046] The dicarboxylic acid-derived component units (A1a) of the crystalline polyamide resin (A1) may contain component units derived from a biomass-derived dicarboxylic acid, and the diamine-derived component units (A1b) may contain component units derived from a biomass-derived diamine. The crystalline polyamide resin (A1) may be a biomass-derived crystalline polyamide resin (A1) obtained by polymerizing raw materials including a biomass-derived raw material.

[0047] In order to improve the thermal stability during compounding or molding and to further increase the mechanical strength, at least some of the molecular terminal groups of the crystalline polyamide resin (A1) may be blocked with a terminal blocking agent. The terminal blocking agent is preferably a monoamine when the molecular terminal is a carboxyl group, and is preferably a monocarboxylic acid when the molecular terminal is an amino group, for example.

[0048] Examples of monoamines include aliphatic monoamines such as methylamine, ethylamine, propylamine, and butylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aromatic monoamines such as aniline and toluidine. Examples of monocarboxylic acids include aliphatic monocarboxylic acids having 2 to 30 carbon atoms such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid; and alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid. The aromatic monocarboxylic acid and alicyclic monocarboxylic acid may have a substituent on the ring structure portion.

[0049] The crystalline polyamide resin (A1) can be produced by the same method as that for known polyamide resins, for example, by polycondensing a dicarboxylic acid and a diamine in a homogeneous solution. Specifically, as described in WO 03 / 085029, the crystalline polyamide resin (A1) can be produced by heating a dicarboxylic acid and a diamine in the presence of a catalyst to obtain a low-order condensate, and then applying shear stress to the melt of the low-order condensate to polycondense it.

[0050] The content of the crystalline polyamide resin (A1) is preferably 50% by mass or more and 90% by mass or less, and more preferably 65% ​​by mass or more and 90% by mass or less, based on the total mass of the polyamide resin contained in the polyamide resin composition. A content of 50% by mass or more can further increase the glass transition temperature and tensile strength at high temperatures of the polyamide resin composition. Furthermore, a content of 90% by mass or less can further shorten the molding time of the polyamide resin composition by incorporating a sufficient amount of the crystalline polyamide resin (A2).

[0051] The content of the crystalline polyamide resin (A1) is preferably 40% by mass or more and 95% by mass or less, and more preferably 50% by mass or more and 90% by mass or less, based on the total mass of the polyamide resin composition. When the content is 40% by mass or more, the glass transition temperature and mechanical strength at high temperatures of the polyamide resin composition can be sufficiently increased. When the content is 95% by mass or less, the polyamide resin composition can sufficiently contain other components described below.

[0052] (Physical Properties) From the viewpoint of further increasing the mechanical strength and heat resistance of the molded article, the melting point of the crystalline polyamide resin (A1) is preferably 280°C or higher, more preferably 290°C or higher, and even more preferably 300°C or higher. Furthermore, from the viewpoint of facilitating molding of the polyamide resin composition without excessively increasing the molding temperature, the melting point of the crystalline polyamide resin (A1) is preferably 340°C or lower. The melting point of the crystalline polyamide resin (A1) can be measured by a differential scanning calorimeter (DSC).

[0053] The melting point of the crystalline polyamide resin (A1) can be adjusted to the above range by adjusting the composition of the crystalline polyamide resin (A1). For example, the melting point can be increased by increasing the content of component units derived from terephthalic acid, which will be described later.

[0054] The crystalline polyamide resin (A1) preferably has a glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) of 130°C to 180°C, more preferably 140°C to 175°C, and even more preferably 150°C to 170°C. A glass transition temperature (Tg) of 130°C or higher increases the temperature at which molecular mobility becomes significantly more active, thereby suppressing molecular mobility and more sufficiently enhancing the heat resistance of the polyamide resin composition and molded articles. A glass transition temperature (Tg) of 180°C or lower makes it easier to maintain the fluidity of the resin composition without excessively increasing the mold temperature during molding, thereby improving molding processability.

[0055] The heat of fusion (ΔH) of the crystalline polyamide resin (A1) measured by differential scanning calorimetry (DSC) is preferably greater than 5 J / g. The heat of fusion is an index of the crystallinity of a resin, and a larger heat of fusion indicates higher crystallinity. When the heat of fusion (ΔH) of the crystalline polyamide resin (A) exceeds 5 J / g, the crystallinity is increased, and the mechanical strength of the resulting molded article can be further increased. The upper limit of the heat of fusion (ΔH) is not particularly limited, but is, for example, 100 J / g.

[0056] The melting point and heat of fusion (ΔH) of the crystalline polyamide resin (A1) can be measured using a differential scanning calorimeter (DSC220C model, manufactured by Seiko Instruments Inc.).

[0057] Specifically, approximately 5 mg of crystalline polyamide resin (A1) is sealed in a measuring aluminum pan and heated from room temperature to 350°C at 10°C / min. To completely melt the resin, it is held at 350°C for 3 minutes and then cooled to 30°C at 10°C / min. After leaving it at 30°C for 5 minutes, it is heated a second time to 350°C at 10°C / min. The temperature (°C) of the endothermic peak during this second heating is taken as the melting point (Tm) of the crystalline polyamide resin (A1), and the inflection point corresponding to the glass transition is taken as the glass transition temperature (Tg). The heat of fusion (ΔH) is determined from the area of ​​the endothermic peak during the first heating process, in accordance with JIS K7122.

[0058] The intrinsic viscosity [η] of the crystalline polyamide resin (A1), measured in 96.5% sulfuric acid at 25°C, is preferably 0.9 dL / g to 1.2 dL / g, more preferably 1.0 dL / g to 1.2 dL / g, and particularly preferably 1.0 dL / g to 1.1 dL / g. When the intrinsic viscosity [η] of the crystalline polyamide resin (A1) is 0.9 dL / g or higher, the mechanical strength (e.g., bending strength) of the molded article is easily increased. When the intrinsic viscosity [η] is 1.2 dL / g or lower, the fluidity of the resin composition during molding is less likely to be impaired. The intrinsic viscosity [η] can be adjusted by adjusting the molar ratio of the dicarboxylic acid-derived component unit (A1a) and the diamine-derived component unit (A1b). Specifically, the closer the molar ratio of the carboxylic acid-derived component unit (A1a) and the diamine-derived component unit (A1b) is to 1:1, the higher the intrinsic viscosity can be. It can also be adjusted by the amount of end-capping of the crystalline polyamide resin (A1).

[0059] The intrinsic viscosity [η] of the crystalline polyamide resin (A1) can be measured as follows. 0.5 g of the crystalline polyamide resin (A1) is dissolved in 50 ml of a 96.5% sulfuric acid solution to prepare a sample solution. The flow time of the obtained solution at 25°C ± 0.05°C is measured using an Ubbelohde viscometer, and the intrinsic viscosity [η] is calculated according to the following formula: [η]=ηSP / (C*(1+0.205ηSP)) [η]: Intrinsic viscosity (dl / g) ηSP: Specific viscosity C: Sample concentration (g / dl) t: Number of seconds for sample solution to flow down (seconds) t0: Number of seconds the blank sulfuric acid flows (seconds) ηSP=(t-t0) / t0

[0060] 1-2. Crystalline polyamide resin (A2) The crystalline polyamide resin (A2) contains a component unit (A2a) derived from a dicarboxylic acid and a component unit (A2b) derived from a diamine.

[0061] (Constituent unit (A2a) derived from dicarboxylic acid) The dicarboxylic acid-derived component unit (A2a) includes a component unit derived from the same dicarboxylic acid as the aromatic dicarboxylic acid or alicyclic dicarboxylic acid contained in the dicarboxylic acid-derived component unit (A1a) in the crystalline polyamide resin (A1).

[0062] The component units (A1a) of the crystalline polyamide resin (A1) may be a combination of different component units derived from multiple dicarboxylic acids, and the component units (A2a) of the crystalline polyamide resin (A2) may be a combination of different component units derived from multiple dicarboxylic acids. In these cases, it is sufficient that at least one of the dicarboxylic acids used as raw materials for the multiple component units contained in the component units (A1a) is the same as at least one of the dicarboxylic acids used as raw materials for the multiple component units contained in the component units (A2a). However, the molar fraction of the component units contained in the component units (A1a) that are the same as the component units (A2a) is preferably 30 mol% to 100 mol%, more preferably 40 mol% to 100 mol%, and even more preferably 50 mol% to 100 mol%. Furthermore, among the component units contained in the component unit (A2a), the molar fraction of component units containing the same component unit as the component unit (A1a) is preferably 30 mol % or more and 100 mol % or less, more preferably 40 mol % or more and 100 mol % or less, and even more preferably 50 mol % or more and 100 mol % or less.

[0063] The type of aromatic dicarboxylic acid or alicyclic dicarboxylic acid in the dicarboxylic acid-derived component unit (A2a) can be the same as that described for the crystalline polyamide resin (A1).

[0064] The aromatic dicarboxylic acid is preferably terephthalic acid or naphthalenedicarboxylic acid, and more preferably terephthalic acid. The content of the component units derived from terephthalic acid is preferably 40 mol% to 100 mol%, more preferably 45 mol% to 99 mol%, even more preferably 50 mol% to 85 mol%, and particularly preferably 55 mol% to 65 mol%, based on the total number of moles of the component units (A2a) derived from dicarboxylic acids.

[0065] The dicarboxylic acid-derived component units (A2a) preferably contain component units derived from an aliphatic dicarboxylic acid having from 4 to 20 carbon atoms, thereby increasing the crystallinity of the crystalline polyamide resin (A2) and further increasing the tensile strength of the molded article at high temperatures.

[0066] Examples of the aliphatic dicarboxylic acid include adipic acid, azelaic acid, and sebacic acid. Among these, adipic acid and sebacic acid are preferred, and adipic acid is more preferred.

[0067] The content of the component units derived from the above aliphatic dicarboxylic acid is preferably from 0 mol % to 60 mol % and more preferably from 0 mol % to 40 mol % relative to the total number of moles of the component units (A2a) derived from dicarboxylic acid.

[0068] (Diamine-derived component unit (A2b)) The diamine-derived component unit (A2b) includes a component unit (A2b2) derived from a linear or branched aliphatic diamine having from 4 to 18 carbon atoms. The component unit (A2b2) includes the same aliphatic diamine-derived component unit as the component unit (A1b2) derived from an aliphatic diamine having from 4 to 18 carbon atoms in the crystalline polyamide resin (A1).

[0069] The component units (A1b2) of the crystalline polyamide resin (A1) may be a combination of different component units derived from multiple diamines, and the component units (A2b2) of the crystalline polyamide resin (A2) may be a combination of different component units derived from multiple diamines. In these cases, it is sufficient that at least one of the diamines used as raw materials for the multiple component units contained in the component unit (A1b2) is the same as at least one of the diamines used as raw materials for the multiple component units contained in the component unit (A2b2). However, the molar fraction of the component units contained in the component unit (A1b2) that are the same as the component units contained in the component unit (A2b2) is preferably 50 mol% to 100 mol%, more preferably 60 mol% to 100 mol%, and even more preferably 65 mol% to 100 mol%. Furthermore, among the component units contained in the component unit (A2b2), the molar fraction of component units that contain the same component unit as the component unit (A1b2) is preferably from 45 mol % to 100 mol %, more preferably from 50 mol % to 100 mol %, and even more preferably from 60 mol % to 100 mol %.

[0070] When the diamine-derived unit (A1b2) in the crystalline polyamide resin (A1) contains a linear alkylenediamine-derived unit, the diamine-derived unit (A2b2) preferably contains only linear alkylenediamine-derived units as aliphatic diamine-derived units, thereby further improving the compatibility between the crystalline polyamide resin (A1) and the crystalline polyamide resin (A2) and further increasing the tensile strength of the molded article at high temperatures.

[0071] Examples of the aliphatic diamine include those mentioned for the crystalline polyamide resin (A1). Among them, the aliphatic diamine is preferably at least one diamine selected from the group consisting of 1,4-diaminobutane, 1,6-diaminohexane, 1,9-diaminononane, 1,10-diaminodecane, 2-methyl-1,5-diaminopentane, and 2-methyl-1,8-diaminooctane.

[0072] The content (molar fraction) of the aliphatic diamine-derived component units (A2b2) derived from diamine is higher than the content (molar fraction) of the aliphatic diamine-derived component units (A1b2) derived from diamine in the crystalline polyamide resin (A1). The content of the aliphatic diamine-derived component units (A2b2) is preferably 50 mol% to 100 mol%, more preferably 70 mol% to 100 mol%, even more preferably 90 mol% to 100 mol%, and particularly preferably 100 mol% (i.e., the diamine-derived component units (A2b) are composed solely of the aliphatic diamine-derived component units (A2b2)). This further increases the crystallization rate of the polyamide resin as a whole, thereby further shortening the molding time of the polyamide resin composition.

[0073] The crystalline polyamide resin (A2) preferably contains only component units having a structure in which the amide bond sites contained in the component units are arranged in a straight line across the main backbone of the component units. Examples of component units (A2a) derived from dicarboxylic acids having this structure include component units derived from terephthalic acid, and examples of component units (A2b2) derived from diamines having this structure include component units derived from aliphatic diamines having a linear structure, such as 1,4-diaminobutane, 1,6-diaminohexane, 1,9-diaminononane, and 1,10-diaminodecane. Such crystalline polyamide resins (A2) have high crystallinity and compatibility with the crystalline polyamide resin (A1). Therefore, even with a small content of crystalline polyamide resin (A2), the tensile strength of molded articles at high temperatures can be further increased.

[0074] When the crystalline polyamide resin (A1) contains, as the dicarboxylic acid-derived component units (A1a), component units derived from terephthalic acid, and contains, as the diamine-derived component units (A1b), component units derived from norbornanediamine and component units derived from 1,6-diaminohexane, specific examples of the crystalline polyamide resin (A2) include polyamide 6T66, polyamide 6T6I, polyamide 6TDT, etc. When the crystalline polyamide resin (A2) is any of the above, the dicarboxylic acid-derived component units (A1a) contained in the crystalline polyamide resin (A1) and the dicarboxylic acid-derived component units (A2a) contained in the crystalline polyamide resin (A2) both contain component units derived from terephthalic acid, and the diamine-derived component units (A1b) contained in the crystalline polyamide resin (A1) and the diamine-derived component units (A2b) contained in the crystalline polyamide resin (A2) both contain component units derived from 1,6-diaminohexane. Among these, polyamide 6T66 is preferred from the viewpoint of further improving compatibility with the crystalline polyamide resin (A1) and further increasing the tensile strength of the molded article at high temperatures. That is, the crystalline polyamide resin (A2) preferably contains, as the dicarboxylic acid-derived component units (A2a), component units derived from terephthalic acid and component units derived from adipic acid, and contains, as the diamine-derived component units (A2b), component units derived from 1,6-diaminohexane.

[0075] The respective constituent units and their ratios of the crystalline polyamide resin (A2) can be calculated from the charge ratios when preparing the crystalline polyamide resin (A2) or measured by the NMR method, which can be the same as that described for the crystalline polyamide resin (A1).

[0076] The dicarboxylic acid-derived component units of the crystalline polyamide resin (A2) may include component units derived from biomass-derived dicarboxylic acids, and the diamine-derived component units may include component units derived from biomass-derived diamines. The crystalline polyamide resin (A2) may also be a biomass-derived crystalline polyamide resin (A2) obtained by polymerizing raw materials including biomass-derived raw materials.

[0077] In order to improve the thermal stability during compounding and molding and to further increase the mechanical strength, at least some of the molecular terminal groups of the crystalline polyamide resin (A2) may be blocked with a terminal blocking agent. For example, when the molecular terminal is a carboxyl group, the terminal blocking agent is preferably a monoamine, and when the molecular terminal is an amino group, the terminal blocking agent is preferably a monocarboxylic acid. The types of monoamine and monocarboxylic acid may be the same as those described for the crystalline polyamide resin (A1).

[0078] The crystalline polyamide resin (A2) can be produced by the same method as that for known polyamide resins, for example, by polycondensing a dicarboxylic acid and a diamine in a homogeneous solution. Specifically, as described in WO 03 / 085029, the dicarboxylic acid and the diamine are heated in the presence of a catalyst to obtain a low-order condensate, and then the melt of the low-order condensate is subjected to shear stress to polycondense the low-order condensate.

[0079] The content of the crystalline polyamide resin (A2) is 5% by mass or more and 60% by mass or less, preferably 5% by mass or more and 55% by mass or less, more preferably 5% by mass or more and 50% by mass or less, even more preferably 5% by mass or more and 40% by mass or less, and particularly preferably 5% by mass or more and 30% by mass or less, based on the total mass of the polyamide resin contained in the polyamide resin composition. By making the content 55% by mass or less, the crystalline polyamide resin (A1) is sufficiently contained, and the glass transition temperature or the tensile strength at high temperatures of the polyamide resin composition can be further increased.

[0080] When the crystalline polyamide resin (A2) is polyamide 6T66, the content of the crystalline polyamide resin (A2) is preferably 5% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 20% by mass or less, relative to the total mass of the polyamide resins contained in the polyamide resin composition. When the crystalline polyamide resin (A2) contains only component units having a linear structure, a content of 30% by mass or less promotes the crystallization of the polyamide resin (A1) and increases the crystallinity of the entire polyamide resin composition, thereby enabling the tensile strength of the molded article at high temperatures to be further increased.

[0081] The content of the crystalline polyamide resin (A2) is preferably from 5 to 50% by mass, and more preferably from 15 to 35% by mass, based on the total mass of the polyamide resin composition.

[0082] (Physical Properties) From the viewpoint of further increasing the mechanical strength and heat resistance of the molded article, the melting point of the crystalline polyamide resin (A2) is preferably 290° C. or higher, and more preferably 300° C. or higher. Furthermore, from the viewpoint of facilitating molding of the polyamide resin composition without excessively increasing the molding temperature, the melting point of the crystalline polyamide resin (A2) is preferably 340° C. or lower.

[0083] The melting point of the crystalline polyamide resin (A2) can be adjusted to the above range by adjusting the composition of the crystalline polyamide resin (A1). For example, the melting point can be increased by increasing the content of the component unit derived from terephthalic acid, which will be described later.

[0084] Furthermore, the crystalline polyamide resin (A1) preferably has a glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) of 70°C or higher and 170°C or lower, more preferably 75°C or higher and 150°C or lower, and even more preferably 80°C or higher and 120°C or lower. When the glass transition temperature (Tg) is 70°C or higher, the temperature at which molecular mobility becomes significantly more active increases, thereby suppressing molecular mobility and more sufficiently improving the heat resistance of the polyamide resin composition and molded article. When the glass transition temperature (Tg) is 145°C or lower, the polyamide resin composition can be filled into a mold without excessively increasing the mold temperature during molding, thereby further shortening the molding time.

[0085] The heat of fusion (ΔH) of the crystalline polyamide resin (A2) measured by differential scanning calorimetry (DSC) is preferably greater than 5 J / g. The heat of fusion is an index of the crystallinity of a resin, and a larger heat of fusion indicates higher crystallinity. When the heat of fusion (ΔH) of the crystalline polyamide resin (A2) exceeds 5 J / g, the crystallinity is increased, and the mechanical strength of the resulting molded article can be further increased. The upper limit of the heat of fusion (ΔH) is not particularly limited, but is, for example, 100 J / g.

[0086] The melting point and heat of fusion (ΔH) of the crystalline polyamide resin (A2) can be measured using a differential scanning calorimeter (DSC220C model, manufactured by Seiko Instruments Inc.).

[0087] Specifically, approximately 5 mg of crystalline polyamide resin (A1) is sealed in a measuring aluminum pan and heated from room temperature to 350°C at 10°C / min. To completely melt the resin, it is held at 350°C for 3 minutes and then cooled to 30°C at 10°C / min. After leaving it at 30°C for 5 minutes, it is heated a second time to 350°C at 10°C / min. The temperature (°C) of the endothermic peak during this second heating is taken as the melting point (Tm) of the crystalline polyamide resin (A2), and the inflection point corresponding to the glass transition is taken as the glass transition temperature (Tg). The heat of fusion (ΔH) is determined from the area of ​​the endothermic peak during the first heating process, in accordance with JIS K7122.

[0088] The intrinsic viscosity [η] of the crystalline polyamide resin (A2), measured in 96.5% sulfuric acid at 25°C, is preferably 0.9 dL / g to 1.2 dL / g, more preferably 1.0 dL / g to 1.2 dL / g, and particularly preferably 1.0 dL / g to 1.1 dL / g. When the intrinsic viscosity [η] of the crystalline polyamide resin (A2) is 0.9 dL / g or higher, the mechanical strength (e.g., bending strength) of the molded article is easily increased. When the intrinsic viscosity [η] is 1.2 dL / g or lower, the fluidity of the resin composition during molding is less likely to be impaired. The intrinsic viscosity [η] can be adjusted by adjusting the molar ratio of the dicarboxylic acid-derived component unit (A2a) and the diamine-derived component unit (A2b). Specifically, the closer the molar ratio of the carboxylic acid-derived component unit (A2a) and the diamine-derived component unit (A2b) is to 1:1, the higher the intrinsic viscosity can be. It can also be adjusted by the amount of end-capping of the crystalline polyamide resin (A2).

[0089] The intrinsic viscosity [η] of the crystalline polyamide resin (A2) can be measured in the same manner as the intrinsic viscosity [η] of the crystalline polyamide resin (A1).

[0090] 1-3.Other ingredients The polyamide resin composition may contain other known components.

[0091] Examples of other components include nucleating agents, copper-based stabilizers, lubricants, colorants, reinforcing agents, heat stabilizers, corrosion resistance improvers, anti-drip agents, ion scavengers, elastomers (rubbers), antistatic agents, mold release agents, antioxidants (phenols, amines, sulfur compounds, phosphorus compounds, etc.), heat stabilizers other than those mentioned above (lactone compounds, vitamin E compounds, hydroquinones, etc.), light stabilizers (benzotriazoles, triazines, benzophenones, benzoates, hindered amines, oxanilides, etc.), other polymers (polyolefins, olefin copolymers such as ethylene-propylene copolymers, ethylene-1-butene copolymers, olefin copolymers such as propylene-1-butene copolymers, polystyrene, polycarbonate, polyacetal, polysulfone, polyphenylene oxide, fluororesin, silicone resin, LCP, etc.).

[0092] (nucleating agent) Examples of nucleating agents include metal salt compounds such as sodium 2,2-methylenebis(4,6-di-t-butylphenyl)phosphate, aluminum tris(pt-butylbenzoate), and stearates; sorbitol compounds such as bis(p-methylbenzylidene)sorbitol and bis(4-ethylbenzylidene)sorbitol; and inorganic substances such as talc, calcium carbonate, and hydrotalcite. Among these, talc is preferred from the viewpoint of further increasing the crystallinity of the resin member. These nucleating agents may be used alone or in combination.

[0093] Talc generally contains hydrous magnesium silicate (SiO2: 58-64%, MgO: 28-32%, Al2O3: 0.5-5%, Fe2O3: 0.3-5%) as its main component. The average particle size of the talc is not particularly limited, but is preferably 1-15 μm. When the average particle size of the talc is within the above range, the talc can be easily dispersed in the polyamide resin (A) without impairing the fluidity of the polyamide resin composition. From the same viewpoint, the average particle size of the talc is more preferably 1-7.5 μm. The average particle size of the talc can be measured by a laser diffraction method, for example, using a Shimadzu particle size distribution analyzer (SALD-2000A) manufactured by Shimadzu Corporation.

[0094] The content of the nucleating agent other than boron nitride is preferably 0.10 parts by mass or more and 5.00 parts by mass or less, and more preferably 0.10 parts by mass or more and 3.00 parts by mass or less, relative to the total mass of the polyamide resin composition. When the content of the nucleating agent is within the above range, the crystallinity of the polyamide resin is easily increased sufficiently, and sufficient mechanical strength is easily obtained.

[0095] (copper stabilizer) The copper-based stabilizer includes (i) a salt of a halogen and a metal element of Group 1 or 2 of the periodic table (a halogen metal salt), and (ii) a copper compound. The copper-based stabilizer can impart heat resistance (heat aging resistance) to the polyamide resin composition, enabling it to withstand high temperatures, for example, of 150°C or higher.

[0096] (i) Examples of the halogen metal salt include potassium iodide, potassium bromide, potassium chloride, sodium iodide, and sodium chloride. Of these, potassium iodide and potassium bromide are preferred as the halogen metal salt. Only one type of halogen metal salt may be included, or two or more types may be included.

[0097] (ii) Examples of copper compounds include copper halides, copper sulfate, acetate, propionate, benzoate, adipate, terephthalate, salicylate, nicotinate, stearate, and copper chelate compounds (compounds of copper with ethylenediamine or ethylenediaminetetraacetic acid, etc.). Of these, copper compounds such as copper iodide, copper (I) bromide, copper (II) bromide, copper (I) chloride, and copper acetate are preferred. Only one type of copper compound may be contained, or two or more types may be contained.

[0098] The mass ratio of (i) the halogen metal salt to (ii) the copper compound is preferably adjusted so that the molar ratio of halogen to copper is 0.5 / 1 to 100 / 1, more preferably 2 / 1 to 40 / 1, from the viewpoint of facilitating improvement in the heat resistance of the molded body and the corrosion resistance during production.

[0099] Examples of copper-based stabilizers include a mixture of 10% by mass of copper(I) iodide and 90% by mass of potassium iodide, and a mixture of 14.3% by mass of copper(I) iodide and 85.7% by mass of potassium iodide / calcium distearate (98:2 mass ratio).

[0100] The content of the copper-based stabilizer is preferably 0.01 mass% or more and 3.00 mass% or less, more preferably 0.02 mass% or more and 1.00 mass% or less, and even more preferably 0.03 mass% or more and 0.50 mass% or less, relative to the total mass of the polyamide resin composition.

[0101] (lubricant) The lubricant can improve the injection flowability of the polyamide resin composition and improve the appearance of the resulting resin part. The lubricant can be a metal salt of a fatty acid, such as a metal salt of an oxycarboxylic acid or a metal salt of a higher fatty acid.

[0102] The hydroxycarboxylic acid constituting the hydroxycarboxylic acid metal salt may be an aliphatic hydroxycarboxylic acid or an aromatic hydroxycarboxylic acid. Examples of the aliphatic hydroxycarboxylic acid include aliphatic hydroxycarboxylic acids having 10 to 30 carbon atoms, such as α-hydroxymyristic acid, α-hydroxypalmitic acid, α-hydroxystearic acid, α-hydroxyeicosanoic acid, α-hydroxydocosanoic acid, α-hydroxytetraeicosanoic acid, α-hydroxyhexaeicosanoic acid, α-hydroxyoctaeicosanoic acid, α-hydroxytriacontanoic acid, β-hydroxymyristic acid, 10-hydroxydecanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid, 12-hydroxystearic acid, and ricinoleic acid. Examples of the aromatic hydroxycarboxylic acid include salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, gallic acid, mandelic acid, and trovic acid.

[0103] Examples of the metal constituting the metal oxycarboxylic acid salt include alkali metals such as lithium, and alkaline earth metals such as magnesium, calcium and barium.

[0104] Of these, the metal oxycarboxylic acid salt is preferably a metal salt of 12-hydroxystearic acid, and more preferably magnesium 12-hydroxystearate and calcium 12-hydroxystearate.

[0105] Examples of the higher fatty acids that constitute the higher fatty acid metal salts include higher fatty acids having 15 to 30 carbon atoms, such as stearic acid, oleic acid, behenic acid, behenic acid, and montanic acid.

[0106] Examples of metals constituting the above higher fatty acid metal salts include calcium, magnesium, barium, lithium, aluminum, zinc, sodium, and potassium.

[0107] Of these, the higher fatty acid metal salts are preferably calcium stearate, magnesium stearate, barium stearate, calcium behenate, sodium montanate, and calcium montanate.

[0108] The content of the lubricant is preferably 0.01% by mass or more and 1.30% by mass or less relative to the total mass of the polyamide resin composition. When the content of the lubricant is 0.01% by mass or more, the fluidity during molding tends to be improved, and the appearance of the obtained molded product tends to be improved. When the content of the lubricant is 1.30% by mass or less, gas due to decomposition of the lubricant is unlikely to be generated during molding, and the appearance of the product tends to be good.

[0109] (Reinforcement material) The reinforcing material can impart high mechanical strength to the polyamide resin composition. The reinforcing material may be an inorganic filler. Examples of the reinforcing material include fibrous reinforcing materials such as glass fiber, wollastonite, potassium titanate whiskers, calcium carbonate whiskers, aluminum borate whiskers, magnesium sulfate whiskers, zinc oxide whiskers, milled fiber, and cut fiber, as well as granular reinforcing materials. One of these may be used alone, or two or more may be used in combination. Among these, wollastonite, glass fiber, and potassium titanate whiskers are preferred because they can easily increase the mechanical strength of the resin member, and wollastonite or glass fiber is more preferred.

[0110] From the viewpoints of moldability of the polyamide resin composition and the mechanical strength and heat resistance of the resulting resin part, the average fiber length of the fibrous reinforcing material may be, for example, from 1 μm to 20 mm, preferably from 5 μm to 10 mm, and the aspect ratio of the fibrous reinforcing material may be, for example, from 5 to 2000, preferably from 30 to 600.

[0111] The average fiber length and average fiber diameter of the fibrous reinforcing material can be measured by the following method. 1) The polyamide resin composition is dissolved in a hexafluoroisopropanol / chloroform solution (0.1 / 0.9% by volume), and then filtered to obtain a filtrate. 2) Disperse the filtered material obtained in 1) above in water, and measure the fiber length (Li) and fiber diameter (di) of each of 300 randomly selected fibers using an optical microscope (magnification: 50x). The number of fibers with fiber length Li is taken as qi, and the weight-average length (Lw) is calculated using the following formula, which is the average fiber length of the fibrous reinforcement. Weight average length (Lw) = (Σqi × Li 2 ) / (Σqi×Li) Similarly, the number of fibers with a fiber diameter Di is taken as ri, and the weight average diameter (Dw) is calculated based on the following formula, and this is taken as the average fiber diameter of the fibrous reinforcing material. Weight average diameter (Dw)=(Σri×Di 2 ) / (Σri×Di)

[0112] The content of the reinforcing material is not particularly limited, but can be, for example, 15% by mass or more and 70% by mass or less relative to the total mass of the polyamide resin composition. From the viewpoint of suppressing a decrease in the initial airtightness and the rate at which the airtightness is maintained after repeated thermal shocks, which is caused by the fluidity and elastic modulus of the polyamide resin composition being changed by the addition of the reinforcing material, the content of the reinforcing material is preferably 15% by mass or more and 50% by mass or less relative to the total mass of the polyamide resin composition.

[0113] 1-6. Method for producing polyamide resin composition The polyamide resin composition can be produced by a known resin kneading method, such as mixing the above-mentioned crystalline polyamide resin (A1), crystalline polyamide resin (A2), and optionally other components, in a Henschel mixer, V-blender, ribbon blender, or tumbler blender, or by melt-kneading the mixture in a single-screw extruder, multi-screw extruder, kneader, or Banbury mixer, followed by granulation or pulverization. In this case, the melting temperature during melt-kneading is preferably at least 10°C above the melting point (Tm) of the polyamide resin (A1) and at most 20°C above the melting point (Tm).

[0114] 2. Molded body The molded article of the present invention is obtained by molding the polyamide resin composition of the present invention. The polyamide resin composition provides the molded article with improved tracking resistance.

[0115] The molded article can be produced using the polyamide resin composition by a conventional melt molding method, such as compression molding, injection molding, etc. For example, the polyamide resin composition of the present invention can be put into a molten state in an injection molding machine whose cylinder temperature is adjusted to the melting point of the crystalline polyamide resin (A) or higher, for example, about 280°C to 350°C, and then introduced into a mold of a predetermined shape to produce a molded article.

[0116] The shape of the molded article produced using the polyamide resin composition of the present invention is not particularly limited, and may take various shapes depending on the application.

[0117] Examples of applications of molded articles of the polyamide resin composition in this embodiment include vehicle structural parts, vehicle-mounted items, housings for electronic devices, housings for home appliances, structural parts, machine parts, various automobile parts, electronic device parts, medical devices, etc. As described above, the polyamide resin composition can improve the tracking resistance of molded articles, and therefore, among these applications, it can be particularly suitably used for electronic device parts. [Example]

[0118] The present invention will be described below with reference to examples, which should not be construed as limiting the scope of the present invention.

[0119] 1. Synthesis / preparation of materials 1-1. Synthesis of polyamide resin (A1) <Preparation of Polyamide Resin (PA-1) (6T / NBDAT)> 259.5 g (1562.0 mmol) of terephthalic acid, 81.3 g (1046.5 mmol) of 1,6-diaminohexane, 26.2 g (515.46 mmol) of norbornanediamine, 0.37 g of sodium hypophosphite monohydrate as a catalyst, and 81.8 g of distilled water were placed in a 1 L autoclave and purged with nitrogen. Stirring was initiated at 190 °C, and the internal temperature was raised to 250 °C over 3 hours. At this time, the internal pressure of the autoclave was increased to 3.0 MPa. After the reaction was continued for 1 hour, the low-order condensation product was discharged into the atmosphere through a spray nozzle installed at the bottom of the autoclave and extracted. The low-order condensation product was then cooled to room temperature, crushed in a crusher to a particle size of 1.5 mm or less, and dried at 110 °C for 24 hours.

[0120] Next, this low-order condensate was placed in a tray-type solid-state polymerization reactor, and after replacing with nitrogen, the temperature was raised to 215°C over about 1 hour and 30 minutes, followed by reaction for 1 hour and 30 minutes, and then the temperature was lowered to room temperature.

[0121] The obtained prepolymer was then melt-polymerized in a twin-screw extruder with a screw diameter of 30 mm and L / D=36 at a barrel set temperature of 330°C, a screw rotation speed of 200 rpm, and a resin feed rate of 6 kg / h to obtain a polyamide resin (PA-1).

[0122] The resulting polyamide resin (PA-1) had an intrinsic viscosity [η] of 0.97 dl / g, a melting point (Tm) of 312°C, a glass transition temperature (Tg) of 160°C, and a heat of fusion (ΔH) of 46 J / g. Furthermore, calculated from the charge ratio, the content of component units derived from terephthalic acid among the component units derived from dicarboxylic acid was 100 mol%, and the content of component units derived from 1,6-diaminohexane among the component units derived from diamine was 65 mol%, and the content of component units derived from norbornanediamine was 35 mol%.

[0123] 1-2. Synthesis of polyamide resin (A2) <Preparation of Polyamide Resin (PA-2) (6T66)> 2515 g (15.1 mol) of terephthalic acid, 2800 g (24.1 mol) of 1,6-diaminohexane, 1325 g (9.0 mol) of adipic acid, 5.7 g of sodium hypophosphite monohydrate, and 554 g of distilled water were placed in a 13.6 L autoclave and purged with nitrogen. Stirring was initiated at 190°C, and the internal temperature was raised to 250°C over 3 hours. At this time, the internal pressure of the autoclave was increased to 3.01 MPa. After the reaction was continued for 1 hour, the low-order condensation product was discharged into the atmosphere through a spray nozzle installed at the bottom of the autoclave and extracted. The extracted low-order condensation product was cooled to room temperature, then pulverized in a pulverizer to a particle size of 1.5 mm or less, and dried at 110°C for 24 hours.

[0124] Next, this low-order condensate was placed in a tray-type solid-state polymerization reactor, and after nitrogen substitution, the temperature was raised to 220°C over approximately 1 hour and 30 minutes. The low-order condensate was then reacted for 1 hour and cooled to room temperature. Subsequently, polyamide (high condensate) was further melt-polymerized in a twin-screw extruder with a screw diameter of 30 mm and L / D = 36 at a barrel setting temperature of 330°C, a screw rotation speed of 200 rpm, and a resin feed rate of 6 kg / hour to obtain polyamide resin (PA-2).

[0125] The resulting polyamide resin (PA-2) had an intrinsic viscosity [η] of 0.8 dl / g, a melting point (Tm) of 320°C, and a glass transition temperature (Tg) of 95°C. The heat of fusion (ΔH) measured by differential scanning calorimetry (DSC) was 50 J / g. The composition of the resulting polyamide resin PA-2 was such that, among the dicarboxylic acid-derived component units, the content of terephthalic acid-derived component units was 62.5 mol%, the content of adipic acid-derived component units was 37.5 mol%, and the content of 1,6-diaminohexane-derived component units among the diamine-derived component units was 100 mol%.

[0126] <Preparation of Polyamide Resin (PA-3) (6T6I)> 2800 g (24.1 mol) of 1,6-diaminohexane, 2774 g (16.7 mol) of terephthalic acid, 1196 g (7.2 mol) of isophthalic acid, 5.7 g of sodium hypophosphite monohydrate as a catalyst, 36.6 g (0.30 mol) of benzoic acid as a molecular weight modifier, and 545 g of distilled water were placed in a 13.6 L autoclave and purged with nitrogen. Stirring was initiated at 190 °C, and the internal temperature was raised to 250 °C over 3 hours. At this time, the internal pressure of the autoclave was increased to 3.03 MPa. After the reaction was continued for 1 hour, the low-order condensation product was discharged into the atmosphere through a spray nozzle installed at the bottom of the autoclave and extracted. The low-order condensation product was then cooled to room temperature, pulverized in a pulverizer to a particle size of 1.5 mm or less, and dried at 110 °C for 24 hours. The intrinsic viscosity [η] of the resulting low-order condensation product was 0.15 dL / g.

[0127] Next, this low-order condensate was placed in a tray-type solid-state polymerization reactor, and after purging with nitrogen, the temperature was raised to 180°C over approximately 1 hour and 30 minutes. After that, the reaction was continued for 1 hour and 30 minutes, and the temperature was lowered to room temperature. The intrinsic viscosity [η] of the resulting prepolymer was 0.20 dL / g.

[0128] The obtained prepolymer was then melt-polymerized in a twin-screw extruder with a screw diameter of 30 mm and L / D=36 at a barrel temperature of 330°C, a screw rotation speed of 200 rpm, and a resin feed rate of 6 kg / h to obtain a polyamide resin (PA-3).

[0129] The resulting polyamide resin (PA-3) had an intrinsic viscosity [η] of 1.0 dl / g, a melting point (Tm) of 330°C, a glass transition temperature (Tg) of 125°C, and a heat of fusion (ΔH) of 50 J / g. The resulting polyamide resin (PA-3) had a composition in which the dicarboxylic acid-derived component units contained 70 mol% of component units derived from terephthalic acid, 30 mol% of component units derived from isophthalic acid, and 100 mol% of component units derived from 1,6-diaminohexane.

[0130] <Preparation of Polyamide Resin (PA-4) (6TDT)> 1,6-diaminohexane 1312 g (11.3 mol), 2-methyl-1,5-pentanediamine 1312 g (11.3 mol), terephthalic acid 3655 g (22.0 mol), sodium hypophosphite 5.5 g as a catalyst, and ion-exchanged water 640 ml were charged into a 1-liter reactor, and after purging with nitrogen, the mixture was heated at 250°C and 35 kg / cm 2 After 1 hour had passed, the reaction product produced in the reactor was transferred to a reactor connected to the reactor and heated to a pressure of about 10 kg / cm. 2 The mixture was extracted into a receiver set at a low temperature to obtain a polyamide precursor having an intrinsic viscosity [η] of 0.15 dL / g. The polyamide precursor was then dried and melt-polymerized using a twin-screw extruder at a cylinder temperature of 330°C to obtain a polyamide resin (PA-4).

[0131] The resulting polyamide resin (PA-4) had an intrinsic viscosity [η] of 0.9 dl / g, a melting point (Tm) of 300°C, a glass transition temperature (Tg) of 140°C, and a heat of fusion (ΔH) of 45 J / g. The composition of the resulting polyamide resin (PA-4) was such that the content of component units derived from terephthalic acid among component units derived from dicarboxylic acid was 100 mol%, and the content of component units derived from 1,6-diaminohexane among component units derived from diamine was 50 mol%, and the content of component units derived from 2-methyl-1,5-pentanediamine was 50 mol%.

[0132] 1-3. Synthesis of other polyamide resins Polyamide 66 was used.

[0133] 1-4.Other ingredients 1-4-1. Copper-based stabilizers A mixture of 10% by mass of copper (I) iodide and 90% by mass of potassium iodide was used.

[0134] 1-4-2. Nucleating agent Talc (average particle size 6 μm) was used.

[0135] 1-4-3. Lubricants Sodium montanate was used.

[0136] 1-4-4. Reinforcement material Glass fiber (FT756D, manufactured by Owing Corning, containing a sizing agent having a carboxyl group) was used as a reinforcing material.

[0137] 2. Measurement The physical properties of each of the above resins were measured by the following methods.

[0138] <Melting point (Tm), glass transition temperature (Tg)> The melting point (Tm) and glass transition temperature (Tg) of the polyamide resin were measured using a differential scanning calorimeter (DSC220C, manufactured by Seiko Instruments Inc.). Specifically, approximately 5 mg of polyamide resin was sealed in an aluminum pan for measurement and set in the differential scanning calorimeter. The polyamide resin was then heated from room temperature to 350°C at 10°C / min. To completely melt the resin, it was held at 350°C for 3 minutes and then cooled to 30°C at 10°C / min. After leaving it at 30°C for 5 minutes, it was heated a second time to 350°C at 10°C / min. The temperature (°C) of the endothermic peak during this second heating was taken as the melting point (Tm) of the polyamide resin, and the inflection point corresponding to the glass transition was taken as the glass transition temperature (Tg).

[0139] <Heat of fusion (ΔH)> The heat of fusion (ΔH) of the polyamide resin was calculated from the area of ​​the exothermic peak of crystallization during the first heating process in accordance with JIS K 7122 (2012).

[0140] <Intrinsic viscosity [η]> The intrinsic viscosity [η] of the polyamide resin was calculated by dissolving 0.5 g of the polyamide resin in 50 ml of a 96.5% sulfuric acid solution, measuring the flow time of the resulting solution at 25°C ± 0.05°C using an Ubbelohde viscometer, and then calculating the intrinsic viscosity [η] based on the formula: [η] = ηSP / (C(1 + 0.205ηSP)). [η]: Intrinsic viscosity (dl / g) ηSP: Specific viscosity C: Sample concentration (g / dl) t: Number of seconds for sample solution to flow down (seconds) t0: Number of seconds the blank sulfuric acid flows (seconds) ηSP=(t-t0) / t0

[0141] 3. Preparation of polyamide resin composition The above materials were mixed in a tumbler blender in the composition ratios (unit: parts by mass) shown in Tables 1 to 4, and melt-kneaded using a 30 mmφ vented twin-screw extruder at a cylinder temperature of 300 to 335°C. The kneaded mixture was then extruded into strands and cooled in a water bath. The strands were then taken up in a pelletizer and cut to obtain pellet-shaped polyamide resin compositions 1 to 17.

[0142] <Glass transition temperature (Tg) of polyamide resin composition> Using about 5 mg of the polyamide resin composition, the glass transition temperature of the polyamide resin composition was measured in the same manner as in the measurement of the glass transition temperature of polyamide resins.

[0143] 4. Evaluation <Tensile strength> The obtained polyamide resin composition was molded using the following injection molding machine under the following molding conditions to obtain an ASTM dumbbell-shaped test piece Type I having a thickness of 3.2 mm. Molding machine: EC75N-2A (manufactured by Toshiba Machine Co., Ltd.) Cylinder temperature: Among the polyamide resins to be added, the melting point of the polyamide resin with the highest melting point + 10°C Mold temperature: 200℃ Injection setting speed: 50mm / sec

[0144] The obtained test pieces were left for 24 hours in a nitrogen atmosphere at 23°C, and then subjected to a tensile test in accordance with ASTM D638 at temperatures of 23°C and 150°C and a relative humidity of 50%, to measure the tensile strength at break (tensile strength) [MPa].

[0145] <Moldability> In molding the above-mentioned ASTM dumbbell-shaped test piece Type I, moldability was evaluated by checking whether or not any polyamide resin composition remained in the mold when the test piece was released from the mold. More specifically, molding of ASTM dumbbell-shaped test piece Type I was performed multiple times while changing the cooling time, and it was checked whether or not any polyamide resin composition remained in the mold after the test piece was removed for each molding. If the cooling time is insufficient, the polyamide resin composition remains in the mold, resulting in poor mold release. The minimum cooling time [s] at which no polyamide resin composition remained in the mold after the test piece was removed was measured.

[0146] [Table 1]

[0147] [Table 2]

[0148] [Table 3]

[0149] [Table 4]

[0150] From the above examples, it was found that by using a polyamide resin (A1) containing component units derived from norbornanediamine and a polyamide resin (A2) containing a larger amount of component units derived from aliphatic diamine and containing component units derived from the same type of aromatic dicarboxylic acid as the polyamide resin (A1) and component units derived from the same type of aliphatic diamine, it is possible to increase the glass transition temperature of the polyamide resin composition and the tensile strength of the molded body at high temperatures while shortening the molding time of the polyamide resin composition. [Industrial Applicability]

[0151] The polyamide resin composition according to the present invention is useful for applications such as electric and electronic parts.

Claims

1. a crystalline polyamide resin (A1) containing a component unit (A1a) derived from a dicarboxylic acid and a component unit (A1b) derived from a diamine; A polyamide resin composition comprising: a crystalline polyamide resin (A2) containing component units (A2a) derived from a dicarboxylic acid and component units (A2b) derived from a diamine, The diamine-derived component units (A1b) comprise component units (A1b1) derived from norbornanediamine, which account for at least 10 mol % and less than 50 mol %, based on the total number of moles of the diamine-derived component units (A1b), and component units (A1b2) derived from a linear or branched aliphatic diamine having from 4 to 18 carbon atoms, which account for at least 50 mol % and less than 90 mol %, based on the total number of moles of the diamine-derived component units (A1b), the diamine-derived component unit (A2b) includes a linear or branched aliphatic diamine-derived component unit (A2b2) having from 4 to 18 carbon atoms, the molar fraction of the aliphatic diamine-derived component unit (A1b2) in the diamine-derived component unit (A2b) is higher than the molar fraction of the aliphatic diamine-derived component unit (A2b2) in the diamine-derived component unit (A1b); the dicarboxylic acid-derived component unit (A1a) and the dicarboxylic acid-derived component unit (A2a) comprise component units derived from the same aromatic dicarboxylic acid or the same alicyclic dicarboxylic acid, the diamine-derived component unit (A1b2) and the diamine-derived component unit (A2b2) comprise component units derived from the same diamine, the content of the crystalline polyamide resin (A2) is 5% by mass or more and 60% by mass or less based on the total mass of the polyamide resins contained in the polyamide resin composition; Polyamide resin composition.

2. In the crystalline polyamide resin (A2), the diamine-derived component units (A2b) contain only the aliphatic diamine-derived component units (A1b1). The polyamide resin composition according to claim 1.

3. The crystalline polyamide resin (A2) contains only constituent units having a structure in which amide bond sites contained in the constituent units are arranged in a straight line on either side of the main skeleton of the constituent units, The polyamide resin composition according to claim 1.

4. the content of the crystalline polyamide resin (A2) is 5% by mass or more and 30% by mass or less based on the total mass of the polyamide resins contained in the polyamide resin composition; The polyamide resin composition according to claim 3.

5. The aromatic dicarboxylic acid is terephthalic acid or naphthalenedicarboxylic acid. The polyamide resin composition according to claim 1.

6. The aliphatic diamine is at least one diamine selected from the group consisting of 1,4-diaminobutane, 1,6-diaminohexane, 1,9-diaminononane, 1,10-diaminodecane, 2-methyl-1,5-diaminopentane, and 2-methyl-1,8-diaminooctane; The polyamide resin composition according to claim 1.

7. The crystalline polyamide resin (A2) is a polyamide resin selected from the group consisting of polyamide 6T66, polyamide 6TDT, and polyamide 6T6I. The polyamide resin composition according to claim 1.

8. The crystalline polyamide resin (A2) is polyamide 6T66. The polyamide resin composition according to claim 7.

9. The method includes a step of melt-kneading a crystalline polyamide resin (A1) containing a component unit (A1a) derived from a dicarboxylic acid and a component unit (A1b) derived from a diamine, and a crystalline polyamide resin (A2) containing a component unit (A2a) derived from a dicarboxylic acid and a component unit (A2b) derived from a diamine, The diamine-derived component units (A1b) comprise component units (A1b1) derived from norbornanediamine, which account for at least 10 mol % and less than 50 mol %, based on the total number of moles of the diamine-derived component units (A1b), and component units (A1b2) derived from a linear or branched aliphatic diamine having from 4 to 18 carbon atoms, which account for at least 50 mol % and less than 90 mol %, based on the total number of moles of the diamine-derived component units (A1b), the diamine-derived component unit (A2b) includes a linear or branched aliphatic diamine-derived component unit (A2b2) having from 4 to 18 carbon atoms, the molar fraction of the aliphatic diamine-derived component unit (A2b1) in the diamine-derived component unit (A2b) is higher than the molar fraction of the aliphatic diamine-derived component unit (A2b2) in the diamine-derived component unit (A1b); the dicarboxylic acid-derived component unit (A1a) and the dicarboxylic acid-derived component unit (A2a) comprise component units derived from the same aromatic dicarboxylic acid or the same alicyclic dicarboxylic acid, the diamine-derived component unit (A1b2) and the diamine-derived component unit (A2b2) comprise component units derived from the same aliphatic diamine, The blending amount of the crystalline polyamide resin (A2) is 5% by mass or more and 60% by mass or less based on the total mass of the polyamide resins. A method for producing a polyamide resin composition.

10. A molded article obtained by molding the polyamide resin composition according to any one of claims 1 to 8.

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