High heat-resistant polyamide resin

Abstract

To provide a crystalline polyamide resin with high heat resistance. [Solution] A crystalline polyamide resin comprising component units (a) derived from dicarboxylic acid and component units (b) derived from diamine, wherein component unit (a) comprises component unit (a1) derived from at least one selected from the group consisting of terephthalic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid, the content of component unit (a1) is more than 50 mol% and 100 mol% or less relative to the total number of moles of component unit (a), and component unit (b) comprises component unit (b1) derived from alkylenediamine having 4 to 18 carbon atoms, and the following formula (1): A crystalline polyamide resin comprising a component unit (b2) derived from a diamine represented by the formula {wherein R1 and R2 are as defined in the specification}, wherein the component unit (b2) content is 25 to 45 mol% relative to the total number of moles of component unit (b).

Description

Technical Field

[0001] This disclosure relates to polyamide resins and the like.

Background Art

[0002] Polyamide resins are known to be thermoplastic resins whose main chains are composed of repeating structures containing amide bonds (-NHCO-), and various types of monomers such as lactams, diamines, and dicarboxylic acids can be used to create a wide variety of molecular skeletons.

[0003] Conventionally, polyamide resins have been widely used as materials for various parts such as clothing, industrial materials, vehicles, electrical and electronic components, and industrial applications because of their excellent moldability, mechanical properties, chemical resistance, etc. In order to exhibit characteristics corresponding to these applications, attempts have been made to change the physical properties of polyamide resins by changing their raw materials.

[0004] In recent years, in the manufacture of bus bar members and the like, integral molding of a member containing a polyamide resin and a conductor has been studied.

[0005] For example, Patent Document 1 describes an insert molded body in which a member made of a thermoplastic resin and a conductor are directly integrated as a bus bar member, and it is also described that the member made of a thermoplastic resin is composed of a thermoplastic resin such as a polyamide resin and a polyphenylene sulfide resin.

Prior Art Documents

Patent Documents

[0008] This disclosure is made in view of the above circumstances and aims to provide a crystalline polyamide resin having high heat resistance. [Means for solving the problem]

[0009] One aspect of this disclosure is listed below. (1) A crystalline polyamide resin comprising a component unit (a) derived from a dicarboxylic acid and a component unit (b) derived from a diamine, The component unit (a) derived from the dicarboxylic acid includes a component unit (a1) derived from at least one selected from the group consisting of terephthalic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid. The content of the aforementioned component unit (a1) is more than 50 mol% and 100 mol% or less relative to the total number of moles of component unit (a) derived from the dicarboxylic acid. The component unit (b) derived from the diamine is, A component unit (b1) derived from alkylenediamine with 4 to 18 carbon atoms, Formula (1): [ka] {In the formula, R1 and R2 are each independently selected from the group consisting of hydrogen atoms, alkyl groups, alkoxy groups, halogenated alkyl groups, halogenated alkoxy groups, and halogen atoms.} It includes a component unit (b2) derived from a diamine represented by and The content of the aforementioned component unit (b2) is 25 mol% or more and 45 mol% or less relative to the total number of moles of component unit (b) derived from the diamine. Crystalline polyamide resin. (2) The crystalline polyamide resin according to item 1, having a glass transition temperature (Tg) of 144°C or higher. (3) The crystalline polyamide resin according to item 1 or 2, having a melting point (Tm) of 270°C or higher and 330°C or lower. (4) The crystalline polyamide resin according to any one of items 1 to 3, having a heat of fusion (ΔH) of 15 J / g or higher. (5) A resin composition containing the crystalline polyamide resin according to any one of items 1 to 4. (6) A molded article containing the resin composition according to item 5. (7) The molded article according to item 6, which is a part of an electric or electronic device. (8) A conductive member including an insulating member containing the resin composition according to item 5 and a conductive metal member on the surface along the insulating member.

Advantages of the Invention

[0010] According to the present disclosure, a crystalline polyamide resin having high heat resistance can be provided, and thus, it is excellent in mechanical strength and moldability even in a high-temperature environment of about 150°C.

Modes for Carrying Out the Invention

[0011] In the present disclosure, the numerical range indicated by using "~" means a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively.

[0012] In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other stepwise descriptions. Also, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.

[0013] The numerical values described in the present disclosure are measured by the methods described in the examples unless otherwise specified.

[0014] <Crystalline polyamide resin> In one embodiment of the present disclosure, a crystalline polyamide resin is provided. The crystalline polyamide resin maintains crystallinity until, for example, undergoing molding processing. Therefore, compared with an amorphous polyamide resin, it has high fluidity and mechanical strength during molding such as injection molding, and tends to easily retain mechanical strength and moldability.

[0015] The crystalline polyamide resin according to one embodiment includes a component unit (a) derived from a dicarboxylic acid and a component unit (b) derived from a diamine. The component unit (a) derived from a dicarboxylic acid includes a component unit (a1) derived from at least one selected from the group consisting of terephthalic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid. The content of the component unit (a1) is more than 50 mol% and 100 mol% or less based on the total number of moles of the component unit (a) derived from a dicarboxylic acid. The component unit (b) derived from a diamine is: a component unit (b1) derived from an alkylenediamine having 4 to 18 carbon atoms; the following formula (1):

Chemical formula

[0016] In crystalline polyamide resins, the content of component units (a1) derived from at least one selected from the group consisting of terephthalic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid is more than 50 mol% and 100 mol% or less relative to the total number of moles of component units (a) derived from dicarboxylic acid, and the content of component units (b2) derived from the diamine represented by the above formula (1) is 25 mol% or more and 45 mol% or less relative to the total number of moles of component units (b) derived from diamine enhances heat resistance, and consequently, the crystalline polyamide resin exhibits excellent mechanical strength and moldability even in high-temperature environments such as around 150°C.

[0017] Generally, polyamide resins containing more than 50 mol% but less than or equal to 100 mol% of component units derived from aromatic or alicyclic dicarboxylic acids other than terephthalic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid, such as isophthalic acid, relative to the total number of moles of component units derived from dicarboxylic acids, tend to be difficult to ensure crystallinity. In contrast, according to this disclosure, from the viewpoint of facilitating the assurance or improvement of crystallinity and facilitating the increase in the melting point (Tm), it has been found that component units (a) derived from dicarboxylic acids include component units (a1) derived from at least one selected from the group consisting of terephthalic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid, and the content of component units (a1) is more than 50 mol% but less than or equal to 100 mol% relative to the total number of moles of component units (a).

[0018] Conventionally, component units derived from diamines represented by the above formula (1) were often incorporated into amorphous transparent polyamide resins. In contrast, according to this disclosure, surprisingly, it has been found that a polyamide resin exhibiting crystalline properties includes not only component units (a) derived from dicarboxylic acids, but also component units (b1) derived from alkylenediamines having 4 to 18 carbon atoms, and component units (b2) derived from diamines represented by the above formula (1), and the content of component units (b2) is 25 mol% to 45 mol% of the total number of moles of component units (b).

[0019] Although we do not wish to be constrained by theory, the alicyclic structure in formula (1) above is sterically hindrance-wise bulky, which reduces the mobility of the molecular chains and may raise the glass transition temperature (Tg) of the crystalline polyamide resin to a desired level. Furthermore, by optimizing the content of the component unit (b2) derived from the diamine represented in formula (1) above, or by the methylene bond portion between the alicyclic structures in formula (1) above, it is conceivable that not only will the Tg rise to a desired level, but the melting point (Tm) of the crystalline polyamide resin will also be adjusted to a temperature range in which moldability can be maintained.

[0020] The glass transition temperature (Tg) of crystalline polyamide resin is preferably 144°C or higher, more preferably 147°C or higher, and even more preferably 150°C or higher. When the Tg of crystalline polyamide resin is within the above range, its heat resistance is less likely to be impaired, and it tends to have excellent mechanical strength and moldability even in high-temperature environments. The upper limit of the Tg of crystalline polyamide resin is not limited, but from the viewpoint of ensuring or maintaining moldability, it may be, for example, 200°C or lower.

[0021] The melting point (Tm) of crystalline polyamide resin is preferably between 270°C and 330°C. A Tm of 270°C or higher makes it easier to maintain mechanical strength, heat resistance, etc., while a Tm of 330°C or lower eliminates the need for excessively high molding temperatures, resulting in better moldability.

[0022] The crystalline polyamide resin of this disclosure contains a component unit (b2) derived from the diamine represented by formula (1) above. By optimizing the content of the alicyclic structure in formula (1), the methylene bond portion between the alicyclic structures in formula (1), and the component unit (b2), not only can the glass transition temperature (Tg) be raised to a desired level, but the melting point (Tm) can also be adjusted to a predetermined temperature range. From the viewpoint of balancing heat resistance, mechanical strength, and moldability, it is preferable that the crystalline polyamide resin has a Tg of 144°C or higher and a Tm of 270°C or higher and 330°C or lower.

[0023] The heat of fusion (ΔH) of crystalline polyamide resin is preferably 15 J / g or more. When the ΔH of crystalline polyamide resin is 15 J / g or more, it tends to have excellent moldability, including release properties, appearance, suppression of shrinkage rate changes, and injection moldability. Following a similar trend, the ΔH of crystalline polyamide resin is more preferably 18 J / g or more, and even more preferably 20 J / g or more. The upper limit of the ΔH of crystalline polyamide resin is not limited, but from the viewpoint of ensuring or maintaining moldability, it may be, for example, 100 J / g or less.

[0024] The crystallization temperature (Tc) of crystalline polyamide resin is preferably 250°C or higher, from the viewpoint of moldability such as release properties, appearance, suppression of changes in shrinkage rate, and injection moldability.

[0025] The melting point (Tm), glass transition temperature (Tg), heat of fusion (ΔH), and crystallization temperature (Tc) of the crystalline polyamide resin are not limited, but can be adjusted by, for example, the structure of the component unit (a) derived from the dicarboxylic acid, the content of the component unit (b2) derived from the diamine represented by formula (1) above, the content ratio of the component unit (b1) derived from the alkylenediamine with 4 to 18 carbon atoms to the component unit (b2) derived from the diamine represented by formula (1) above, the number of carbon atoms of the alkylenediamine, etc.

[0026] For example, from the viewpoint of setting the melting point (Tm) of the crystalline polyamide resin within the range of 270°C to 330°C, or from the viewpoint of use as an insulating material and improvement of electrical resistance, it is preferable that the crystalline polyamide resin be a semi-aromatic polyamide resin. On the other hand, although we do not wish to be bound by theory, it is thought that all-aromatic polymers such as polyethersulfone (PES), polyphenylene sulfide (PPS), and polyetheretherketone (PEEK) are prone to short circuits (tracking) due to carbonization of the aromatic rings and tend to have low electrical resistance.

[0027] From the viewpoint of controlling Tm, the semi-aromatic polyamide resin is preferably a semi-aromatic polyamide resin whose main component unit is a repeating unit consisting of component units derived from aromatic dicarboxylic acids and optionally alicyclic dicarboxylic acids, and component units derived from aliphatic diamines, and more preferably a semi-aromatic polyamide resin whose main component unit is a repeating unit consisting of component units derived from aromatic dicarboxylic acids and component units derived from aliphatic diamines.

[0028] For example, from the viewpoint of making the heat of fusion (ΔH) of the crystalline polyamide resin 15 J / g or more, the component unit (b2) derived from the diamine represented by the above formula (1) is preferably 45 mol% or less, more preferably 40 mol% or less, relative to the total number of moles of component unit (b).

[0029] For example, from the viewpoint of setting the glass transition temperature (Tg) of the crystalline polyamide resin to 144°C or higher and adjusting the melting point (Tm) to within the range of 270°C to 330°C, the component unit (b2) derived from the diamine represented by formula (1) above is preferably 25 mol% or more, more preferably 30 mol% or more, relative to the total number of moles of component unit (b).

[0030] The intrinsic viscosity [η] of the crystalline polyamide resin is preferably 0.6 dl / g or more and 1.5 dl / g or less. An intrinsic viscosity [η] of crystalline polyamide resin of 0.6 dl / g or more makes it easier to increase the mechanical strength of the molded article, such as toughness, while an intrinsic viscosity [η] of 1.5 dl / g or less makes it easier to maintain the fluidity of the resin composition during molding. From a similar viewpoint, the intrinsic viscosity [η] of crystalline polyamide resin is more preferably 0.7 dl / g or more and 1.2 dl / g or less, and even more preferably 0.75 dl / g or more and 1.1 dl / g or less. The intrinsic viscosity [η] can be adjusted, for example, by the amount of end-encapsulation of the crystalline polyamide resin, the molar ratio of dicarboxylic acid and diamine when polymerizing the crystalline polyamide resin, etc.

[0031] The amount of terminal carboxyl groups in the crystalline polyamide resin is preferably 20 mmol / kg to 200 mmol / kg, and more preferably 40 mmol / kg to 170 mmol / kg.

[0032] The amount of terminal carboxyl groups mentioned above is a value measured using NMR. Specifically, for example, 30 mg of crystalline polyamide resin is dissolved in 0.5 mL of deuterated hexafluoroisopropanol (HFIP) to prepare a sample for NMR measurement. The prepared sample is subjected to NMR measurement using a nuclear magnetic resonance spectrometer (ECA-500, manufactured by JEOL Ltd.), and the molecular weight of the crystalline polyamide resin is calculated from the hydrogen-derived peak area of ​​each component constituting the crystalline polyamide resin in the obtained spectrum. The amount of terminal carboxyl groups ([COOH], unit: mmol / kg) is then calculated using the hydrogen-derived peak area and molecular weight value specific to terminal carboxyl groups.

[0033] Furthermore, the amount of terminal amino groups in the crystalline polyamide resin is preferably 10 mmol / kg to 200 mmol / kg, more preferably 30 mmol / kg to 200 mmol / kg, and even more preferably 50 mmol / kg to 150 mmol / kg.

[0034] The amount of terminal amino groups is measured by the following method: Dissolve 1 g of crystalline polyamide resin in 35 mL of phenol and mix with 2 mL of methanol to prepare the sample solution. Using thymol blue as an indicator, titrate the sample solution with a 0.01 N aqueous hydrochloric acid solution using a potentiometric titrator (Metrohm) until the solution changes from blue to yellow, and measure the amount of terminal amino groups ([NH2], unit: mmol / kg).

[0035] The crystalline polyamide resin of this disclosure can be used in a variety of applications, such as resin compositions or molded articles containing them, and components of electrical or electronic equipment, and is preferably used as an insulating material from the viewpoint of improving tracking resistance.

[0036] Crystalline polyamide resins may contain other components as desired.

[0037] The constituent units of a crystalline polyamide resin and their ratios can be calculated from the mixing ratio during the preparation of the polyamide resin, or measured by NMR spectroscopy.

[0038] 1 For H-NMR measurements, for example, a nuclear magnetic resonance spectrometer (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 observed nucleus is 1 The conditions are as follows: H (400 MHz), sequence is single pulse, pulse width is 5.12 μs (45° pulse), repetition time is 7.0 seconds, and number of integrations is 500 or more. The reference chemical shift is set to 0 ppm for hydrogen of tetramethylsilane, but similar results can also be obtained by setting the peak derived from residual hydrogen of deuterated orthodichlorobenzene to 7.10 ppm as the reference value for the chemical shift. 1 Peaks such as H can be assigned using conventional methods.

[0039] 13 For 13C-NMR measurements, for example, a nuclear magnetic resonance spectrometer (ECP500 model, manufactured by JEOL Ltd.) is used as the measuring instrument, an orthodichlorobenzene / deuterated benzene (80 / 20 vol%) mixed solvent is used, the measurement temperature is 120°C, and the observed nucleus is 13 The conditions are as follows: C (125MHz), single-pulse proton decoupling, 45° pulse, repetition time 5.5 seconds, integration count of 10,000 or more, and a chemical shift reference value of 27.50 ppm. Various signals are assigned based on conventional methods, and quantitative analysis can be performed based on the integrated signal intensity.

[0040] Furthermore, the component unit (a) derived from dicarboxylic acid in the crystalline polyamide resin may include component units derived from biomass-derived dicarboxylic acid, and the component unit (b) derived from diamine may include component units derived from biomass-derived diamine. In addition, the crystalline polyamide resin may be a biomass-derived polyamide resin obtained by polymerizing a group of raw materials including biomass-derived raw materials.

[0041] The specific composition of crystalline polyamide resin and its manufacturing method are described below.

[0042] • Component unit (a) derived from dicarboxylic acid The component unit (a) derived from a dicarboxylic acid may contain a component unit (a1) derived from at least one selected from the group consisting of terephthalic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid, in an amount greater than 50 mol% and less than or equal to 100 mol% of the total number of moles of component unit (a).

[0043] Component units (a1) derived from at least one selected from the group consisting of terephthalic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid are more likely to enhance the crystallinity and melting point (Tm) of the polyamide resin compared to component units derived from, for example, isophthalic acid. The content of component units (a1) is preferably more than 50 mol% and 100 mol% or less relative to the total number of moles of component units (a) derived from dicarboxylic acid, from the viewpoint of ensuring the crystallinity of the polyamide resin, and preferably 60 mol% to 100 mol%, more preferably 70 mol% to 100 mol%, even more preferably 80 mol% to 100 mol%, and particularly preferably 90 mol% to 100 mol% from the viewpoint of enhancing the crystallinity of the polyamide resin.

[0044] The component unit (a1) may optionally be derived from terephthalic acid and naphthalenedicarboxylic acid, and their esters, or from cyclohexanedicarboxylic acid and its esters.

[0045] The cyclohexanedicarboxylic acid is not limited to, but may be at least one selected from the group consisting of, for example, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

[0046] The component unit (a1) is preferably derived from terephthalic acid or naphthalenedicarboxylic acid, and more preferably from terephthalic acid, from the viewpoint of high crystallinity and high heat resistance, among terephthalic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid.

[0047] The component unit (a) derived from a dicarboxylic acid may optionally include, in addition to component unit (a1), component unit (a2) other than component unit (a1), such as component units derived from aromatic dicarboxylic acids other than terephthalic acid and naphthalenedicarboxylic acid and their esters, component units derived from alicyclic dicarboxylic acids other than cyclohexanedicarboxylic acid and its esters, and component units derived from aliphatic chain dicarboxylic acids.

[0048] When component unit (a) derived from a dicarboxylic acid contains component unit (a1) and component unit (a2), the content of component unit (a2) is preferably 1 mol% or more and less than 20 mol%, more preferably 1 mol% or more and 10 mol%, relative to the total number of moles of component unit (a), from the viewpoint of maintaining the crystallinity of the polyamide resin.

[0049] Other aromatic carboxylic acid components besides terephthalic acid and naphthalenedicarboxylic acid and their esters include, for example, isophthalic acid and 2-methylterephthalic acid and their esters. Among these, isophthalic acid-derived component units are preferred, and their content is preferably 1 mol% or more and less than 20 mol%, more preferably 1 mol% or more and 10 mol%, and even more preferably 1 mol% or more and 5 mol%, relative to the total number of moles of component units (a) derived from dicarboxylic acid.

[0050] Examples of component units derived from alicyclic dicarboxylic acids other than cyclohexanedicarboxylic acid and its esters include monocyclic cycloalkanedicarboxylic acids other than cyclohexane, monocyclic cycloalkenedicarboxylic acids, polycyclic alkanedicarboxylic acids, polycyclic alkenedicarboxylic acids, and component units derived from their esters, etc.

[0051] As component units derived from aliphatic chain dicarboxylic acids, for example, component units derived from aliphatic dicarboxylic acids having 4 to 20 carbon atoms may be used, and from the viewpoint of adjusting the glass transition temperature (Tg) and melting point (Tm), improving crystallinity, and improving tracking resistance, component units derived from aliphatic dicarboxylic acids having an alkylene group with 6 to 12 carbon atoms are preferred.

[0052] Examples of aliphatic chain dicarboxylic acids include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, and suberic acid. Among these, adipic acid and sebacic acid are preferred from the viewpoint of adjusting the glass transition temperature (Tg) and melting point (Tm), improving crystallinity, and improving tracking resistance.

[0053] From the viewpoint of ensuring the crystallinity of the polyamide resin, the content of component units derived from aliphatic chain dicarboxylic acids is preferably 1 mol% or more and less than 20 mol%, more preferably 1 mol% or more and 10 mol%, and even more preferably 1 mol% or more and 5 mol%, relative to the total number of moles of component units (a) derived from dicarboxylic acids.

[0054] If the crystalline polyamide resin is a semi-aromatic polyamide resin, the semi-aromatic polyamide resin may further contain small amounts of tribasic or higher polycarboxylic acid component units, such as trimellitic acid or pyromellitic acid, in addition to the component units (a1) and (a2) described above. The content of such polycarboxylic acid component units can be 0 mol% to 5 mol%, or greater than 0 mol% and less than or equal to 5 mol%, relative to the total number of moles of component units (a) derived from dicarboxylic acid.

[0055] • Component units derived from diamines (b) The component unit (b) derived from the diamine is a component unit (b1) derived from an alkylenediamine with 4 to 18 carbon atoms, and the following formula (1): [ka] {In the formula, R1 and R2 are each independently selected from the group consisting of hydrogen atoms, alkyl groups, alkoxy groups, halogenated alkyl groups, halogenated alkoxy groups, and halogen atoms.} It contains a component unit (b2) derived from a diamine represented by , and .

[0056] In crystalline polyamide resins, the combined use of a component unit (b1) derived from alkylenediamines with 4 to 18 carbon atoms and a component unit (b2) derived from diamines represented by the above formula (1) maintains high heat resistance, and consequently enables the achievement of both mechanical strength and moldability even in high-temperature environments of, for example, around 150°C.

[0057] The component unit (b) derived from the diamine may optionally further include component units (b1) and (b2) in addition to component unit (b3) derived from another diamine.

[0058] • Component unit (b1) derived from alkylenediamines with 4 to 18 carbon atoms. The component unit (b1) is derived from an alkylenediamine having preferably 4 to 18 carbon atoms, more preferably 4 to 10 carbon atoms, from the viewpoint of not lowering the glass transition temperature (Tg) of the crystalline polyamide resin.

[0059] The alkylenediamine having 4 to 18 carbon atoms constituting the component unit (b1) may include, for example, linear alkylenediamines having 4 to 18 carbon atoms, branched alkylenediamines having 4 to 18 carbon atoms, and among these, from the viewpoint of improving the crystallinity of the polyamide resin, it is preferable to include linear alkylenediamines having 4 to 18 carbon atoms, and more preferably to include linear alkylenediamines having 4 to 10 carbon atoms.

[0060] Examples of alkylenediamines having 4 to 18 carbon atoms include linear alkylenediamines such as 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-diaminoundecane, and 1,12-diaminododecane; and branched alkylenediamines such as 2-methyl-1,5-pentanediamine and 2-methyl-1,8-octanediamine. Among these, from the viewpoint of controlling Tm or Tg, 1,4-diaminobutane, 1,6-diaminohexane, 1,9-nonanediamine, 1,10-decanediamine, and 2-methyl-1,5-pentanediamine are preferred, 1,6-diaminohexane and 1,10-decanediamine are more preferred, and 1,6-diaminohexane is even more preferred.

[0061] The alkylenediamines listed above may be one type or two or more types.

[0062] The content of component unit (b1) derived from alkylenediamine having 4 to 18 carbon atoms can be determined according to component unit (b2) derived from diamine represented by the above formula (1), and is preferably 55 mol% to 75 mol%, and more preferably 60 mol% to 70 mol%, relative to the total number of moles of component unit (b).

[0063] • Component unit (b2) derived from the diamine represented by the above formula (1) Although we do not wish to be constrained by theory, the component unit (b2) derived from the diamine represented by formula (1) above is thought to be sterically hindered by the bulkiness of the alicyclic structure in formula (1), which reduces the mobility of the molecular chain, increases the glass transition temperature (Tg) of the crystalline polyamide resin, and furthermore, the bonding portion between the alicyclic structures may adjust the melting point (Tm) of the crystalline polyamide resin to a temperature range that maintains moldability.

[0064] In formula (1), R1 and R2 are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, and a halogen atom. The number of carbon atoms in the alkyl group or alkoxy group is not limited, but may be, for example, 1 to 30, 1 to 26, 1 to 22, 1 to 18, 1 to 12, 1 to 6, or 1 to 4.

[0065] Examples of alkyl groups include linear or branched unsubstituted alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group, 1-methylheptyl group, and 2-ethylhexyl group. Among these, from the viewpoint of optimizing steric hindrance, controlling Tg and Tm, and improving crystallinity and moldability, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group are preferred, methyl group, ethyl group, n-propyl group, and isopropyl group are more preferred, and methyl group is even more preferred.

[0066] Examples of alkoxy groups include linear, branched, or cyclic unsubstituted alkoxy groups such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tert-butyloxy, sec-butyloxy, n-pentyloxy, isopentyloxy, n-hexyloxy, 2-methylpentyloxy, 1,1-dimethylbutyloxy, 1,2,2-trimethylpropyloxy, 2-ethylbutyloxy, 1,3-dimethylhexyloxy, cyclohexyloxy, methylcyclopentyloxy, n-heptyloxy, n-heptyloxy, n-octyloxy, 3,5,5-trimethylhexyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, 1-adamantyloxy, and n-pentadecyloxy.

[0067] Examples of halogenated alkyl groups include those obtained by substituting some or all of the hydrogen atoms of the above-mentioned alkyl group with halogen atoms.

[0068] Examples of halogenated alkoxy groups include those in which some or all of the hydrogen atoms of the above-mentioned alkoxy group are substituted with halogen atoms.

[0069] Examples of halogen atoms include chlorine atoms, fluorine atoms, bromine atoms, and iodine atoms. Among these, chlorine atoms and fluorine atoms are preferred.

[0070] In formula (1), R1 and R2 are preferably at least one selected independently from the group consisting of a hydrogen atom and an alkyl group, from the viewpoint of controlling the glass transition temperature (Tg) and melting point (Tm) of the crystalline polyamide resin, as well as moldability and mechanical strength. More preferably, R1 and R2 are at least one selected independently from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. It is even more preferable that both R1 and R2 are at least one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.

[0071] Furthermore, if the diamine represented by formula (1) has geometric isomers (such as a trans isomer and a cis isomer), either isomer may be used, and the ratio of the isomers is not particularly limited.

[0072] Preferred specific examples of the diamine represented by formula (1) include the following: Bis(4-aminocyclohexyl)methane (PACM); 4,4'-Diamino-3,3'-Dimethyldicyclohexylmethane (MACM); 4,4'-diamino-3,3'-diethyldicyclohexylmethane; 4,4'-diamino-3,3'-di(n-propyl)dicyclohexylmethane; 4,4'-diamino-3,3'-di(isopropyl)dicyclohexylmethane; 4,4'-diamino-3,3'-di(n-butyl)dicyclohexylmethane; 4,4'-diamino-3,3'-di(sec-butyl)dicyclohexylmethane; 4,4'-diamino-3,3'-di(isobutyl)dicyclohexylmethane; 4,4'-diamino-3,3'-di(tert-butyl)dicyclohexylmethane; 4,4'-diamino-3-methyl-dicyclohexylmethane; 4,4'-diamino-3-ethyl-dicyclohexylmethane; 4,4'-diamino-3-n-propyl-dicyclohexylmethane; 4,4'-diamino-3-isopropyl-dicyclohexylmethane; 4,4'-diamino-3-n-butyl-dicyclohexylmethane; 4,4'-diamino-3-sec-butyl-dicyclohexylmethane; 4,4'-diamino-3-isobutyl-dicyclohexylmethane; 4,4'-diamino-3-tert-butyl-dicyclohexylmethane; and These include their isomers, etc.

[0073] The content of component unit (b2) derived from the diamine represented by formula (1) above can be determined according to the optimization of the glass transition temperature (Tg) and melting point (Tm) of the crystalline polyamide resin, as well as the desired moldability. Preferably, it is 25 mol% to 45 mol%, and more preferably 30 mol% to 40 mol%, relative to the total number of moles of component unit (b).

[0074] • Component units derived from other diamines (b3) Examples of component units (b3) derived from other diamines include alkylenediamines having 4 to 18 carbon atoms, aliphatic diamines other than the diamine represented by formula (1) above, and aromatic diamines. The content of component units (b3) derived from other diamines may be 50 mol% or less relative to the total number of moles of component units (b) derived from diamines.

[0075] Aliphatic diamines other than alkylenediamines having 4 to 18 carbon atoms and diamines represented by formula (1) above include, for example, alkylenediamines having 3 or fewer carbon atoms, alkylenediamines having 19 or more carbon atoms, and alicyclic diamines other than the diamine represented by formula (1) above. Alicyclic diamines other than the diamine represented by formula (1) above include, for example, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 2,5-bisaminomethylnorbornane, and 2,6-bisaminomethylnorbornane.

[0076] Examples of aromatic diamines include metaxylylenediamine.

[0077] • End-cap encapsulant In crystalline polyamide resins, at least some of the end groups of the molecules can be encapsulated with an end-capturing agent, from the viewpoint of improving thermal stability during compounding or molding and achieving high mechanical strength.

[0078] The end-capturing agent is preferably a monoamine if the molecular end is a carboxyl group, and preferably a monocarboxylic acid if the molecular end is an amino group.

[0079] 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.

[0080] 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, tridecyl 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.

[0081] Aromatic monocarboxylic acids and alicyclic monocarboxylic acids may optionally have substituents on the cyclic structure.

[0082] • Method for producing crystalline polyamide resin Crystalline polyamide resins can be produced, for example, by polycondensing the aforementioned dicarboxylic acid and the aforementioned diamine in a homogeneous solution. Specifically, a lower-order condensate can be obtained by heating the dicarboxylic acid and the diamine in the presence of a known catalyst, and then a crystalline polyamide resin can be produced by applying shear stress to the molten lower-order condensate and causing polycondensation.

[0083] From the viewpoint of adjusting the intrinsic viscosity or molecular weight of the crystalline polyamide resin, the aforementioned end-capturing agent may be added to the reaction system of dicarboxylic acid and diamine. The intrinsic viscosity [η] or molecular weight of the crystalline polyamide resin can be adjusted according to the amount of end-capturing agent added. The amount of end-capturing agent added is preferably 0.07 moles or less, and more preferably 0.05 moles or less, per 1 mole of the total amount of dicarboxylic acid.

[0084] <Resin composition> In another embodiment, a resin composition comprising the crystalline polyamide resin of the Disclosure is provided. By comprising the crystalline polyamide resin of the Disclosure, the glass transition temperature (Tg), melting point (Tm), heat of fusion (ΔH), and crystallization temperature (Tc) of the resin composition can be controlled and improved, and the resin composition exhibits excellent mechanical strength and moldability even in high-temperature environments of, for example, about 150°C.

[0085] The content of crystalline polyamide resin in the resin composition can be determined according to the application of the resin composition. For example, it can be adjusted to 5 to 95 parts by mass, 10 to 90 parts by mass, 20 to 85 parts by mass, or 30 to 80 parts by mass per 100 parts by mass of the resin composition.

[0086] The resin composition may further contain other components besides the crystalline polyamide resin, if necessary.

[0087] Other examples of components include reinforcing agents (fibrous fillers, etc.), nucleating agents, lubricants, elastomers (rubber), flame retardants (brominated, chlorinated, phosphorus, antimony, and inorganic, etc.), antistatic agents, mold release agents, antioxidants (phenols, amines, sulfurs, and phosphorus, etc.), stabilizers (lactone compounds; vitamin E; hydroquinones; copper-based stabilizers such as copper halides; iodine compounds; light stabilizers such as benzotriazoles, triazines, benzophenones, benzoates, hindered amines, and oxanilides; and mixtures thereof), and other polymers (amorphous polyamide resins, polyolefins, olefin copolymers such as ethylene-propylene copolymers and ethylene-1-butene copolymers, olefin copolymers such as propylene-1-butene copolymers, polystyrene, polyamides, polycarbonates, polyacetals, polysulfones, polyphenylene oxides, fluororesins, silicone resins, and liquid crystal polymers (LCPs)).

[0088] In particular, the resin composition may contain a reinforcing agent from the viewpoint of increasing the mechanical strength of the molded article, such as tensile strength, tensile modulus, and toughness; a lubricant from the viewpoint of increasing the injection flowability of the resin composition and improving the appearance of the molded article; a nucleating agent from the viewpoint of increasing the crystallinity of the molded article; and a stabilizer from the viewpoint of ensuring heat resistance.

[0089] As a reinforcing agent, fibrous fillers are preferred from the viewpoint of increasing mechanical strength such as tensile strength, tensile modulus, and toughness. Fibrous fillers can impart high mechanical strength to the resin composition. Examples of fibrous fillers include glass fibers, wollastonite, potassium titanate whiskers, calcium carbonate whiskers, aluminum borate whiskers, magnesium sulfate whiskers, zinc oxide whiskers, milled fibers, and cut fibers. Of these, one type may be used alone, or two or more types may be used in combination. Among these, wollastonite, glass fibers, and potassium titanate whiskers are preferred because they easily increase the mechanical strength of the molded article, and wollastonite or glass fibers are more preferred.

[0090] The average fiber length of the fibrous filler can be, for example, 1 μm to 20 mm, preferably 5 μm to 10 mm, from the viewpoint of moldability of the resin composition and mechanical strength or heat resistance of the resulting molded article. Furthermore, the aspect ratio of the fibrous filler can be, for example, 5 to 2000, preferably 30 to 600.

[0091] The average fiber length and average fiber diameter of fibrous fillers can be measured by the following method. 1) The resin composition is dissolved in a hexafluoroisopropanol / chloroform solution (10 / 90 vol%), and the resulting filtrate is collected after filtration. 2) The filtrate obtained in 1) above is dispersed in water, and the fiber length (Li) and fiber diameter (di) of any 300 fibers are measured using an optical microscope (magnification: 50x). The number of fibers with a fiber length of Li is denoted as qi, and the weight-average length (Lw) is calculated based on the following formula, and this is taken as the average fiber length of the fibrous filler. Weight-average length (Lw) = (Σqi × Li 2 ) / (Σqi×Li) Similarly, let ri be the number of fibers with a fiber diameter of Di, and calculate the weight-average diameter (Dw) based on the following formula, and use this as the average fiber diameter of the fibrous filler. Weight average diameter (Dw)=(Σri×Di 2 ) / (Σri×Di)

[0092] The content of the fibrous filler is not limited, but it can be, for example, 15 parts by mass or more and 70 parts by mass or less per 100 parts by mass of the total of the crystalline polyamide resin and the fibrous filler.

[0093] Copper-based stabilizers can be used as stabilizers.

[0094] The resin composition may be produced by mixing the crystalline polyamide resin of this disclosure and, if necessary, other components using known resin mixing methods, such as a Henschel mixer, V-blender, ribbon blender, or tumbler blender; or by further melt-kneading the mixed components using a single-screw extruder, multi-screw extruder, kneader, or Banbury mixer, followed by granulation or pulverization.

[0095] <Application> The crystalline polyamide resin and resin compositions containing the same can be used as various molded articles by molding them using known molding methods such as compression molding, injection molding, and extrusion molding.

[0096] Molded articles comprising the crystalline polyamide resin or resin composition of the present disclosure can be used in a variety of applications. Such applications include, for example, automotive exterior parts such as radiator grilles, rear spoilers, wheel covers, wheel caps, cowl vent grilles, air outlet louvers, air scoops, hood bulges, sunroofs, sunroof rails, fenders and tailgates; automotive engine compartment components such as cylinder head covers, engine mounts, air intake manifolds, throttle bodies, air intake pipes, radiator tanks, radiator supports, water pumps, water pump inlets, water pump outlets, thermostat housings, cooling fans, fan shrouds, oil pans, oil filter housings, oil filler caps, oil level gauges, oil pumps, timing belts, timing belt covers and engine covers; and fuel caps, fuel filler tubes, automotive fuel tanks, fuel sender modules, fuel cutoff valves and quick releases. Automotive fuel system components such as connectors, canisters, fuel delivery pipes and fuel filler necks; automotive drivetrain components such as shift lever housings and propeller shafts; automotive chassis components such as stabilizer bars, linkage rods and engine mount brackets; automotive functional components such as window regulators, door locks, door handles, outside door mirror stays, wipers and their components, accelerator pedals, pedal modules, fittings, plastic screws, nuts, bushings, seal rings, bearings, bearing retainers, gears and actuators; automotive electronic components such as wire harness connectors, relay blocks, sensor housings, fuse components, enclosures, ignition coils and distributor caps; fuel system components for general-purpose equipment such as fuel tanks for general-purpose equipment (e.g., brush cutters, lawnmowers and chainsaws); electrical equipment components and / or electronic equipment components such as connectors, busbars and LED reflectors.Examples include electric vehicle components such as connectors for Battery Management Systems (BMS), motor busbars, and motor-generator busbars; building material components, industrial equipment components, and various enclosures or exterior components such as small enclosures (including those for personal computers and mobile phones) and molded exterior parts.

[0097] In particular, the resin composition of this disclosure and the molded articles containing the same exhibit excellent mechanical strength and moldability even in high-temperature environments of approximately 150°C, and also have tracking resistance, making them suitable for use as insulating members or components of electrical or electronic equipment.

[0098] In another embodiment, a conductive member can be provided that includes an insulating member comprising a resin composition according to the present disclosure and a conductive metal member located creepage of the insulating member.

[0099] In another embodiment, the conductive member, due to the heat resistance and tracking resistance of the aforementioned crystalline polyamide resin in the resin composition, suppresses the temperature rise of the conductive metal member, improving tracking resistance (i.e., high CTI), and also enabling a reduction in the creepage distance between conductive metal members, which in turn allows for miniaturization of the conductive member or a reduction in excess members such as ribs.

[0100] The insulating member may include, for example, a molded article obtained by molding the resin composition of the present disclosure by at least one selected from the group consisting of injection molding, compression molding, and extrusion molding, or may consist of such a molded article.

[0101] The conductive metal member is not particularly limited as long as it contains a conductive metal, and can be formed from known conductive metal materials. For example, it may include at least one metal selected from the group consisting of copper, aluminum, copper alloys, and aluminum alloys. The conductive metal member may contain only one type of metal or two or more types of metal.

[0102] The conductive metal member may take the form of, for example, a metal terminal. The conductive metal member may optionally have a plating layer on at least a portion of its surface or exposed surface.

[0103] In the manufacture of conductive members, an insulating member containing a resin composition or molded body and a conductive metal member can be joined and integrated, preferably without adhesives or screws, by, for example, subjecting the conductive metal member to polishing, roughening, or plating, and positioning at least a portion of the conductive metal member on the creepage surface of the insulating member. [Examples]

[0104] The present disclosure will be described in more detail below with reference to the examples. The scope disclosed herein is not to be limited by the examples.

[0105] 1. Measurement

[0106] 1-1. Physical properties of resins The physical properties of each resin were measured using the following method.

[0107] <Intrinsic viscosity [η]> In accordance with JIS K6810-1977, 0.5 g of polyamide resin was dissolved in 50 ml of 96.5% sulfuric acid solution to prepare the sample solution. The flow time of the obtained sample solution was measured using an Ubbelohde viscometer under conditions of 25 ± 0.05 °C. The measurement results are expressed by the following formula: [η]=ηSP / [C(1+0.205ηSP)] ηSP = (t - t0) / t0 {In formula: [η]: Intrinsic viscosity (dl / g) ηSP: Specific viscosity C: Sample concentration (g / dl) t: Number of seconds (seconds) the sample solution flows down. t0: Number of seconds (seconds) of the blank sulfuric acid flowing down the slope. The intrinsic viscosity [η] of the polyamide resin was calculated by applying this formula.

[0108] <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 model, Seiko Instruments Inc.). Specifically, approximately 5 mg of polyamide resin was sealed in a measuring aluminum pan, placed in the differential scanning calorimeter, and heated from room temperature to 350°C at a rate of 10°C / min. To completely melt the resin, it was held at 350°C for 3 minutes, and then cooled to 30°C at a rate of 10°C / min. After being left at 30°C for 5 minutes, a second heating was performed to 350°C at a rate of 10°C / min. The temperature of the endothermic peak (°C) during this second heating was defined as the melting point (Tm) of the polyamide resin, and the displacement point corresponding to the glass transition was defined as the glass transition temperature (Tg).

[0109] <Heat of fusion (ΔH)> The heat of fusion (ΔH) of polyamide resins was determined from the area of ​​the endothermic peak during the first heating process, in accordance with JIS K7122 (2012). The presence or absence of crystallinity was evaluated from the endothermic peak of crystallinity, its area, and the heat of fusion (ΔH), and indicated in Table 1 as ○ (crystallinity present) or × (non-crystallinity). All polyamide resins evaluated as ○ (crystallinity present) in Table 1 had a heat of fusion (ΔH) of 15 J / g or more.

[0110] 1-2. Physical properties and evaluation of polyamide resin compositions The physical properties of each polyamide resin composition were measured and evaluated using the following method.

[0111] <Melting point (Tm), glass transition temperature (Tg), crystallization temperature (Tc)> The melting point (Tm) and glass transition temperature (Tg) of the polyamide resin composition were measured using a differential scanning calorimeter (DSC220C model, Seiko Instruments Inc.). Specifically, approximately 5 mg of the polyamide resin composition was sealed in a measuring aluminum pan, placed in the differential scanning calorimeter, and heated from room temperature to 350°C at a rate of 10°C / min. To completely melt the polyamide resin composition, it was held at 350°C for 5 minutes, and then cooled to 30°C at a rate of 10°C / min. After being left at 30°C for 5 minutes, a second heating was performed to 350°C at a rate of 10°C / min. The temperature of the endothermic peak (°C) during this second heating was defined as the melting point (Tm) of the polyamide resin composition, the displacement point corresponding to the glass transition was defined as the glass transition temperature (Tg) of the polyamide resin composition, and the temperature of the exothermic peak (°C) during the cooling process was defined as the crystallization temperature (Tc) of the polyamide resin composition.

[0112] <Heat of fusion (ΔH)> The heat of fusion (ΔH) of the polyamide resin composition was determined from the area of ​​the endothermic peak during crystallization in the first heating process, in accordance with JIS K7122 (2012).

[0113] <Tensile strength and tensile modulus at 150°C> The obtained polyamide resin compositions were injected under the following conditions to form ISO dumbbell-shaped test specimens of Type A with a thickness of 4.0 mm. Molding machine: Sumitomo Heavy Industries, Ltd. SG50M3 Molding machine cylinder temperature: Melting point of polyamide resin + 10°C Mold temperature: 160℃

[0114] The obtained test specimens were left for 24 hours at a temperature of 23°C in a nitrogen atmosphere. Then, in accordance with ISO 527, tensile tests were performed at a temperature of 150°C and a relative humidity of 50%, and the tensile strength (breaking strength) (MPa) and tensile modulus (GPa) were measured.

[0115] 2. Resin synthesis

[0116] 2-1. Synthesis of polyamide resin (example)

[0117] (Synthesis example PA1) 257.52 g (1551.1 mmol) of terephthalic acid, 130.0 g (1120.7 mmol) of 1,6-diaminohexane, 100.85 g (480.2 mmol) of bis(4-aminocyclohexyl)methane (PACM), 0.37 g of sodium hypophosphate monohydrate, and 81.8 g of distilled water were placed in a 1 L autoclave and purged with nitrogen. Stirring was started 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 continuing the reaction for 1 hour, the mixture was released into the atmosphere through a spray nozzle installed at the bottom of the autoclave, and the lower condensate was extracted. After the lower condensate was cooled to room temperature, it was 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 obtained lower-order condensate was 0.12 dl / g.

[0118] Next, this lower-order condensate was placed in a shelf-type solid-phase polymerization apparatus, and after purging with nitrogen, the temperature was raised to 215°C over approximately 1 hour and 30 minutes. After that, the reaction was allowed to continue for another 1 hour and 30 minutes, and then the temperature was lowered to room temperature. The intrinsic viscosity [η] of the obtained prepolymer was 0.45 dl / g.

[0119] Subsequently, the obtained prepolymer was melt-polymerized in a twin-screw extruder with a screw diameter of 30 mm and an L / D ratio of 36, at a barrel temperature of 330°C, a screw rotation speed of 200 rpm, and a resin supply rate of 6 kg / h to obtain polyamide resin PA1.

[0120] The obtained polyamide resin PA1 had an intrinsic viscosity [η] of 0.97 dl / g, a melting point (Tm) of 317°C, a glass transition temperature (Tg) of 150°C, and a heat of fusion (ΔH) of 56 J / g.

[0121] (Synthesis Examples PA2 to PA4) Polyamide resins PA2 to PA4 were obtained in the same manner as in synthesis example PA1, except that the total amount of 1,6-diaminohexane and PACM added to the autoclave was maintained, while their ratios were changed as shown in Table 1.

[0122] (Synthesis example PA5) 251.6 g (1515.7 mmol) of terephthalic acid, 127.0 g (1094.8 mmol) of 1,6-diaminohexane, 111.6 g (468.9 mmol) of bis(4-amino-3-methylcyclohexyl)methane (MACM), 0.37 g of sodium hypophosphite monohydrate, and 81.8 g of distilled water were placed in a 1 L autoclave and purged with nitrogen. Stirring was started 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 continuing the reaction for 1 hour, the mixture was released into the atmosphere through a spray nozzle installed at the bottom of the autoclave, and the lower condensate was extracted. After the lower condensate was cooled to room temperature, it was 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 obtained lower-order condensate was 0.12 dl / g.

[0123] Next, this lower-order condensate was placed in a shelf-type solid-phase polymerization apparatus, and after purging with nitrogen, the temperature was raised to 215°C over approximately 1 hour and 30 minutes. After that, the reaction was allowed to continue for another 1 hour and 30 minutes, and then the temperature was lowered to room temperature. The intrinsic viscosity [η] of the obtained prepolymer was 0.45 dl / g.

[0124] Subsequently, the obtained prepolymer was melt-polymerized in a twin-screw extruder with a screw diameter of 30 mm and an L / D ratio of 36, at a barrel temperature of 330°C, a screw rotation speed of 200 rpm, and a resin supply rate of 6 kg / h to obtain polyamide resin PA5.

[0125] The obtained polyamide resin PA5 had an intrinsic viscosity [η] of 0.97 dl / g, a melting point (Tm) of 327°C, a glass transition temperature (Tg) of 162°C, and a heat of fusion (ΔH) of 42 J / g.

[0126] (Synthesis examples PA6 to PA8) Polyamide resins PA6 to PA8 were obtained in the same manner as in synthesis example PA5, except that the total amount of 1,6-diaminohexane and MACM added to the autoclave was maintained, while their ratios were changed as shown in Table 1.

[0127] Table 1 shows the evaluation results for polyamide resins PA1 to PA8.

[0128] [Table 1]

[0129] 2-1. Synthesis of polyamide resin (comparative example)

[0130] • Polyamide resin PA9 (6T / 6I=70 / 30) Polyamide resin PA9 was obtained in the same manner as in synthesis example PA1, except that the raw materials placed in the autoclave consisted of 280 g (2410 mmol) of 1,6-hexanediamine, 277.4 g (1670 mmol) of terephthalic acid, and 119.6 g (720 mmol) of isophthalic acid, with the addition of 3.66 g (30 mmol) of benzoic acid, 5.7 g of sodium hypophosphate monohydrate, and 545 g of distilled water.

[0131] The obtained polyamide resin PA9 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.

[0132] • Polyamide resin PA10 (6T / 66=70 / 30) Polyamide resin PA10 was obtained in the same manner as in synthesis example PA1, except that the raw materials placed in the autoclave were 280 g (2410 mmol) of 1,6-hexanediamine, 277.4 g (1670 mmol) of terephthalic acid, and 119.6 g (720 mmol) of adipic acid, 3.66 g (30 mmol) of benzoic acid were added, and the amount of sodium hypophosphate monohydrate was 5.7 g and the amount of distilled water was 545 g.

[0133] The obtained polyamide resin PA10 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.

[0134] 3. Materials, preparation, and evaluation of polyamide resin compositions

[0135] 3-1.Materials

[0136] 3-1-1. Polyamide resin Polyamide resin PA1 (6T / (PACM)T=70 / 30) Polyamide resin PA5 (6T / (MACM)T=70 / 30) Polyamide resin PA9 (6T / 6I=70 / 30) Polyamide resin PA10 (6T / 66=70 / 30)

[0137] 3-1-2. Copper-based stabilizers A mixture of 10% by mass of copper(I) iodide and 90% by mass of potassium iodide was used as a copper-based heat stabilizer.

[0138] 3-1-3. Nuclear Agents Talc (fine particle talc) was used as a crystal nucleating agent.

[0139] 3-1-4. Lubricant Sodium montanoate (manufactured by Clariant, LICOMONT NAV101 ("LICOMONT" is a registered trademark of the company)) was used as a lubricant.

[0140] 3-1-5. Reinforcement material Glass fiber (Owens Corning, FT756D) was used as a reinforcing material.

[0141] 3-2. Preparation and Evaluation of Polyamide Resin Compositions The above materials were mixed in a tumbler blender in the composition ratio (units are parts by mass) shown in Table 2, and then melt-kneaded using a 30 mmφ vented twin-screw extruder under cylinder temperature conditions of 300°C to 335°C. The kneaded material was then extruded into strands and cooled in a water bath. The strands were then taken up and cut with a pelletizer to obtain a pelletized polyamide resin composition.

[0142] The physical properties of the obtained polyamide resin composition were measured and evaluated as described above. The measurement and evaluation results of the polyamide resin composition are shown in Table 2.

[0143] [Table 2]

Claims

1. A crystalline polyamide resin comprising a component unit (a) derived from a dicarboxylic acid and a component unit (b) derived from a diamine, The component unit (a) derived from the dicarboxylic acid includes a component unit (a1) derived from at least one selected from the group consisting of terephthalic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid. The content of the aforementioned component unit (a1) is more than 50 mol% and 100 mol% or less relative to the total number of moles of component unit (a) derived from the dicarboxylic acid. The component unit (b) derived from the diamine is, A component unit (b1) derived from an alkylenediamine with 4 to 18 carbon atoms, The following formula (1): 【Chemistry 1】 {In the formula, R1 and R2 are each independently selected from the group consisting of hydrogen atoms, alkyl groups, alkoxy groups, alkyl halides, alkoxy halides, and halogen atoms.} It includes a component unit (b2) derived from a diamine represented by and The content of the aforementioned component unit (b2) is 25 mol% or more and 45 mol% or less relative to the total number of moles of the component unit (b) derived from the diamine. Crystalline polyamide resin.

2. The crystalline polyamide resin according to claim 1, wherein the glass transition temperature (Tg) is 144°C or higher.

3. A crystalline polyamide resin according to claim 1 or 2, wherein the melting point (Tm) is 270°C or higher and 330°C or lower.

4. A crystalline polyamide resin according to claim 1 or 2, wherein the heat of fusion (ΔH) is 15 J / g or more.

5. A resin composition comprising the crystalline polyamide resin according to claim 1 or 2.

6. A molded article comprising the resin composition described in claim 5.

7. A molded body according to claim 6, which is a component of an electrical or electronic device.

8. An insulating member comprising the resin composition described in claim 5, A conductive metal member located on the surface of the insulating member, A conductive component, including a conductive component.

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