Polyamide resin composition

Abstract

This disclosure aims to provide a polyamide resin composition that can improve reflow heat resistance, and a molded article containing the same. [Solution] A polyamide resin composition comprising a semi-aromatic polyamide resin (A), a hydrophilic zeolite (B), and a halogen-based flame retardant (C).

Description

[Technical Field]

[0001] This disclosure relates to polyamide resin compositions, molded articles, methods for manufacturing electronic devices, and the like. [Background technology]

[0002] Polyamide resin compositions are widely used as materials for various components in industrial materials, automobiles, electrical and electronic equipment, and other industrial applications due to their excellent moldability, mechanical properties, and chemical resistance.

[0003] When modifying a polyamide resin composition or imparting various properties to it, it is known that fillers or additives such as zeolites are added to the polyamide resin.

[0004] For example, Patent Document 1 describes how to improve the blister resistance of a thermoplastic resin composition by adding hydrophobic zeolite to a semi-aromatic polyamide resin.

[0005] For example, Patent Document 2 describes an automotive thermoplastic resin composition that, by adding zeolite and a copper halide-based heat stabilizer to a semi-aromatic polyamide resin, has excellent heat resistance and hydrolysis resistance over a long period of time, and can maintain mechanical strength for a long time even in an environment with a temperature of 220°C.

[0006] For example, Patent Document 3 describes a semi-aromatic polyamide resin composition for plated molded products that has good plating properties, low water absorption, and solder reflow resistance by adding zeolite to a semi-aromatic polyamide resin. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2001-115048 [Patent Document 2] Japanese Patent Publication No. 2015-227449 [Patent Document 3] International Publication No. 2021 / 054050 [Overview of the project] [Problems that the invention aims to solve]

[0008] For example, in solder reflow processes using surface mount technology (SMT), the polyamide molded body, substrate, and solder may be heated to temperatures of 240°C or higher.

[0009] However, conventional semi-aromatic polyamide resin compositions, such as those described in Patent Documents 1 to 3, still have room for improvement in terms of reflow heat resistance.

[0010] This disclosure has been made in view of the above circumstances and aims to provide a polyamide resin composition that can improve reflow heat resistance, and a molded article containing the same. [Means for solving the problem]

[0011] One aspect of this disclosure is listed below. (1) Semi-aromatic polyamide resin (A), Hydrophilic zeolite (B) and, Halogen-based flame retardant (C), A polyamide resin composition containing the following: (2) The polyamide resin composition according to item 1, wherein the molar ratio of SiO2 / Al2O3 contained in the hydrophilic zeolite (B) is less than 30. (3) The polyamide resin composition according to item 1 or 2, wherein the content of the hydrophilic zeolite (B) is 0.1% by mass or more and 10% by mass or less based on 100% by mass of the polyamide resin composition. (4) The polyamide resin composition according to any one of items 1 to 3, wherein the halogen content of the halogen-based flame retardant (C) is 65% by mass or more relative to the total mass of the halogen-based flame retardant (C). (5) A polyamide molded body comprising the polyamide resin composition according to any one of Items 1 to 4. (6) The polyamide molded body according to Item 5, which is a component of an electronic device. (7) A step of disposing the polyamide molded body according to Item 6 on a substrate, A step of heating the polyamide molded body and the substrate and fixing the polyamide molded body and the substrate by reflow soldering, A method for manufacturing an electronic device, comprising: (8) In the fixing step, the polyamide molded body, the substrate, and the solder are heated at a temperature of 240°C or higher in a reflow furnace. The method for manufacturing an electronic device according to Item 7.

Advantages of the Invention

[0012] According to the present disclosure, it is possible to provide a polyamide resin composition capable of improving reflow heat resistance, a molded body containing the same, and an electronic device.

Brief Description of the Drawings

[0013] [Figure 1] FIG. 1 is a graph showing the relationship between the temperature and time of the reflow process of the reflow heat resistance test performed in Examples and Comparative Examples.

Modes for Carrying Out the Invention

[0014] In the present disclosure, the numerical range indicated using "~" means a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively.

[0015] 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.

[0016] Unless otherwise specified, the numerical values ​​described herein are measured by the methods described in the Examples.

[0017] Polyamide resins can be any resin containing multiple amide bonds, and by using various types of monomers such as lactams, diamines, and dicarboxylic acids, a wide variety of molecular frameworks can be created, thereby changing their physical properties.

[0018] Furthermore, a semi-aromatic polyamide is a polyamide containing structural units derived from a diamine and structural units derived from a dicarboxylic acid, wherein the structural units derived from the diamine include structural units derived from an aliphatic diamine or a alicyclic diamine, and the structural units derived from the dicarboxylic acid include structural units derived from an aromatic dicarboxylic acid, or a polyamide in which the structural units derived from the diamine include structural units derived from an aromatic diamine, and the structural units derived from the dicarboxylic acid include structural units derived from an aliphatic dicarboxylic acid or a alicyclic dicarboxylic acid.

[0019] <Polyamide resin composition> In one embodiment of the present disclosure, a polyamide resin composition is provided. The polyamide resin composition is a resin composition in which the main component of the resin components is a polyamide resin. The fact that the main component is a polyamide resin means that the polyamide resin accounts for the largest proportion of the resin components. In the polyamide resin composition, it is preferable that the proportion of polyamide resin among the resin components is 50% by mass or more.

[0020] The proportion of polyamide resin in the resin components of the polyamide resin composition is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit of the proportion of polyamide resin in the resin components of the polyamide resin composition is not particularly limited, but may be, for example, 100% by mass or less, less than 100% by mass, 99% by mass or less, etc.

[0021] A polyamide resin composition according to one embodiment consists of the following components: Semi-aromatic polyamide resin (A), Hydrophilic zeolite (B) and, Halogen-based flame retardant (C), It can include...

[0022] The inclusion of a semi-aromatic polyamide resin (A), a hydrophilic zeolite (B), and a halogen-based flame retardant (C) in the polyamide resin composition was discovered from the viewpoint of improving reflow heat resistance. As a result, in molding processes of polyamide resin compositions, molded articles, or surface mount technology (SMT) for electronic devices, it is possible to improve reflow heat resistance while ensuring mechanical strength and flame retardancy at desired levels, and consequently suppress the occurrence of blisters.

[0023] According to this disclosure, although we do not wish to be bound by theory, it is conceivable that, in a polyamide resin composition, a unique formulation or combination of components (A) and (C) and the microporous structure of hydrophilic zeolite (B) may not only adsorb water or a wetting medium during reflow soldering or molding, but also reduce the vapor pressure when moisture evaporates. As a result, during reflow soldering or molding, water may be trapped within the polyamide resin composition or component (B) and less likely to evaporate, suppressing the occurrence of blisters in the polyamide resin composition and molded articles or electronic devices containing it, and improving the reflow heat resistance.

[0024] The polyamide resin composition may optionally contain other components, such as polyamide resins other than the semi-aromatic polyamide resin (A), resins other than polyamide resins, inorganic fillers or additives other than hydrophilic zeolite (B), flame retardants other than halogenated flame retardants (C), reinforcing materials, etc.

[0025] <Semi-aromatic polyamide resin (A)> The semi-aromatic polyamide resin (A) of this disclosure was discovered from the viewpoint of improving reflow heat resistance in a polyamide resin composition through a unique formulation or combination with a hydrophilic zeolite (B) and a halogen-based flame retardant (C).

[0026] The semi-aromatic polyamide resin (A) may be a semi-aromatic polyamide resin obtained by polymerizing mainly aromatic dicarboxylic acids with aliphatic or alicyclic diamines, or it may be a semi-aromatic polyamide resin obtained by polymerizing mainly aliphatic or alicyclic dicarboxylic acids with aromatic diamines. The semi-aromatic polyamide resin (A) may consist of one or more types.

[0027] The content of the semi-aromatic polyamide resin (A) in the polyamide resin composition is not limited, but may be, for example, within the range of 20% to 90% by mass, 25% to 85% by mass, 30% to 80% by mass, or 35% to 75% by mass, relative to the total mass of the polyamide resin composition.

[0028] The semi-aromatic polyamide resin (A) preferably contains component units (Aa) derived from a dicarboxylic acid and component units (Ab) derived from a diamine, from the viewpoint of improving reflow heat resistance and adjusting the melting point (Tm) measured by differential scanning calorimeter (DSC).

[0029] Specific examples of semi-aromatic polyamide resins (A) are not limited to, but include, for example, polyamide 4T (polybutamethylene terephthalamide) (Tm: approx. 325°C), polyamide 6T (polyhexamethylene terephthalamide) (Tm: approx. 370°C), polyamide 6I (polyhexamethylene isophthalamide), polyamide 9T (polynonane methylene terephthalamide) (Tm: approx. 306°C), polyamide 10T (polydecamethylene terephthalamide) (Tm: approx. 316°C), polyamide 11T (polyundecamethylene terephthalamide), polyamide 11T(H) (polyundecamethylene hexahydroterephthalamide), and polyamide MXD6 (polymetaxylylene Examples include polyamide 6T / 66 (polyhexamethylene terephthalamide) (Tm: approximately 237°C), polyamide TMHT (polytrimethylhexamethylene terephthalamide), 6T / 66 (polyhexamethylene terephthalamide / polyhexamethylene adipamide copolymer), 6T / 6I (polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer), 6T / DT (polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer), polyamide 6T / 6I / 66 (polyhexamethylene terephthalamide / polyhexamethylene isophthalamide / polyhexamethylene adipamide copolymer), etc., or combinations of multiple component units comprising these. From these, a semi-aromatic polyamide resin suitable for blending with components (B) and (C) as described above may be selected, for example, polyamide 6T / 66 can be used.

[0030] • Component unit (Aa) derived from dicarboxylic acid The component unit (Aa) derived from the dicarboxylic acid is not limited as long as it constitutes the semi-aromatic polyamide resin (A), and may include, for example, component units derived from aromatic dicarboxylic acids and / or aliphatic dicarboxylic acids. More specifically, it may include component units derived from aromatic dicarboxylic acids, component units derived from alicyclic dicarboxylic acids, component units derived from aliphatic dicarboxylic acids, etc. The component unit (Aa) derived from the dicarboxylic acid can be determined from the viewpoint of adjusting Tm and compounding or combining with components (B) and (C).

[0031] Examples of aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride, and their esters. From the viewpoint of crystallinity, terephthalic acid, naphthalenedicarboxylic acid, and their esters can be used. In particular, from the viewpoint of obtaining a semi-aromatic polyamide resin (A) with high crystallinity and heat resistance, it is preferable that the component units derived from the aromatic dicarboxylic acid include component units derived from terephthalic acid.

[0032] The semi-aromatic polyamide resin (A) may optionally contain component units derived from an aliphatic dicarboxylic acid. The number of carbon atoms in the aliphatic dicarboxylic acid is not limited and may be determined from the viewpoint of compounding or combination with components (B) and (C), adjustment of Tm, and crystallinity, for example, in the range of 4 to 20, 6 to 12, or 6 to 10.

[0033] The hydrocarbon structure in aliphatic dicarboxylic acid may be branched, but it is preferably linear. That is, it is more preferable that the aliphatic dicarboxylic acid is a linear aliphatic dicarboxylic acid. Examples of aliphatic 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, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, etc. The semi-aromatic polyamide resin (A) may contain only one component derived from these, or it may contain two or more. Among these, adipic acid and sebacic acid are preferred, with adipic acid being more preferred, from the viewpoint of compounding or combination with components (B) and (C), adjustment of Tm, and crystallinity.

[0034] The semi-aromatic polyamide resin (A) may optionally contain component units derived from an alicyclic dicarboxylic acid. The number of carbon atoms in the alicyclic dicarboxylic acid is not limited but may be determined from the viewpoint of compounding or combination with components (B) and (C), adjustment of Tm, and crystallinity, and may be in the range of 4 to 20, 6 to 12, or 6 to 10, for example. Examples of alicyclic dicarboxylic acids include cyclohexanedicarboxylic acid and its esters.

[0035] The content of component units derived from aliphatic dicarboxylic acids is not limited, but for example, it may be 0 mol% to 70 mol%, 0 mol% to 60 mol%, or 0 mol% to 50 mol%, or 1 mol% to 70 mol%, 1 mol% to 60 mol%, 1 mol% to 50 mol%, or 1 mol% to 45 mol% relative to the total number of moles of component units (Aa) derived from dicarboxylic acids.

[0036] The content of component units derived from aromatic dicarboxylic acids and / or alicyclic dicarboxylic acids (preferably the content of component units derived from aromatic dicarboxylic acids, more preferably the content of component units derived from terephthalic acid) is preferably 30 mol% to 100 mol%, more preferably 40 mol% to 100 mol%, and preferably 50 mol% to 100 mol%, relative to the total number of moles of component units (Aa) derived from dicarboxylic acids. When the content of the above component units is 30 mol% or more, the crystallinity of the semi-aromatic polyamide resin (A) tends to increase.

[0037] The component unit (Aa) derived from the dicarboxylic acid may include component units other than the above-mentioned component unit to the extent that it does not impair the effects of the present disclosure.

[0038] • Component unit (Ab) derived from diamine The component units (Ab) derived from diamines are not limited as long as they constitute the semi-aromatic polyamide resin (A), and may include, for example, component units derived from aliphatic diamines, component units derived from aromatic diamines, etc. The semi-aromatic polyamide resin (A) may contain only one type of component unit (Ab) derived from diamines in a single molecule, or it may contain two or more types of component units (Ab) derived from diamines. From the viewpoint of compounding or combining with components (B) and (C), and controlling Tm, it is preferable that the semi-aromatic polyamide resin (A) contains component units derived from aliphatic diamines.

[0039] The component unit (Ab) derived from the diamine can be determined to include component units derived from aliphatic chain diamines and / or component units derived from alicyclic diamines, from the viewpoint of compounding or combining with components (B) and (C), controlling Tm or glass transition temperature (Tg), improving mechanical strength, and improving moldability.

[0040] The number of carbon atoms in the aliphatic diamine is not limited, but may be determined from the viewpoint of formulation or combination with components (B) and (C), adjustment of Tm, and crystallinity. For example, it may be 4 to 6 or 7 to 18.

[0041] Examples of aliphatic diamines with 4 to 6 carbon atoms include 1,4-diaminobutane, 1,6-diaminohexane, and 2-methyl-1,5-diaminopentane. The amount of component units derived from aliphatic diamines with 4 to 6 carbon atoms is not limited, but may be, for example, 40 mol% to 100 mol%, 50 mol% to 100 mol%, or 60 mol% to 100 mol% relative to the total number of moles of component units (Ab) derived from the diamine.

[0042] The polyamide resin (A) may contain component units derived from aliphatic diamines other than those derived from aliphatic diamines having 4 to 6 carbon atoms, for example, component units derived from aliphatic diamines having 7 to 18 carbon atoms. The hydrocarbon structure in these aliphatic diamines may be branched, but it is more preferable that it be linear.

[0043] Examples of aliphatic diamines with 7 to 18 carbon atoms include linear aliphatic diamines such as 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane; and branched aliphatic diamines such as 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane, and 2-methyl-1,11-diaminoundecane.

[0044] The aliphatic diamines listed above may be one type or two or more types.

[0045] The content of component units derived from aliphatic diamines having 4 to 18 carbon atoms is preferably more than 50 mol% and 100 mol% or less, and more preferably more than 50 mol% and 90 mol% or less, relative to the total number of moles of component units (Ab) derived from diamines. When the above content is greater than 50 mol%, the fluidity and mechanical strength of the polyamide resin during molding can be improved.

[0046] The polyamide resin (A) may optionally contain component units derived from alicyclic diamines. Examples of component units derived from alicyclic diamines include 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2,5-bisaminomethylnorbornane, 2,6-bisaminomethylnorbornane, isophoronediamine, piperazine, 2,5-dimethylpiperazine, bis(4-aminocyclohexyl)methane, 1,3-bis(aminocyclohexyl)methane, bis(4-aminocyclohexyl)propane, 4,4'-diamino-3,3'-dimethyldicyclohexylpropane, and 4,4'-di The compounds include amino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-dimethyldicyclohexylpropane, α,α'-bis(4-aminocyclohexyl)-p-diisopropylbenzene, α,α'-bis(4-aminocyclohexyl)-m-diisopropylbenzene, α,α′-bis(4-aminocyclohexyl)-1,4-cyclohexane, and component units derived from α,α'-bis(4-aminocyclohexyl)-1,3-cyclohexane.

[0047] The content of component units derived from alicyclic diamines is not limited, but for example, it may be 80 mol% or less, more than 10 mol% and 70 mol% or less, or 20 mol% to 60 mol% or less, relative to the total number of moles of component units (Ab) derived from diamines.

[0048] The component units (Ab) derived from the diamine may further contain component units derived from other diamines, to the extent that this does not impair the effects of the present disclosure. Examples of other diamines include aromatic diamines. Examples of aromatic diamines include metaxylylenediamine. The content of component units derived from other diamines may be 50 mol% or less relative to the total number of moles of component units (Ab) derived from the diamine.

[0049] The constituent units of the semi-aromatic polyamide resin (A) and their ratios can be calculated from the charging ratio during the preparation of the semi-aromatic polyamide resin (A), or measured by NMR spectroscopy.

[0050] 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.

[0051] 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, accumulation count of 10,000 or more, and a chemical shift reference value of 27.50 ppm. The assignment of various signals is performed based on conventional methods, and quantification can be performed based on the accumulated value of the signal intensity.

[0052] Furthermore, the component unit (Aa) derived from dicarboxylic acid in the semi-aromatic polyamide resin (A) may include component units derived from biomass-derived dicarboxylic acid, and the component unit (Ab) derived from diamine may include component units derived from biomass-derived diamine. In addition, the semi-aromatic polyamide resin (A) may be a biomass-derived semi-aromatic polyamide resin (A) obtained by polymerizing a group of raw materials including biomass-derived raw materials.

[0053] • End-cap encapsulant The semi-aromatic polyamide resin (A) can have at least some of its molecular end groups encapsulated with an end encapsulant, from the viewpoint of compounding or mixing with other components, improving thermal stability during molding, and increasing mechanical strength.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] Aromatic monocarboxylic acids and alicyclic monocarboxylic acids may optionally have substituents on the cyclic structure.

[0058] • Properties of semi-aromatic polyamide resin (A) The melting point (Tm) of the semi-aromatic polyamide resin (A), as measured by differential scanning calorimeter (DSC), is not limited. For example, its lower limit can be determined from the viewpoint of mechanical strength and reflow heat resistance in the high-temperature range of the polyamide resin composition or molded article, and may be 280°C or higher, or 290°C or higher. Its upper limit can be determined from the viewpoint of moldability, and may be, for example, less than 350°C, 348°C or lower, 345°C or lower, 340°C or lower, 335°C or lower, or 330°C or lower. By setting the Tm of the semi-aromatic polyamide resin (A) to 330°C or lower, the decomposition of amide bonds in the semi-aromatic polyamide resin (A) during the melting and molding of the polyamide resin composition can be suppressed.

[0059] The glass transition temperature (Tg) of the semi-aromatic polyamide resin (A), as measured by DSC, is not limited but can be determined according to the desired moldability or reflow heat resistance, and may be in the range of, for example, 45°C to 150°C, 48°C to 145°C, 49°C to 145°C, or 50°C to 145°C.

[0060] The heat of fusion (ΔH) of the semi-aromatic polyamide resin (A), determined from the area of ​​the exothermic peak of crystallization during the first heating process measured by DSC at a heating rate of 10°C / min in accordance with JIS K 7122 (2012), is not limited but can be determined according to the desired crystallinity, fluidity during injection molding, and mechanical strength or moldability. For example, its lower limit may be greater than 5 mJ / mg, 10 mJ / mg or more, 15 mJ / mg or more, or 20 mJ / mg or more, and its upper limit may be 100 mJ / mg or less, or 95 mJ / mg or less.

[0061] The melting point (Tm), glass transition temperature (Tg), and heat of fusion (ΔH) of the semi-aromatic polyamide resin (A) can be adjusted, for example, by the structure or type of component units (Aa) derived from dicarboxylic acid, the structure or type of component units (Ab) derived from diamine, or their respective content ratios, and the molecular weight of the polyamide resin (A).

[0062] The intrinsic viscosity [η] of the semi-aromatic polyamide resin (A), measured at a temperature of 25°C ± 0.05°C in 96.5% sulfuric acid, is preferably 0.5 dl / g or more and 1.5 dl / g or less. An intrinsic viscosity [η] of the semi-aromatic polyamide resin (A) of 0.5 dl / g or more makes it easier to sufficiently 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. The intrinsic viscosity [η] of the semi-aromatic polyamide resin (A) can be adjusted, for example, by the amount of end-encapsulation of the polyamide resin, or by the molar ratio of dicarboxylic acid to diamine when polymerizing the semi-aromatic polyamide resin (A).

[0063] The amount of terminal carboxyl groups in the semi-aromatic polyamide resin (A) is not limited, but can be, for example, in the range of 20 mmol / kg to 200 mmol / kg.

[0064] The amount of terminal carboxyl groups mentioned above is a value measured using NMR. Specifically, for example, 30 mg of 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 polyamide resin is calculated from the hydrogen-derived peak area of ​​each component constituting the 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.

[0065] The amount of terminal amino groups in the semi-aromatic polyamide resin (A) is not limited, but can be, for example, in the range of 30 mmol / kg to 200 mmol / kg.

[0066] The amount of terminal amino groups is measured by the following method: Dissolve 1 g of 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).

[0067] • Manufacturing of semi-aromatic polyamide resin (A) The semi-aromatic polyamide resin (A) 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 the semi-aromatic polyamide resin (A) can be produced by applying shear stress to the molten lower-order condensate and causing polycondensation.

[0068] From the viewpoint of adjusting the intrinsic viscosity of the semi-aromatic polyamide resin (A), the aforementioned end-capturing agent may be added to the reaction system of dicarboxylic acid and diamine. The intrinsic viscosity or molecular weight of the semi-aromatic polyamide resin (A) can be adjusted depending on the amount of end-capturing agent added. The amount of end-capturing agent added is not limited, but for example, it may be 0.07 moles or less, or 0.05 moles or less, per 1 mole of the total amount of dicarboxylic acid.

[0069] <Hydrophilic zeolite (B)> Hydrophilic zeolites are zeolites that possess hydrophilic properties. Generally, the lower the molar ratio of SiO2 / Al2O3 in a zeolite, the higher its hydrophilicity.

[0070] The hydrophilic zeolite (B) of this disclosure was discovered from the viewpoint of improving reflow heat resistance in polyamide resin compositions through a unique formulation or combination with a semi-aromatic polyamide resin (A) and a halogen-based flame retardant (C). In molding processes, surface mount technology (SMT) of molded articles or electronic devices using polyamide resin compositions containing components (A) and (C) and the hydrophilic zeolite (B), it is possible to improve reflow heat resistance while ensuring mechanical strength and flame retardancy at a desired level, and consequently suppress the occurrence of blisters, etc.

[0071] Although we do not wish to be bound by theory, hydrophilic zeolite (B) can, due to its microporous structure, have the effect of a molecular sieve and / or the ability to adsorb any medium, such as water. In the polyamide resin composition of this disclosure, the unique formulation or combination of components (A) to (C) is thought to not only adsorb water or a wetting medium during reflow soldering or molding, but also reduce the vapor pressure when water evaporates. As a result, during reflow soldering or molding, water is trapped within the polyamide resin composition or component (B) and is less likely to evaporate, which is thought to suppress water absorption, moisture absorption, dimensional changes, strength reduction, blistering, etc., of the polyamide resin composition and molded articles or electronic devices containing it, and improve the reflow heat resistance.

[0072] From the above viewpoint, it is preferable that the hydrophilic zeolite (B) has a nano-order microporous structure. When the hydrophilic zeolite (B) has a nano-order microporous structure, its effect as a molecular sieve becomes more pronounced, and consequently, its reflow heat resistance also tends to improve or be enhanced.

[0073] The molar ratio of SiO2 / Al2O3 contained in hydrophilic zeolite (B) is preferably less than 30, more preferably 20 or less, and even more preferably 10 or less. When the molar ratio of SiO2 / Al2O3 contained in hydrophilic zeolite (B) is less than 30, the improvement or enhancement of reflow heat resistance is significant in unique formulations or combinations with components (A) and (C). The lower limit of the molar ratio of SiO2 / Al2O3 contained in hydrophilic zeolite (B) is usually 1.0 or higher, and preferably 2.0 or higher.

[0074] From the viewpoint of further improving reflow heat resistance or controlling water absorption, the content of hydrophilic zeolite (B) is preferably 0.1% to 10% by mass per 100% by mass of the polyamide resin composition.

[0075] <Halogenated flame retardant (C)> The polyamide resin composition of this disclosure may contain a halogenated flame retardant (C), thereby improving the flame retardancy of the polyamide resin composition.

[0076] Examples of halogen elements included in halogen-based flame retardants (C) are, but are not limited to, at least one selected from the group consisting of fluorine, chlorine, bromine, and iodine.

[0077] The halogen content of the halogen-based flame retardant (C) is preferably 65% ​​by mass or more relative to the total mass of the halogen-based flame retardant (C). According to this disclosure, it has been found that a halogen-based flame retardant (C) with a halogen content of 65% by mass or more is well compatible with a hydrophilic zeolite (B). A polyamide resin composition containing a semi-aromatic polyamide resin (A), a hydrophilic zeolite (B), and a halogen-based flame retardant (C) with a halogen content of 65% by mass or more exhibits significant improvement in reflow heat resistance and can also achieve a balance between fluidity and strength or toughness.

[0078] In this disclosure, the halogen content of a halogenated flame retardant (C) refers to the mass fraction (mass%) of halogen elements in the halogenated flame retardant (C). For example, if the halogenated flame retardant (C) is a brominated flame retardant, the halogen content will be the bromine content. In this case, the bromine content is the mass fraction of bromine in the brominated flame retardant. The halogen content can be measured by collecting the gas generated by the combustion decomposition of the halogenated flame retardant (C) using the oxygen flask combustion method in an absorbent solution, and then analyzing the absorbent solution by ion chromatography to quantify the halogen.

[0079] There is no upper limit to the halogen content of halogen-based flame retardant (C), but for example, it may be 100% by mass or less, less than 100% by mass, 99% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, or 80% by mass or less, relative to the total mass of halogen-based flame retardant (C).

[0080] The content of the halogenated flame retardant (C) is preferably 1% by mass or more and 40% by mass or less based on the total mass of the polyamide resin composition. When the content of the halogenated flame retardant (C) is 1% by mass or more based on the total mass of the polyamide resin composition, the flame retardancy and fluidity of the polyamide resin composition can be improved. When the content of the halogenated flame retardant (C) is 40% by mass or less based on the total mass of the polyamide resin composition, the amount of semi-aromatic polyamide resin (A) in the resin composition can be increased, thereby improving various properties such as the toughness of the polyamide resin composition. From the above viewpoint, the content of the halogenated flame retardant (C) is more preferably 5% by mass or more and 30% by mass or less based on the total mass of the polyamide resin composition, and even more preferably 12% by mass or more and 25% by mass or less.

[0081] Furthermore, the content of the halogenated flame retardant (C) is preferably 10 parts by mass or more and 70 parts by mass or less per 100 parts by mass of the semi-aromatic polyamide resin (A) contained in the polyamide resin composition. When the content of the halogenated flame retardant (C) is 10 parts by mass or more per 100 parts by mass of the semi-aromatic polyamide resin (A) contained in the polyamide resin composition, the flame retardancy and fluidity of the polyamide resin composition can be improved. When the content of the halogenated flame retardant (C) is 70 parts by mass or less per 100 parts by mass of the semi-aromatic polyamide resin (A) contained in the polyamide resin composition, the amount of semi-aromatic polyamide resin (A) in the resin composition can be increased, thereby improving various properties such as the toughness of the polyamide resin composition. From the above viewpoint, the content of the halogenated flame retardant (C) is more preferably 20 parts by mass or more and 60 parts by mass or less per 100 parts by mass of the semi-aromatic polyamide resin (A) contained in the polyamide resin composition, and even more preferably 25 parts by mass or more and 55 parts by mass or less.

[0082] As a halogen-based flame retardant, bromine-based flame retardants are preferred from the viewpoint of flame retardancy. A bromine-based flame retardant is a flame retardant that contains at least one bromine atom.

[0083] From the viewpoint of compatibility with hydrophilic zeolite (B) and improvement of reflow heat resistance, the bromine content of the brominated flame retardant is preferably 65% ​​by mass or more, more preferably 65% ​​by mass or more and 100% by mass or less, even more preferably 65% ​​by mass or more and 90% by mass or less, and particularly preferably 65% ​​by mass or more and 80% by mass or less, based on the total mass of the brominated flame retardant.

[0084] Examples of brominated flame retardants include polybrominated styrene, brominated polystyrene, or brominated polyphenylene.

[0085] Polybrominated styrene is a polymer containing component units derived from brominated styrene or brominated α-methylstyrene. Examples of brominated styrene include dibromostyrene, tribromostyrene, and pentabromostyrene. Examples of brominated α-methylstyrene include tribromo-α-methylstyrene. Polybrominated styrene may also be a copolymer of brominated styrene or brominated α-methylstyrene with an epoxy group-containing (meth)acrylic acid ester compound. Furthermore, polybrominated styrene may be a copolymer obtained by graft copolymerization of the above-mentioned polymers with an unsaturated carboxylic acid or its derivative.

[0086] In these polybrominated styrenes, bromine atoms are present in the (co)polymer by substituting hydrogen atoms bonded to carbon atoms that form aromatic rings. Typically, the hydrogen atoms forming the alkyl chain that constitutes the main skeleton of the (co)polymer are not substantially substituted with bromine atoms. This means that the proportion of hydrogen atoms bonded to carbon atoms constituting the alkyl chain that forms the main skeleton of the (co)polymer that are substituted with bromine atoms is 0.0% by mass or more and 0.5% by mass or less. In polybrominated styrene, it is preferable that the proportion of hydrogen atoms substituted with bromine atoms is 0.0% by mass or more and 0.2% by mass or less.

[0087] Brominated polystyrene is a (co)polymer obtained by brominating polystyrene or poly-α-methylstyrene. Like polybrominated styrene, brominated polystyrene contains bromine atoms that have substituted hydrogen atoms bonded to carbon atoms forming aromatic rings, and also contains bromine atoms that have substituted hydrogen atoms forming the alkyl chain that forms the main backbone of the (co)polymer. Specifically, in brominated polystyrene, the proportion of hydrogen atoms substituted with bromine atoms among the hydrogen atoms bonded to carbon atoms constituting the alkyl chain that forms the main backbone of the (co)polymer is greater than 0.5% by mass.

[0088] Brominated polyphenylene is a (co)polymer obtained by brominating polyphenylene ether resin. Brominated polyphenylene has the following general formula (1): [ka] {In the formula, X is Br, p is a number between 1 and 4, and q is a number greater than or equal to 1} It is preferable that the compound is represented by [formula].

[0089] In general formula (1), q is preferably 2 or greater, and preferably 5 or greater. The upper limit of q is not particularly limited, but is preferably 100 or less, more preferably 80 or less, even more preferably 60 or less, even more preferably 40 or less, still preferably 20 or less, and particularly preferably 10 or less.

[0090] Examples of brominated polyphenylenes represented by general formula (1) include polydibromo-p-phenylene oxide, polytribromo-p-phenylene oxide, polymonobromo-p-phenylene oxide, and polydibromo-o-phenylene oxide.

[0091] The above-mentioned brominated flame retardants may be used in order to determine the desired properties of the polyamide resin composition and molded article. From the viewpoint of flame retardancy, polybrominated styrene and / or brominated polystyrene are preferred.

[0092] The brominated flame retardant preferably has a weight-average molecular weight (Mw) of 1,000 to 400,000, more preferably 2,000 to 100,000, and even more preferably 2,000 to 60,000. The above weight-average molecular weight is the weight-average molecular weight in polystyrene terms, measured using GPC (gel permeation chromatography) with a mobile phase of chloroform, at a column temperature of 40°C, and using a differential refractometer detector.

[0093] The content of the brominated flame retardant is preferably 1% by mass or more and 40% by mass or less based on the total mass of the polyamide resin composition. When the content of the brominated flame retardant is 1% by mass or more based on the total mass of the polyamide resin composition, the flame retardancy and fluidity of the polyamide resin composition can be improved. When the content of the brominated flame retardant is 40% by mass or less based on the total mass of the polyamide resin composition, the amount of semi-aromatic polyamide resin (A) in the resin composition can be increased, thereby improving various properties such as the toughness of the polyamide resin composition. From the above viewpoint, the content of the brominated flame retardant is more preferably 5% by mass or more and 30% by mass or less based on the total mass of the polyamide resin composition, and even more preferably 12% by mass or more and 25% by mass or less.

[0094] Furthermore, the content of the brominated flame retardant is preferably 10 parts by mass or more and 70 parts by mass or less per 100 parts by mass of the semi-aromatic polyamide resin (A) contained in the polyamide resin composition. When the content of the brominated flame retardant is 10 parts by mass or more per 100 parts by mass of the semi-aromatic polyamide resin (A) contained in the polyamide resin composition, the flame retardancy and fluidity of the polyamide resin composition can be improved. When the content of the brominated flame retardant is 70 parts by mass or less per 100 parts by mass of the semi-aromatic polyamide resin (A) contained in the polyamide resin composition, the amount of semi-aromatic polyamide resin (A) in the resin composition can be increased, thereby improving various properties such as the toughness of the polyamide resin composition. From the above viewpoint, the content of the brominated flame retardant is more preferably 20 parts by mass or more and 60 parts by mass or less per 100 parts by mass of the semi-aromatic polyamide resin (A) contained in the polyamide resin composition, and even more preferably 25 parts by mass or more and 55 parts by mass or less.

[0095] <Other ingredients> The polyamide resin composition may optionally contain other components.

[0096] Other examples of components include polyamide resins other than semi-aromatic polyamide resin (A), flame retardants other than halogenated flame retardants (C), reinforcing agents, flame retardant aids, nucleating agents, lubricants, colorants, heat stabilizers (halogen metal salts, copper compounds, higher fatty acid metal salts, etc.), corrosion resistance improvers, drip inhibitors, ion scavenging agents, elastomers (rubber), antistatic agents, mold release agents, antioxidants (phenols, amines, sulfurs and phosphoruses, etc.), other heat stabilizers (lactone compounds, vitamin E, hydroquinones, etc.), light stabilizers ( This includes benzotriazoles, triazines, benzophenones, benzoates, hindered amines, and oxanilides, as well as other polymers (polyolefins, ethylene-propylene copolymers, ethylene-1-butene copolymers, and other olefin copolymers, propylene-1-butene copolymers, polystyrene, polycarbonate, polyacetal, polysulfone, polyphenylene oxide, fluororesins, silicone resins, and liquid crystal polymers (LCPs), etc.).

[0097] Examples of polyamide resins other than semi-aromatic polyamide resin (A) include fully aromatic polyamide resins, fully aliphatic polyamide resins, and aliphatic polyamide resins having component units derived from aliphatic diamines with 4 carbon atoms and component units derived from aliphatic dicarboxylic acids with 6 carbon atoms (aliphatic polyamide resins including PA46).

[0098] Furthermore, the component units derived from dicarboxylic acids in polyamide resins other than semi-aromatic polyamide resin (A) may include component units derived from biomass-derived dicarboxylic acids, and the component units derived from diamines may include component units derived from biomass-derived diamines. In addition, polyamide resins other than semi-aromatic polyamide resin (A) may be biomass-derived polyamide resins formed by polymerizing a group of raw materials including biomass-derived raw materials.

[0099] Other flame retardants besides halogen-based flame retardants (C) include, for example, halogen-free flame retardants.

[0100] When a polyamide resin composition contains a halogen-free flame retardant, the content of the halogen-free flame retardant is preferably 0.1 parts by mass or more and 22 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less, per 100 parts by mass of the polyamide resin contained in the polyamide resin composition. When the content of the halogen-free flame retardant per 100 parts by mass of the polyamide resin is within the above range, a balance can be struck between the stable manifestation of flame retardancy and the suppression of decomposition of the halogen-free flame retardant.

[0101] Examples of halogen-free flame retardants include inorganic hydrates other than hydrophilic zeolites (B); calcined kaolin; magnesium oxide; aluminum hydroxide; phosphinate compounds shown in formula (2) or bisphosphinate compounds shown in formula (3) below; or polymers thereof: [ka] [ka] {In equations (2) and (3), R 7 and R 8 These are independently linear or branched alkyl or aryl groups having 1 to 6 carbon atoms. R 9 These are independently linear or branched alkylene groups having 1 to 10 carbon atoms, arylene groups having 6 to 10 carbon atoms, alkylarylene groups having 6 to 10 carbon atoms, or arylalkylene groups having 6 to 10 carbon atoms. M is one atom or group of atoms selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, and protonated nitrogen bases. m represents an integer between 1 and 4, n represents an integer between 1 and 4, and x represents an integer between 1 and 4.

[0102] Examples of phosphinate compounds shown in formula (2) and bisphosphinate compounds shown in formula (3) include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, zinc methyl-n-propylphosphinate, methane ( Examples include calcium methylphosphinate, magnesium methanedi(methylphosphinate), aluminum methanedi(methylphosphinate), zinc methanedi(methylphosphinate), calcium benzene-1,4-(dimethylphosphinate), magnesium benzene-1,4-(dimethylphosphinate), aluminum benzene-1,4-(dimethylphosphinate), zinc benzene-1,4-(dimethylphosphinate), calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate.

[0103] Of these, calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate are preferred, and aluminum diethylphosphinate is more preferred.

[0104] Examples of commercially available phosphinate compounds shown in formula (2) and bisphosphinate compounds shown in formula (3) include EXOLIT OP1230 ("EXOLIT" is a registered trademark of Clariant), OP1311, OP1312, OP930, and OP935, among others.

[0105] The content of the phosphinate compound shown in formula (2) and the bisphosphinate compound shown in formula (3) is preferably 0.1% by mass or more and 22% by mass or less based on the total mass of the polyamide resin composition. When the content of the above flame retardant is 0.1% by mass or more, the fluidity and electrical properties of the polyamide resin composition in the high-temperature range can be improved. When the content of the above flame retardant is 22% by mass or less, the amount of semi-aromatic polyamide resin (A) in the resin composition can be increased, thereby improving various properties such as the toughness of the polyamide resin composition, and furthermore, it becomes easier to suppress the decrease in toughness due to the addition of the flame retardant. From the above viewpoint, the content of these flame retardants is more preferably 2% by mass or more and 18% by mass or less based on the total mass of the polyamide resin composition, and even more preferably 5% by mass or more and 15% by mass or less.

[0106] Furthermore, the content of the phosphinate compound shown in formula (2) and the bisphosphinate compound shown in formula (3) is preferably 0.1 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the semi-aromatic polyamide resin (A) contained in the polyamide resin composition. When the content of the above flame retardant is 0.1 parts by mass or more, the fluidity and electrical properties in the high-temperature range of the polyamide resin composition can be improved. When the content of the above flame retardant is 50 parts by mass or less, the amount of semi-aromatic polyamide resin (A) in the resin composition can be increased, thereby improving various properties such as the toughness of the polyamide resin composition, and it becomes easier to suppress the decrease in toughness due to the addition of the flame retardant. From the above viewpoint, the content of these flame retardants is more preferably 3 parts by mass or more and 40 parts by mass or less per 100 parts by mass of the semi-aromatic polyamide resin (A) contained in the polyamide resin composition, and even more preferably 5 parts by mass or more and 35 parts by mass or less.

[0107] Reinforcing materials can impart high mechanical strength to the resin composition. Examples of reinforcing materials include fibrous reinforcing materials such as glass fibers, wollastonite, potassium titanate whiskers, calcium carbonate whiskers, aluminum borate whiskers, magnesium sulfate whiskers, zinc oxide whiskers, milled fibers, and cut fibers, 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 fibers, and potassium titanate whiskers are preferred, with wollastonite or glass fibers being more preferred, as they easily increase the mechanical strength of the molded article.

[0108] The amount of reinforcing material is not particularly limited, but can be, for example, 15% to 70% by mass relative to the total mass of the polyamide resin composition.

[0109] Examples of flame retardant additives include metal oxides and metal hydroxides, and specifically, at least one selected from the group consisting of sodium antimonate, zinc borate, boehmite, zinc stanate, iron oxide, zinc oxide, and tin oxide is preferred, and more preferably at least one selected from the group consisting of sodium antimonate, zinc borate, and zinc oxide.

[0110] The flame retardant additive content is preferably 0.2 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of the polyamide resin composition, more preferably 0.5 parts by mass or more and 4.0 parts by mass or less, and even more preferably 0.5% by mass or more and 3.0% by mass or less.

[0111] The polyamide resin composition may optionally contain a nucleating agent. The nucleating agent can promote the crystallization of the polyamide resin. As a result, the mechanical strength of the molded article, such as tensile strength, tensile elongation, modulus of elasticity, and toughness, can be increased.

[0112] 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 stearate; sorbitol compounds such as bis(p-methylbenzylidene)sorbitol and bis(4-ethylbenzylidene)sorbitol; and inorganic substances such as talc, calcium carbonate, and hydrotalcite. Of these, talc is preferred from the viewpoint of further increasing the crystallinity of the molded article. These nucleating agents may be used individually or in combination of two or more types.

[0113] Talc generally consists mainly of hydrated magnesium silicate (SiO2: 58-64%, MgO: 28-32%, Al2O3: 0.5-5%, Fe2O3: 0.3-5%). The average particle size of talc is not particularly limited, but is preferably 1 μm to 15 μm, more preferably 1 μm to 10 μm, and even more preferably 1 μm to 7.5 μm. When the average particle size of talc is within the above range, it is easy to disperse the talc in the polyamide resin without impairing the fluidity of the polyamide resin composition. The average particle size of talc can be measured by laser diffraction, for example, by laser diffraction using a Shimadzu SALD-2000A particle size analyzer manufactured by Shimadzu Corporation.

[0114] The nucleating agent content is preferably 0.10 parts by mass or more and 5.00 parts by mass or less, and more preferably 0.15 parts by mass or more and 3.00 parts by mass or less, per 100 parts by mass of the polyamide resin composition. When the nucleating agent content is within the above range, it is easy to sufficiently increase the crystallinity of the molded article and obtain sufficient mechanical strength.

[0115] The lubricant enhances the injection flowability of the polyamide resin composition and improves the appearance of the resulting molded article. The lubricant can be a fatty acid metal salt, such as an oxycarboxylic acid metal salt or a higher fatty acid metal salt.

[0116] The oxycarboxylic acid constituting the above oxycarboxylic acid metal salt may be an aliphatic oxycarboxylic acid or an aromatic oxycarboxylic acid. Examples of aliphatic oxycarboxylic acids include 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 aliphatic oxycarboxylic acids having 10 to 30 carbon atoms. Examples of aromatic oxycarboxylic acids include salicylic acid, m-oxybenzoic acid, p-oxybenzoic acid, gallic acid, mandelic acid, and trovaic acid.

[0117] Examples of metals that make up the above-mentioned oxycarboxylic acid metal salts include alkali metals such as lithium, and alkaline earth metals such as magnesium, calcium, and barium.

[0118] Of these, the oxycarboxylic acid metal salt is preferably a metal salt of 12-hydroxystearic acid, and more preferably magnesium 12-hydroxystearate, barium 12-hydroxystearate, and calcium 12-hydroxystearate.

[0119] Examples of higher fatty acids that make up the above-mentioned higher fatty acid metal salts include higher fatty acids with 15 to 30 carbon atoms, such as stearic acid, oleic acid, behenic acid, behenic acid, and montanic acid.

[0120] Examples of metals that make up the above-mentioned higher fatty acid metal salts include calcium, magnesium, barium, lithium, aluminum, zinc, sodium, and potassium.

[0121] Of these, at least one selected from the group consisting of calcium stearate, magnesium stearate, barium stearate, calcium behenate, sodium montanaate, and calcium montanaate is preferred as the above-mentioned higher fatty acid metal salt.

[0122] The lubricant content is preferably 0.01 parts by mass or more and 1.30 parts by mass or less per 100 parts by mass of the polyamide resin composition. When the lubricant content is 0.01 parts by mass or more, the fluidity during molding tends to increase, and the appearance of the resulting molded product tends to improve. When the lubricant content is 1.30 parts by mass or less, gas due to the decomposition of the lubricant is less likely to be generated during molding, and the appearance of the product tends to be good.

[0123] Ion scavengers capture halogen components in polyamide resin compositions, such as hydrogen chloride (chloride ions), to suppress the degradation of the polyamide resin composition. Examples of ion scavengers include hydrotalcite and zeolites other than hydrophilic zeolite (B). Examples of zeolites other than hydrophilic zeolite (B) include hydrophobic zeolites. These ion scavengers can be layered compounds and likely enhance the flame retardancy of the polyamide resin composition and molded article through actions such as dehydration of interlayer water.

[0124] The ion scavenging agent content is preferably 0.01 parts by mass or more and 3 parts by mass or less, and more preferably 0.1 parts by mass or more and 1 part by mass or less, relative to the total mass of the polyamide resin composition. When the ion scavenging agent content is within the above range, the stability and flame retardancy of the polyamide resin composition and molded article are more easily enhanced.

[0125] Drip inhibitors prevent the resin, which has melted and liquefied due to the heat of combustion, from dripping. Examples of drip inhibitors include fluororesins and modified polyolefins having carboxyl groups, acid anhydride groups, and amino groups in their molecules. Examples of fluororesins include polytetrafluoroethylene (PTFE). Examples of modified polyolefins include polyethylene, aromatic vinyl compound-conjugated diene copolymers such as SEBS or their hydrogenates, and modified polyolefin elastomers such as ethylene-propylene copolymers. Of these, modified polyolefins are preferred, and maleic acid-modified SEBS (m-SEBS) is more preferred.

[0126] The amount of the drip inhibitor is preferably 0.1 parts by mass or more and 5 parts by mass or less, and more preferably 0.5 parts by mass or more and 5 parts by mass or less, relative to the total mass of the polyamide resin composition. When the amount of the drip inhibitor is within the above range, the dripping of the resin during combustion can be sufficiently suppressed.

[0127] Corrosion resistance improvers include, for example, metal oxides or metal hydroxides. These compounds can suppress high-temperature corrosion and wear of steel materials (e.g., screws, cylinders, dies, and nozzles used in molding machines) made from polyamide resin compositions.

[0128] The metal oxide or metal hydroxide used as a corrosion resistance improver is preferably an oxide or hydroxide of a metal from groups 1 to 12 of the periodic table, and more preferably an oxide or hydroxide of a metal from groups 2 to 12 of the same periodic table. In particular, the metal oxide is preferably an oxide of a metal element from groups 4 to 12 of the periodic table, and more preferably an oxide of a metal element from groups 7 to 12.

[0129] The metal oxide or metal hydroxide used as a corrosion resistance improver is preferably an oxide or hydroxide of iron, magnesium, or zinc, and more preferably an oxide or hydroxide of magnesium or zinc. These metal oxides or metal hydroxides may also be composite oxides of metals such as zinc stannate and zinc hydroxystannate. Of these, magnesium hydroxide, magnesium oxide, and zinc oxide are preferred, with zinc oxide being more preferred. In particular, when using the phosphinate compound shown in formula (2) or the bisphosphinate compound shown in formula (3) above, or polymers thereof, as a flame retardant, the combined use of zinc oxide significantly enhances corrosion and wear suppression in molding machines.

[0130] The metal oxide or metal hydroxide used as a corrosion resistance improver is preferably in particulate form.

[0131] The content of the corrosion resistance improver is preferably 0.05% by mass or more and 2% by mass or less, more preferably 0.1% by mass or more and 1% by mass or less, and even more preferably 0.1% by mass or more and 0.5% by mass or less, based on the total mass of the polyamide resin composition.

[0132] <Method for producing polyamide resin composition> The polyamide resin composition can be produced by mixing the aforementioned components (A) to (C), and other components as needed, using known resin mixing methods, such as a Henschel mixer, V-blender, ribbon blender, or tumbler blender; or by melt-kneading the above components in a single-screw extruder, multi-screw extruder, kneader, or Banbury mixer, followed by granulation or pulverization. The melting temperature during melt-kneading can be determined, for example, according to the melting point of the polyamide resin containing component (A).

[0133] <Molded body> The molded articles of this disclosure may contain the polyamide resin compositions described above.

[0134] The shape of the molded article containing the polyamide resin composition of this disclosure is not particularly limited and can take various shapes depending on the application.

[0135] The molded articles of this disclosure can suppress odor, discoloration, yellowing, or staining, and reduce or suppress water absorption or moisture absorption, due to the combined use of components (A) and (B) in the polyamide resin composition. As a result, the molded articles of this disclosure can be used preferably as components of electronic or electrical equipment, and more preferably as components of electronic equipment.

[0136] <Application> The polyamide resin composition of this disclosure can be used as various polyamide molded articles by molding using known molding methods such as compression molding, injection molding, and extrusion molding.

[0137] In another embodiment, a method for manufacturing an electronic device using a polyamide molded article of the present disclosure is provided. The method for manufacturing an electronic device includes, for example, the following steps: The present disclosure includes a step of placing a polyamide molded body on a substrate, A process of heating the polyamide molded body and the substrate and fixing the polyamide molded body and the substrate by reflow soldering, It can include...

[0138] The method for manufacturing electronic equipment is not limited, but for example, it can be carried out by printing solder paste onto a substrate to form a printed circuit pattern, then placing the polyamide molded body of the present disclosure on the substrate as a component of electronic equipment, and heating it to reflow solder it.

[0139] In the fixing process described above, it is preferable that the polyamide molded body, substrate, and solder are heated to a temperature of 240°C or higher in a reflow oven. The effects of this disclosure become more pronounced when the fixing process described above involves heating to a temperature of 240°C or higher in a reflow oven.

[0140] The method for manufacturing electronic equipment may optionally include a cooling step after the fixing step described above. This allows the electronic equipment components embedded in molten solder, or fixed via molten solder, to be positioned relative to the substrate.

[0141] Examples of applications for molded articles containing a polyamide resin composition according to one embodiment include vehicle structural components, vehicle-mounted accessories, electronic equipment components, electronic equipment housings, home appliance housings, structural components, machine components, various automotive parts, medical devices, and the like.

[0142] More specifically, vehicle-related parts include high-voltage fuses, pyroswitches, pyrofuses, instrument panels, console boxes, door handles, door trims, shift levers, pedals, glove boxes, bumpers, hoods, fenders, trunks, doors, roofs, pillars, seats, steering wheels, busbars, terminals, terminal blocks, high-voltage connectors, motors, power converters (inverters, converters), ECU boxes, electrical components, engine-related parts, drivetrain and gear-related parts, intake and exhaust system parts, and cooling system parts. Precision electronic components include connectors, relays, gears, busbars, LED reflectors, etc.

[0143] The polyamide molded article of this disclosure has dimensions of 64 mm in length, 6 mm in width, and 0.8 mm in thickness. When molded at a temperature range of the melting point (Tm) of the contained polyamide resin to Tm + 30°C, and then conditioned at a temperature of 40°C and relative humidity of 95% for 96 hours, the water absorption rate calculated from the weight change before and after conditioning is, unusually, sometimes higher than that of a molded article without hydrophilic zeolite (B), yet the reflow heat resistance tends to improve. [Examples]

[0144] 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.

[0145] 1. Synthesis / Preparation of materials

[0146] 1-1. Synthesis of polyamide resin (A) <Polyamide resin PA-1 (6T66)> 2,515 g (15.1 mol) of terephthalic acid, 2,800 g (24.1 mol) of 1,6-diaminohexane, 1,325 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 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 3.01 MPa. After continuing the reaction for 1 hour, the lower condensates were extracted by releasing the mixture into the atmosphere through a spray nozzle installed at the bottom of the autoclave. The extracted lower condensates were cooled to room temperature, then pulverized to a particle size of 1.5 mm or less using a pulverizer, and dried at 110°C for 24 hours.

[0147] Next, this lower condensate was placed in a tray-type solid-phase polymerization apparatus, and after nitrogen purging, the temperature was raised to 220°C over approximately 1 hour and 30 minutes. After that, the lower condensate was reacted for 1 hour and then cooled to room temperature. Subsequently, the polyamide (high condensate) was further 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 / hour, to obtain polyamide resin PA-1.

[0148] The obtained polyamide resin PA-1 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. Furthermore, the heat of fusion (ΔH), measured by a scanning calorimeter (DSC), was 50 J / g.

[0149] The composition of the obtained polyamide resin PA-1 was such that the content of terephthalic acid-derived component units relative to the total number of moles of component units derived from dicarboxylic acid 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 relative to the total number of moles of component units derived from diamine was 100 mol%. In addition, the amount of terminal amino groups in polyamide resin PA-1 was 113 mmol / kg, and the amount of terminal carboxyl groups was 52 mmol / kg.

[0150] 1-2. Hydrophilic zeolite (B) Hydrophilic zeolite 1 (manufactured by Tosoh Zeoram Co., Ltd., Zeoram F-9 powder 100#, SiO2 / Al2O3=2.5) was used.

[0151] 1-3. Flame retardants

[0152] 1-3-1: Halogen-based flame retardant (C) Brominated polystyrene (HP-3010, manufactured by Albemarle, bromine content: 68.5% by mass) was used.

[0153] 1-4. Other ingredients

[0154] 1-4-1. Fibrous Reinforcement The following components were used as fibrous reinforcing materials. 1-4-1-1: Glass fiber (ECS03-615, manufactured by Central Glass Fiber Co., Ltd., sizing agent: urethane-based, weight-average fiber diameter (Dw): 9.0 μm, aspect ratio: 1.0)

[0155] 1-4-2. Flame retardant additives The following components were used as flame retardant additives. 1-4-2-1: Sodium antimonate (manufactured by Nippon Seikou Co., Ltd., SA-A) was used.

[0156] 1-4-3. Nuclear Agents Talc (manufactured by Matsumura Sangyo Co., Ltd., High Filler #5000PJ, average particle size 6 μm) was used.

[0157] 1-4-4. Lubricants The following ingredients were used as lubricants. 1-4-4-1: Calcium montane (Licomont CAV102, manufactured by Clariant Japan) was used.

[0158] 1-4-5. Drip prevention agent m-SEBS (ToughTec M1913, maleated SEBS, manufactured by Asahi Chemicals Co., Ltd.) was used.

[0159] 1-4-6. Halogen scavengers Hydrotalcite (manufactured by Toda Kogyo Co., Ltd., NAOX-33) was used.

[0160] 2. Measurement The physical properties of the resin or resin composition were measured by the following method.

[0161] <Melting point (Tm), glass transition temperature (Tg)> The melting point (Tm) and glass transition temperature (Tg) of the polyamide resin were measured using differential scanning calorimetry (DSC220C model, Seiko Instruments Inc.). Specifically, approximately 5 mg of polyamide resin was sealed in an aluminum pan for measurement and set up on the differential scanning calorimetry machine. It was then 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, it was heated a second time 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).

[0162] <Heat of fusion (ΔH)> The heat of fusion (ΔH) of the polyamide resin was determined from the area of ​​the exothermic peak during crystallization in the first heating process, in accordance with JIS K 7122 (2012).

[0163] <Intrinsic viscosity [η]> The intrinsic viscosity [η] of the polyamide resin was measured by dissolving 0.5 g of the polyamide resin in 50 ml of 96.5% sulfuric acid solution, and measuring the flow-down seconds of the resulting solution under the condition of 25°C ± 0.05°C using an Ubbelohde viscometer. The following formula: [η]=ηSP / [C(1 + 0.205ηSP)] ηSP=(t - t0) / t0 {In the formula, [η]: Intrinsic viscosity (dl / g) ηSP: Specific viscosity C: Sample concentration (g / dl) t: Flow-down seconds of the sample solution (seconds) t0: Flow-down seconds of the blank sulfuric acid (seconds)} was calculated based on this.

[0164] <Flow length> Each polyamide resin composition was injection-molded under the following conditions using a bar flow mold with a width of 10 mm and a thickness of 0.5 mm, and the flow length (mm) of the resin in the mold was measured. Injection molding machine: Toshiba TR40S3A (manufactured by Sodick Plastic Co., Ltd.) Injection setting pressure: 2000 kg / cm 2 Molding machine cylinder temperature: Melting point of the polyamide resin + 10°C Mold temperature: 120°C

[0165] 3. Preparation of polyamide resin composition The above materials were mixed in a tumbler blender at the composition ratios (unit: parts by mass) shown in Table 1, and melt-kneaded under the condition of a cylinder temperature of 300°C to 335°C using a 30 mmφ vented twin-screw extruder. Then, the kneaded product was extruded into strands and cooled in a water tank. Then, the strands were taken up by a pelletizer and cut to obtain pelletized polyamide resin compositions 1 to 3.

[0166] 4. Evaluation

[0167] <Flexural strength and toughness> Test specimens measuring 64 mm in length, 6 mm in width, and 0.8 mm in thickness were prepared by injection molding. The molding machine used, along with the molding machine cylinder temperature and mold temperature, are shown below. Molding machine: SE50DU, manufactured by Sumitomo Heavy Industries, Ltd. Molding machine cylinder temperature: Polyamide resin PA-1 330℃ Mold temperature: Polyamide resin PA-1 120℃ The prepared test specimens were left for 24 hours at a temperature of 23°C in a nitrogen atmosphere. Subsequently, a bending test was performed using a bending tester (NTESCO AB5) at a temperature of 23°C and a relative humidity of 50%. The test conditions were a span of 26 mm and a bending speed of 5 mm / min. From the bending test, the bending strength and the energy required to break the test specimen (toughness) were measured.

[0168] <Measurement of water absorption rate and reflow heat resistance temperature> A polyamide resin composition was injection molded under the following conditions to prepare test specimens with a length of 64 mm, a width of 6 mm, and a thickness of 0.8 mm. Molding machine: Sumitomo Heavy Industries SE50DU Molding machine cylinder temperature: Melting point of each polyamide resin + 10°C Mold temperature: 120℃ The prepared test specimens were conditioned at a temperature of 40°C and a relative humidity of 95% for 96 hours. The water absorption rate was calculated from the change in weight of the test specimens before and after conditioning.

[0169] A test specimen that had undergone humidity control treatment was placed on a 1 mm thick glass epoxy substrate. A temperature sensor was installed on this substrate. The glass epoxy substrate on which the test specimen was placed was set in an air reflow soldering machine (AIS-20-82-C, manufactured by Aitechtectron Co., Ltd.), and a reflow process was performed according to the temperature profile shown in Figure 1. As shown in Figure 1, the temperature was raised to 230°C at a predetermined rate. Then, after heating to predetermined set temperatures (a: 265°C, b: 263°C, c: 260°C) for 20 seconds, the temperature was lowered to 230°C. At this time, the maximum set temperature at which the test specimen did not melt and no blistering occurred on the surface was determined, and this maximum set temperature was defined as the reflow heat resistance temperature. Note that the reflow heat resistance temperature of a moisture-absorbing test specimen tends to be lower than that of a completely dry specimen.

[0170] Table 1 shows the composition and evaluation results of each polyamide resin composition.

[0171] [Table 1]

Claims

1. Semi-aromatic polyamide resin (A), Hydrophilic zeolite (B) and Halogen-based flame retardant (C), A polyamide resin composition containing the following:

2. The SiO contained in the hydrophilic zeolite (B) ２ / Al ２ O ３ The polyamide resin composition according to claim 1, wherein the molar ratio of is less than 30.

3. The polyamide resin composition according to claim 1 or 2, wherein the content of the hydrophilic zeolite (B) is 0.1% by mass or more and 10% by mass or less based on 100% by mass of the polyamide resin composition.

4. The polyamide resin composition according to claim 1 or 2, wherein the halogen content of the halogen-based flame retardant (C) is 65% by mass or more relative to the total mass of the halogen-based flame retardant (C).

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

6. A polyamide molded article according to claim 5, which is a component of an electronic device.

7. A step of placing the polyamide molded body according to claim 6 onto a substrate, A step of heating the polyamide molded body and the substrate and fixing the polyamide molded body and the substrate by reflow soldering, A method for manufacturing electronic devices, including

8. The method for manufacturing an electronic device according to claim 7, wherein in the fixing step, the polyamide molded body, the substrate, and the solder are heated in a reflow oven at a temperature of 240°C or higher.

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