Method for manufacturing resin compositions, pellets, molded articles, and plated molded articles

Abstract

To provide a resin composition, pellets, molded articles, and a method for manufacturing plated molded articles that have excellent flame retardancy and a high temperature of deflection under load. [Solution] The resin composition according to the present disclosure comprises (A) 30 to 65% by mass of a semi-aromatic polyamide resin, (B) 10 to 50% by mass of flake-like glass with a thickness of 0.1 to 2.0 μm, (C) 5 to 15% by mass of a phosphorus-based flame retardant containing at least one of a phosphinate and a diphosphinate, (D) 1 to 20% by mass of a laser direct structuring additive, and (E) 0 to 20% by mass of at least one other additive, wherein the total of (A) to (E) is 100% by mass, and (A) the semi-aromatic polyamide resin contains structural units having linear aliphatic chains with 4 to 7 carbon atoms, and the content of reinforcing fibers in the resin composition is less than 1% by mass.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing resin compositions, pellets, molded articles, and plated molded articles. [Background technology]

[0002] In recent years, with the development of mobile phones, including smartphones, various methods for incorporating antennas into mobile phones have been considered. In particular, there is a need for methods to incorporate antennas that can be designed in 3D into mobile phones. One technology that has attracted attention for forming such 3D antennas is laser direct structuring (hereinafter sometimes referred to as "LDS") technology. LDS technology is a technology in which, for example, a laser is irradiated onto the surface of a resin molded product containing an LDS additive to activate it, and then a metal is applied to the activated portion to form a plating. The characteristic of this technology is that metal structures such as antennas can be manufactured directly on the surface of a resin molded product without using adhesives or the like. Such LDS technology is disclosed in, for example, Patent Document 1 and Patent Document 2. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. O2019 / 167854 [Patent Document 2] Japanese Patent Publication No. 2015-120908 [Overview of the project] [Problems that the invention aims to solve]

[0004] In this context, flame retardancy is sometimes required for resin compositions used in laser direct structuring (LDS). In particular, high flame retardancy is sometimes required when used in thin-walled molded products. Furthermore, depending on the application, a high temperature of deflection under load may also be required. The present invention aims to solve these problems and to provide a method for manufacturing a resin composition, pellets, molded articles, and plated molded articles that have excellent flame retardancy and a high temperature of deflection under load. [Means for solving the problem]

[0005] Under these circumstances, the inventors conducted investigations and found that the above problems can be solved by blending a predetermined semi-aromatic polyamide resin, a glass reinforcing material of a predetermined shape, a predetermined flame retardant, and an LDS additive in predetermined proportions. Specifically, the above problem was solved by the following means. [1] (A) 30-65% by mass of semi-aromatic polyamide resin, (B) Flake-shaped glass with a thickness of 0.1 to 2.0 μm and a mass of 10 to 50 percent, (C) A phosphorus-based flame retardant comprising 5-15% by mass of at least one phosphinate and diphosphinate, (D) 1-20% by mass of laser direct structuring additive, (E) Consists of 0 to 20% by mass of at least one other additive, A resin composition wherein the sum of (A) to (E) above is 100% by mass, wherein (A) the semi-aromatic polyamide resin contains constituent units having linear aliphatic chains with 4 to 7 carbon atoms, and the content of reinforcing fibers in the resin composition is less than 1% by mass. [2] The resin composition according to [1], wherein the thickness of the (B) flake-like glass is 0.35 μm or more. [3] The resin composition according to [1] or [2], wherein the content of halogen atoms in the resin composition is less than 0.001% by mass. [4] The resin composition according to any one of [1] to [3], wherein the flame retardancy according to the UL-94 standard is V-0 when the resin composition is molded into a test piece with a thickness of 0.4 mm. [5] The resin composition according to any one of [1] to [4], wherein the (A) semi-aromatic polyamide resin contains a diamine unit and a dicarboxylic acid unit, and at least 70 mol% of the diamine unit is a xylylenediamine unit. [6] The resin composition according to any one of [1] to [5], wherein the (C) phosphorus-based flame retardant contains at least one compound represented by formula (I) and a compound represented by formula (II). [Chemical formula] (In formula (I), R 1 and R 2 each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. M represents a calcium ion, an aluminum ion, a magnesium ion, or a zinc ion. m is a natural number representing the valence of M.) [Chemical formula] (In formula (II), R 4 and R 5 each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. R 3 represents a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 10 carbon atoms, or an arylalkylene group having 7 to 10 carbon atoms. M represents a calcium ion, an aluminum ion, a magnesium ion, or a zinc ion. n is a natural number representing the valence of M. n, a, and b are natural numbers satisfying the relational expression 2 × b = n × a.) [7] The resin composition according to any one of [1] to [6], wherein the (B) laser direct structuring additive contains copper chromate. [8] The resin composition according to any one of [1] to [7], further comprising a nucleating agent. [9] The thickness of the (B) flaky glass is 0.35 μm or more, the content of halogen atoms in the resin composition is less than 0.001% by mass, When the resin composition is molded into a test piece with a thickness of 0.4 mm, the flame retardancy according to the UL-94 standard satisfies V-0. The (A) semi-aromatic polyamide resin contains a diamine unit and a dicarboxylic acid unit, and the polyamide resin contains a polyamide resin in which 70 mol% or more of the diamine units are xylylenediamine units. The (C) phosphorus-based flame retardant contains at least one compound represented by the formula (I) and a compound represented by the formula (II). The (B) laser direct structuring additive contains copper chromate. Furthermore, the resin composition according to any one of [1] to [8], which contains a nucleating agent.

Chemical formula

Chemical formula

[10] Pellets of the resin composition according to any one of [1] to [9].

[11] A molded article formed from the resin composition according to any one of [1] to [9]. A molded product formed from the pellets described in

[12]

[10] .

[13] The molded article according to

[11] or

[12] , having a plating on the surface of the molded article.

[14] The molded article according to

[13] , wherein the plating has the properties of an antenna.

[15] A molded product described in any one of

[11] to

[14] , which is a component of a portable electronic device. A method for manufacturing a plated molded article, comprising irradiating the surface of a molded article formed from any one of the resin compositions described in

[16] , [1], to a laser, and then applying a metal to form a plating. [Effects of the Invention]

[0006] The present invention makes it possible to provide a resin composition, pellets, molded articles, and a method for manufacturing plated molded articles that have excellent flame retardancy and a high temperature of deflection under load. [Brief explanation of the drawing]

[0007] [Figure 1] This is a schematic diagram showing the process of applying plating to the surface of a resin molded product. [Modes for carrying out the invention]

[0008] The following describes in detail embodiments for carrying out the present invention (hereinafter simply referred to as "this embodiment"). Note that the following embodiment is illustrative for explaining the present invention, and the present invention is not limited to this embodiment. In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits. "A~B" means that it is greater than or equal to A and less than or equal to B. Furthermore, the upper and lower limits of the numerical values ​​in this specification are given as examples of this embodiment, regardless of the combination of upper and lower limits.

[0009] In this specification, a preferred combination of embodiments is a more preferred embodiment. In this specification, all physical properties and characteristic values ​​shall be those at 23°C unless otherwise specified.

[0010] In this specification, unless otherwise specified, weight-average molecular weight and number-average molecular weight are polystyrene-converted values ​​measured by GPC (gel permeation chromatography). In this specification, unless otherwise specified, weight-average molecular weight and number-average molecular weight may be measured in accordance with paragraph 0047 of Japanese Patent Application Publication No. 2018-165298, which is incorporated herein by reference. In this specification, the melting point (Tm) and glass transition temperature (Tg, sometimes referred to as the glass transition point) shall be values ​​measured by differential scanning calorimetry (DSC) in accordance with ISO 11357, unless otherwise specified. Specifically, they may be measured in accordance with paragraph 0036 of International Publication No. 2016 / 084475, which is incorporated herein by reference.

[0011] If the measurement methods, etc., described in the standards shown in this specification differ from year to year, unless otherwise specified, the standards as of January 1, 2024 shall apply. If the measurement methods, etc., described in the standards shown in this specification have been discontinued as of January 1, 2024, the standards in effect at the time of discontinuation shall apply. Figure 1 may not accurately reflect reality due to its scale and other factors.

[0012] The resin composition of this embodiment comprises (A) 30 to 65% by mass of a semi-aromatic polyamide resin, (B) 10 to 50% by mass of flake-like glass with a thickness of 0.1 to 2.0 μm, (C) 5 to 15% by mass of a phosphorus-based flame retardant containing at least one of a phosphinate and a diphosphinate, (D) 1 to 20% by mass of a laser direct structuring additive, and (E) 0 to 20% by mass of at least one other additive, wherein the total of (A) to (E) is 100% by mass, and (A) the semi-aromatic polyamide resin contains structural units having linear aliphatic chains with 4 to 7 carbon atoms, and the content of reinforcing fibers in the resin composition is less than 1% by mass. By adopting this configuration, a resin composition with excellent flame retardancy and a high load deflection temperature can be obtained for LDS (Laser Deposition Stabilizer) applications. Furthermore, a resin composition with excellent flame retardancy can be obtained even when formed into thin-walled molded products. To impart flame retardancy to a resin composition containing a semi-aromatic polyamide resin, an LDS additive, and a glass reinforcing agent, it is conceivable to incorporate a flame retardant. However, it has been found that simply incorporating a flame retardant is not always sufficient. In particular, it has been found to be insufficient for producing thin-walled molded products. The inventors investigated and concluded that thin-walled molded products formed from LDS resin compositions containing glass fibers tended to sag during combustion. To prevent sagging, polytetrafluoroethylene (PTFE), known as an anti-dripping agent, could be incorporated. However, due to recent demands for halogen-free and organofluorine compound (PFAS)-free materials, it is desirable to avoid halogen-based flame retardants and PTFE. On the other hand, it was suspected that in thin-walled combustion test specimens formed from LDS resin compositions containing glass fibers, the glass fibers were oriented in the direction of the short side of the combustion test specimen, which promoted sagging during combustion. Therefore, the inventors succeeded in solving this problem by using flake-shaped glass. Specifically, it is suspected that because flake-shaped glass has low anisotropy during reinforcement, it does not have the same biased orientation as glass fibers in thin-walled combustion test specimens, thus maintaining vertical melt tension during combustion and preventing sagging.

[0013] Furthermore, in resin compositions for LDS, from the viewpoint of heat resistance, polyamide resins synthesized from para-xylylenediamine and sebacic acid have often been used as semi-aromatic polyamide resins. However, polyamide resins containing sebacic acid tend to be flammable because they contain structural units with long aliphatic chains. In this embodiment, it is presumed that the use of a semi-aromatic polyamide resin containing structural units having straight aliphatic chains with 4 to 7 carbon atoms made it less flammable.

[0014] Furthermore, by adopting the above configuration, the load deflection temperature could also be increased. In this embodiment, in particular, the load deflection temperature after water absorption treatment was also high. That is, in this embodiment, it is presumed that a high load deflection temperature was achieved by using flake-shaped glass as the glass reinforcing material and setting its thickness to 0.1 to 2.0 μm. If the thickness of the flake-shaped glass is too thick, it cannot adequately reinforce the deterioration of the physical properties of the water-absorbing polyamide resin, on the other hand, if the thickness is too thin, the surface area of ​​the flake-shaped glass becomes large, increasing the interface with the polyamide resin, making it easier for water to enter the interface and reducing the reinforcing effect. In this embodiment, it is presumed that this problem was solved by adjusting the thickness of the flake-shaped glass.

[0015] The embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is merely one example of an embodiment of the present invention and is not limited to these.

[0016] <(A) Semi-aromatic polyamide resin> The resin composition of this embodiment contains (A) a semi-aromatic polyamide resin in a proportion of 30 to 65% by mass. The (A) semi-aromatic polyamide resin contains constituent units having linear aliphatic chains with 4 to 7 carbon atoms. By using such a semi-aromatic polyamide resin, a resin composition with excellent flame retardancy can be obtained. Here, semi-aromatic polyamide resin refers to monomer units constituting the semi-aromatic polyamide resin in which 30 mol% or more of the total monomer units excluding terminal groups are aromatic monomer units, preferably 40 mol% or more are aromatic monomer units, more preferably 45 mol% or more are aromatic monomer units, preferably 70 mol% or less are aromatic monomer units, more preferably 65 mol% or less are aromatic monomer units, even more preferably 60 mol% or less are aromatic monomer units, and even more preferably 55 mol% or less are aromatic monomer units. Aromatic monomers refer to monomers having an aromatic ring, and include aromatic diamines such as xylylenediamine, aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid, and aromatic aminocarboxylic acids.

[0017] The (A) semi-aromatic polyamide resin used in this embodiment contains diamine units and dicarboxylic acid units, and it is preferable that more than 50 mol% of the dicarboxylic acid units are constituent units having a linear aliphatic chain with 4 to 7 carbon atoms. By using dicarboxylic acids with short aliphatic chains in this way, the burning time of the molded article can be shortened. In particular, in this embodiment, it is preferable that the (A) semi-aromatic polyamide resin does not substantially contain monomer units containing linear aliphatic chains with 8 or more carbon atoms. Here, substantially does not contain means that the proportion of monomer units containing linear aliphatic chains with 8 or more carbon atoms among all monomer units constituting the (A) semi-aromatic polyamide resin, excluding terminal groups, is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. By adopting such a configuration, it becomes possible to manufacture molded articles with superior flame retardancy, in particular, with a shorter burning time.

[0018] In this embodiment, it is preferable that 70 mol% or more of the diamine units contained in the (A) semi-aromatic polyamide resin are xylylenediamine units (meaning constituent units derived from xylylenediamine). Hereinafter, such (A) semi-aromatic polyamide resin may be referred to as xylylenediamine-based polyamide resin.

[0019] In xylylenediamine-based polyamide resins, it is preferable to use metaxylylenediamine and / or paraxylylenediamine as the xylylenediamine. In this embodiment, it is preferable that the xylylenediamine is either metaxylylenediamine alone or a mixture (copolymer) of metaxylylenediamine and paraxylylenediamine. In xylylenediamine, the molar ratio of metaxylylenediamine to paraxylylenediamine is preferably 100:0 to 10:90, more preferably 100:0 to 15:85, even more preferably 100:0 to 50:50, even more preferably 100:0 to 60:40, and even more preferably 80:20 to 65:45. In xylylenediamine-based polyamide resins, the diamine units are preferably 75 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and even more preferably 98 mol% or more.

[0020] Other diamines that can be used as raw material diamine components for xylylenediamine-based polyamide resins include aliphatic diamines such as tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine, as well as 1,3-bis(aminomethyl) Examples include alicyclic diamines such as chlorohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminomethyl)decalin, and bis(aminomethyl)tricyclodecane, as well as aromatic ring-containing diamines such as bis(4-aminophenyl) ether, paraphenylenediamine, and bis(aminomethyl)naphthalene. These can be used individually or in combination of two or more.

[0021] In xylylenediamine-based polyamide resins, it is preferable that the dicarboxylic acid units are preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and even more preferably 98 mol% or more, and are dicarboxylic acid units having a linear aliphatic chain with 4 to 7 carbon atoms, and more preferably adipic acid units.

[0022] In addition, examples of dicarboxylic acids other than those mentioned above include phthalate compounds such as isophthalic acid, terephthalic acid, and orthophthalic acid, and naphthalenedicarboxylic acids such as 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid, and can be used individually or in combination of two or more.

[0023] The (A) semi-aromatic polyamide resin used in this embodiment mainly consists of diamine units and dicarboxylic acid units, but this does not exclude the inclusion of other monomer units. It goes without saying that it may also contain lactams such as ε-caprolactam and laurolactam, and aliphatic aminocarboxylic acid units such as aminocaproic acid and aminoundecanoic acid. Here, "main component" means that among the monomer units constituting the semi-aromatic polyamide resin, the total number of diamine units and dicarboxylic acid units is the largest among all monomer units. In this embodiment, the total of diamine units and dicarboxylic acid units in the semi-aromatic polyamide resin preferably accounts for 90% by mass or more of the total monomer units, more preferably 95% by mass or more, and may also account for 99% by mass or more.

[0024] The melting point of the semi-aromatic polyamide resin used in the resin composition of this embodiment is preferably 200°C or higher, and more preferably 300°C or lower. Using such a semi-aromatic polyamide resin tends to more effectively improve mechanical strength and flame retardancy.

[0025] The (A) semi-aromatic polyamide resin used in the resin composition of this embodiment preferably has a lower limit of number average molecular weight (Mn) of 6,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, even more preferably 15,000 or more, and even more preferably 20,000 or more. The upper limit of Mn is preferably 35,000 or less, more preferably 30,000 or less, and even more preferably 28,000 or less.

[0026] It is also preferable to use polyamide resins manufactured using biomass raw materials (biomass polyamide resins) for xylylenediamine-based polyamide resins. By using biomass polyamide resins, it is possible to reduce the environmental impact. In the polyamide resin of this embodiment, biododecanedioic acid and xylylenediamine can be used as biomass raw materials. Furthermore, xylylenediamine certified under Mass Balance Certification (ISCC PLUS) can also be used. Mass balance certification means that the extent to which renewable and bio-based raw materials are used in each factory or production facility, and how much of the resulting product is produced or shipped, is quantified and guaranteed along with quality.

[0027] The resin composition of this embodiment is a resin composition in which the sum of (A) to (E) above is 100% by mass, and contains (A) semi-aromatic polyamide resin in a proportion of 30 to 65% by mass. By setting it above the lower limit, flame retardancy tends to improve while maintaining mechanical properties. The content of (A) semi-aromatic polyamide resin in the resin composition of this embodiment is preferably 35% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, even more preferably 50% by mass or more, and preferably 65% ​​by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less. The resin composition of this embodiment may contain only one type of (A) semi-aromatic polyamide resin, or it may contain two or more types. If it contains two or more types, it is preferable that the total amount is within the above range.

[0028] The resin composition of this embodiment preferably contains less than 1% by mass of aliphatic polyamide resin, and more preferably 0.5% by mass or less. By reducing the content of aliphatic polyamide resin in the resin composition in this way, the burning time when the resin composition burns can be shortened. The content of aliphatic polyamide resin in the resin composition of this embodiment is also preferably less than 1% by mass of the content of (A) semi-aromatic polyamide resin in the resin composition, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less. In this embodiment, the aliphatic polyamide resin refers to a polyamide resin in which more than 70 mol% of the monomer units constituting the polyamide resin are aliphatic monomer units. Aliphatic monomers refer to monomers other than aromatic monomers, and include lactams, aliphatic diamines, aliphatic dicarboxylic acids, aliphatic aminocarboxylic acids, etc. Specific examples of aliphatic polyamide resins include polyamide 6, polyamide 66, polyamide 11, and polyamide 12.

[0029] <(B) Flake-shaped glass> The resin composition of this embodiment contains flake-shaped glass with a thickness of 0.1 to 2.0 μm. The thickness of the flake-shaped glass refers to the average thickness. The thickness of the flake-shaped glass is preferably 0.35 μm or more, more preferably 0.4 μm or more, even more preferably 0.5 μm or more, and even more preferably 0.6 μm or more. Furthermore, the thickness of the flake-shaped glass is preferably 1.8 μm or less, more preferably 1.6 μm or less, even more preferably 1.4 μm or less, even more preferably 1.2 μm or less, even more preferably 1.0 μm or less, and even more preferably 0.8 μm or less. The average thickness is measured by the following method. That is, a scanning electron microscope (SEM) is used to measure the thickness of 100 or more flake-shaped glass pieces, and the average of these measured values ​​is used to determine the average thickness. The sample stage of the scanning electron microscope is adjusted using a sample stage fine adjustment device so that the cross-section (thickness surface) of the flake-shaped glass is perpendicular to the irradiation electron beam axis of the scanning electron microscope.

[0030] The glass composition of the above-mentioned flake-shaped glass generally uses commercially available glass such as E glass (Electrical glass), C glass (Chemical glass), A glass (Alkali glass), S glass (High strength glass), and alkali-resistant glass, but it is preferable to include E glass.

[0031] In this embodiment, the (B) flake-shaped glass is preferably surface-treated with a surface treatment agent. The amount of surface treatment agent applied is preferably 0.01 to 1% by mass of the (B) flake-shaped glass fibers.

[0032] The content of (B) flake-shaped glass in the resin composition of this embodiment is 10 to 50% by mass or more. The content of (B) flake-shaped glass is preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. The resin composition of this embodiment may contain only one type of (B) flake-shaped glass, or it may contain two or more types. When it contains two or more types of (B) flake-shaped glass, it is preferable that the total amount is within the above range.

[0033] The resin composition of this embodiment has a reinforcing fiber content of less than 1% by mass, preferably less than 0.1% by mass, and more preferably less than 0.01% by mass. Reinforcement fibers include glass fibers, carbon fibers, etc. Reinforcement fibers also include those referred to as milled fibers and chopped strands. This configuration allows for the production of molded products with excellent flame retardancy and a high temperature of deflection under load.

[0034] <(C) Phosphorus-based flame retardant> The resin composition of this embodiment contains (C) a phosphorus-based flame retardant in a proportion of 5 to 15% by mass. By including (C) a phosphorus-based flame retardant, flame retardancy can be achieved in the resulting molded article. In this embodiment, (C) the phosphorus-based flame retardant comprises at least one of a phosphinate and a diphosphinate.

[0035] In this embodiment, it is preferable that the (C) phosphorus-based flame retardant further includes at least one compound represented by formula (I) and a compound represented by formula (II). [ka] (In formula (I), R 1 and R 2 Each of these independently represents a linear or branched alkyl group with 1 to 6 carbon atoms, or an aryl group with 6 to 10 carbon atoms. M represents a calcium ion, aluminum ion, magnesium ion, or zinc ion. m is a natural number representing the valency of M. [ka] (In formula (II), R 4 and R 5Each of these independently represents a linear or branched alkyl group with 1 to 6 carbon atoms, or an aryl group with 6 to 10 carbon atoms. 3 represents a linear or branched alkylene group with 1 to 10 carbon atoms, an arylene group with 6 to 10 carbon atoms, an alkylarylene group with 7 to 10 carbon atoms, or an arylalkylene group with 7 to 10 carbon atoms. M represents a calcium ion, aluminum ion, magnesium ion, or zinc ion. n is a natural number representing the valence of M. n, a, and b are natural numbers satisfying the relationship 2 × b = n × a.

[0036] In equation (I), R 1 and R 2 Each of these independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably a methyl group, an ethyl group, a propyl group, or a phenyl group. M represents a calcium ion, an aluminum ion, a magnesium ion, or a zinc ion. m is a natural number representing the valency of M, preferably 2 or 3.

[0037] In equation (II), R 4 and R 5 Each of these independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably a methyl group, an ethyl group, a propyl group, or a phenyl group. 3 represents a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 10 carbon atoms, or an arylalkylene group having 7 to 10 carbon atoms, preferably a methylene group, an ethylene group, a propylene group, or a phenylene group. M represents a calcium ion, an aluminum ion, a magnesium ion, or a zinc ion. n is a natural number representing the valence of M. n, a, and b are natural numbers that satisfy the relationship 2 × b = n × a. n is preferably 2 or 3. b is preferably 1, 2, or 3, and more preferably 1 or 3. a is preferably 1 or 2.

[0038] Phosphinates or diphosphinates specifically include those produced in an aqueous medium using phosphinic acid and metal carbonates, metal hydroxides, or metal oxides. Phosphinates or diphosphinates are basically monomeric compounds, but depending on the reaction conditions, they may also become polymeric phosphinates with a degree of condensation of 1 to 3 under certain environmental conditions.

[0039] Examples of phosphinic acids or diphosphinic acids include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methanedi(methylphosphinic acid), benzene-1,4-di(methylphosphinic acid), methylphenylphosphinic acid, and diphenylphosphinic acid.

[0040] Examples of phosphinates 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, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate.

[0041] Examples of diphosphinates include calcium methanedi(methylphosphinate), magnesium methanedi(methylphosphinate), aluminum methanedi(methylphosphinate), zinc methanedi(methylphosphinate), calcium benzene-1,4-di(methylphosphinate), magnesium benzene-1,4-di(methylphosphinate), aluminum benzene-1,4-di(methylphosphinate), and zinc benzene-1,4-di(methylphosphinate).

[0042] Among these phosphinates or diphosphinates, aluminum ethylmethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate are particularly preferred from the viewpoint of flame retardancy and electrical properties. Specific examples of such products include Clariant's EXOLIT OP 1230 (phosphinate metal salt) and EXOLIT OP 1400 (both trade names).

[0043] The content of (C) phosphorus-based flame retardant in the resin composition of this embodiment is 5% by mass or more, preferably 6% by mass or more, more preferably 7% by mass or more, even more preferably 8% by mass or more, and even more preferably 9% by mass or more. The upper limit of the content of (C) phosphorus-based flame retardant is 15% by mass or less, preferably 13% by mass or less, and even more preferably 12% by mass or less in the resin composition. If the amount of (C) phosphorus-based flame retardant is too high, the resulting molded product will have excellent flame retardancy, but its mechanical strength will be poor, and it will be prone to causing gas and mold contamination during molding. The resin composition of this embodiment may contain only one type of (C) phosphorus-based flame retardant, or it may contain two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0044] The resin composition of this embodiment may or may not contain flame retardants other than (C) phosphorus-based flame retardants. The resin composition of this embodiment preferably contains substantially no halogen-based flame retardants. Substantially no halogen-based flame retardants means that the content of halogen-based flame retardants in the resin composition is preferably less than 10% by mass, more preferably less than 7% by mass, even more preferably less than 5% by mass, even more preferably less than 3% by mass, and even more preferably less than 1% by mass. Here, halogenated flame retardants include anti-dripping agents such as PTFE. Furthermore, it is preferable that the resin composition of this embodiment substantially contains no flame retardants other than phosphorus-based flame retardants. Substantially containing no flame retardants means that the content of flame retardants other than phosphorus-based flame retardants in the resin composition is preferably less than 10% by mass, more preferably less than 7% by mass, even more preferably less than 5% by mass, even more preferably less than 3% by mass, and even more preferably less than 1% by mass.

[0045] <(D) Laser Direct Structuring Additive> The resin composition of this embodiment includes (D) a laser direct structuring additive (LDS additive). This configuration provides a resin composition with excellent plating properties. In this embodiment, the LDS additive is a compound obtained by adding 10 parts by mass of an additive considered to be an LDS additive to 100 parts by mass of a semi-aromatic polyamide resin, irradiating it with a YAG laser with a wavelength of 1064 nm at an output of 10 W, a frequency of 80 kHz, and a speed of 3 m / s, and then immersing it in an electroless plating bath as a subsequent plating process, thereby selectively forming plating only on the laser-irradiated area. The LDS additive used in this embodiment may be a synthetic product or a commercially available product. In addition to commercially available products that are sold as LDS additives, commercially available products may also be substances sold for other uses, as long as they meet the requirements of the LDS additive in this embodiment. Only one type of LDS additive may be used, or two or more types may be used in combination.

[0046] The first embodiment of the LDS additive used in this embodiment is a compound containing copper and chromium. The LDS additive of the first embodiment preferably contains 10 to 30% by mass of copper. It is also preferably containing 15 to 50% by mass of chromium. The LDS additive in the first embodiment is preferably an oxide containing copper and chromium, and more preferably a copper-chromium oxide.

[0047] The preferred form of copper and chromium is the spinel structure. The spinel structure is one of the representative crystal structures found in complex oxides of the AB2O4 type (where A and B are metallic elements).

[0048] The LDS additive of the first embodiment may contain trace amounts of other metals in addition to copper and chromium. Examples of other metals include antimony, tin, lead, indium, iron, cobalt, nickel, zinc, cadmium, silver, bismuth, arsenic, manganese, magnesium, and calcium, with manganese being preferred. These metals may exist as oxides. A preferred example of the LDS additive in the first embodiment is an LDS additive in which the content of metal oxides other than copper-chromium oxide is 10% by mass or less.

[0049] A second embodiment of the LDS additive used in this embodiment is an oxide containing at least one of antimony and phosphorus, and tin, preferably an oxide containing antimony and tin.

[0050] In the second embodiment, the LDS additive is more preferably one in which the tin content is greater than the phosphorus and antimony content, and even more preferably one in which the amount of tin relative to the total amount of tin, phosphorus and antimony is 80% by mass or more.

[0051] In particular, as the LDS additive of the second embodiment, an oxide containing antimony and tin is preferred, an oxide in which the tin content is greater than the antimony content is more preferred, and an oxide in which the amount of tin relative to the total amount of tin and antimony is 80% by mass or more is even more preferred.

[0052] More specifically, examples of LDS additives in the second embodiment include antimony-doped tin oxide, antimony oxide-doped tin oxide, phosphorus-doped tin oxide, and phosphorus oxide-doped tin oxide, with antimony-doped tin oxide and antimony oxide-doped tin oxide being preferred, and antimony oxide-doped tin oxide being more preferred. For example, in an LDS additive containing phosphorus and tin oxide, the phosphorus content is 1 to 20% by mass. In an LDS additive containing antimony and tin oxide, the antimony content is preferably 1 to 20% by mass. In an LDS additive containing phosphorus, antimony, and tin oxide, the phosphorus content is preferably 0.5 to 10% by mass, and the antimony content is preferably 0.5 to 10% by mass.

[0053] The third embodiment of the LDS additive used in this embodiment contains at least two metals and has a resistivity of 5 × 10 3 It is preferable to include conductive oxides with a resistivity of Ω·cm or less. The resistivity of the conductive oxide is 8 × 10⁻⁶. 2 Ω·cm or less is more preferable, 7 × 10 2 It is even more preferable that the value be Ω·cm or less, and 5 × 10 2 A value of Ω·cm or less is even more preferable. There are no particular restrictions on the lower limit, but for example, 1 × 10 1 It may be greater than or equal to Ω·cm, and furthermore, 1 × 10 2 It is acceptable if it is greater than Ω·cm. In this embodiment, the resistivity of the conductive oxide usually refers to the powder resistivity. 10 g of fine conductive oxide powder is placed inside a 25 mm diameter cylinder with a Teflon® coating on its inner surface and measured at 100 kgf / cm². 2 It can be pressurized (filled to 20%) and measured using a Yokogawa Electric "3223" tester.

[0054] The LDS additive used in the third embodiment has a resistivity of 5 × 10 3The composition is not particularly limited as long as it contains conductive oxides with a conductivity of Ω·cm or less, but it is preferable to include at least two types of metals, specifically, a metal from group n of the periodic table (where n is an integer from 3 to 16) and a metal from group n+1. An integer n from 10 to 13 is more preferable, and 12 or 13 is even more preferable. In the third embodiment, the LDS additive used has a preferred content of 15 mol% or less, more preferably 12 mol% or less, and even more preferably 10 mol% or less, when the total content of metals from group n (where n is an integer from 3 to 16) and group n+1 of the periodic table in the LDS additive is set to 100 mol%. There is no particular lower limit, but 0.0001 mol% or more is preferred. By setting the content of two or more metals within this range, the plating properties can be improved. In this embodiment, in particular, group n metal oxides doped with group n+1 metals are preferred. Furthermore, in the third embodiment, it is preferable that 98% by mass or more of the metal components contained in the LDS additive consist of metals from group n and group n+1 of the periodic table.

[0055] Examples of metals in Group n of the periodic table include Group 3 (scandium, yttrium), Group 4 (titanium, zirconium, etc.), Group 5 (vanadium, niobium, etc.), Group 6 (chromium, molybdenum, etc.), Group 7 (manganese, etc.), Group 8 (iron, ruthenium, etc.), Group 9 (cobalt, rhodium, iridium, etc.), Group 10 (nickel, palladium, platinum), Group 11 (copper, silver, gold, etc.), Group 12 (zinc, cadmium, etc.), Group 13 (aluminum, gallium, indium, etc.), Group 14 (germanium, tin, etc.), Group 15 (arsenic, antimony, etc.), and Group 16 (selenium, tellurium, etc.). Among these, metals in Group 12 (n=12) are preferred, and zinc is more preferred.

[0056] Examples of metals in Group n+1 of the periodic table include Group 4 (titanium, zirconium, etc.), Group 5 (vanadium, niobium, etc.), Group 6 (chromium, molybdenum, etc.), Group 7 (manganese, etc.), Group 8 (iron, ruthenium, etc.), Group 9 (cobalt, rhodium, iridium, etc.), Group 10 (nickel, palladium, platinum), Group 11 (copper, silver, gold, etc.), Group 12 (zinc, cadmium, etc.), Group 13 (aluminum, gallium, indium, etc.), Group 14 (germanium, tin, etc.), Group 15 (arsenic, antimony, etc.), and Group 16 (selenium, tellurium, etc.). Among these, metals in Group 13 (n+1=13) are preferred, aluminum or gallium are more preferred, and aluminum is even more preferred.

[0057] The LDS additive used in the third embodiment may contain metals other than conductive metal oxides. Examples of metals other than conductive oxides include antimony, titanium, indium, iron, cobalt, nickel, cadmium, silver, bismuth, arsenic, manganese, chromium, magnesium, and calcium. These metals may exist as oxides. The content of each of these metals is preferably 0.01% by mass or less relative to the LDS additive.

[0058] Among the above, in this embodiment, the LDS additive preferably contains at least one of copper, antimony, tin, aluminum, and zinc, and more preferably contains copper. Therefore, the LDS additive of the first embodiment is more preferred.

[0059] The number-average particle size of the LDS additive used in this embodiment is preferably 0.01 to 100 μm, more preferably 0.05 to 30 μm, and even more preferably 0.05 to 15 μm. By using such a number-average particle size, the surface of the plating can be made more uniform.

[0060] The resin composition of this embodiment contains 1% by mass or more of (D)LDS additive (preferably copper chromium oxide), preferably 2% by mass or more, more preferably 3% by mass or more, even more preferably 4% by mass or more, and also contains 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less, and even more preferably 7% by mass or less. The resin composition of this embodiment may contain only one (D)LDS additive or two or more. When two or more are included, it is preferable that the total amount is within the above range.

[0061] <(E) Other additives> The resin composition of this embodiment contains (E) other additives other than (A) to (D) above in an amount of 0 to 20% by mass. That is, the resin composition of this embodiment may consist only of the components (A) to (D) above, or it may also contain (E) other additives in an amount of 20% by mass or less of the resin composition.

[0062] (E) Examples of other additives include nucleating agents, release agents, colorants, stabilizers, alkalis, elastomers, titanium dioxide, hydrolysis resistance modifiers, matting agents, plasticizers, dispersants, antistatic agents, colorant inhibitors, gelation inhibitors, and colorants. Details of these can be found in paragraphs 0130-0155 of Japanese Patent No. 4894982 and paragraphs 0047-0103 of International Publication No. 2021 / 241471, and this information is incorporated herein. (E) The total amount of other additives is preferably 18% by mass or less of the resin composition, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and may be 1% by mass or less. The lower limit of the content of (E) other additives is preferably 0.1% by mass or more. (E) Other additives may be used alone or in combination of two or more. The resin composition of this embodiment preferably contains substantially no halogen atoms. Substantially, the content of halogen atoms in the resin composition is less than 0.001% by mass, preferably less than 0.0009% by mass, more preferably less than 0.0007% by mass, even more preferably less than 0.0005% by mass, even more preferably less than 0.0003% by mass, and even more preferably less than 0.0001% by mass.

[0063] <<Nuclear agent>> As described above, the resin composition of this embodiment may contain a nucleating agent. Including a nucleating agent can improve the appearance. Talc is preferred as the nucleating agent. The talc may be surface-treated with at least one compound selected from polyorganohydrogensiloxanes and organopolysiloxanes. In this case, the amount of siloxane compound attached to the talc is preferably 0.1 to 5% by mass of the talc.

[0064] The content of the nucleating agent in the resin composition of this embodiment is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, with an upper limit of 1% by mass or less, preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less, based on 100% by mass of the resin composition.

[0065] <<Release agent>> The resin composition of this embodiment may contain a mold release agent. Release agents are primarily used to improve the productivity of molding resin compositions. Examples of release agents include aliphatic carboxylic acid amides, aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number average molecular weight of 200 to 15000, polysiloxane-based silicone oils, and higher fatty acid metal salts.

[0066] For further details regarding the release agent, please refer to paragraphs 0037-0042 of Japanese Patent Publication No. 2016-196563, paragraphs 0067-0070 of Japanese Patent Publication No. 2021-161125, and paragraphs 0048-0058 of Japanese Patent Publication No. 2016-078318, in addition to the above, and these contents are incorporated herein by reference.

[0067] The release agent content is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, based on 100% by mass of the resin composition, and the upper limit is 1% by mass or less, preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less. By setting the content within this range, good release properties can be achieved when performing mold molding such as injection molding, and mold contamination can be effectively suppressed. The release agent may be used alone or in combination of two or more types. When using two or more types, it is preferable that the total amount be within the above range.

[0068] <Physical properties of the resin composition> The resin composition of this embodiment preferably has a high load deflection temperature. Specifically, when the resin composition of this embodiment is molded into an ISO tensile test specimen (4 mm thick), the load deflection temperature is preferably 210°C or higher, more preferably 215°C or higher, and even more preferably 218°C or higher, under bending stress conditions of 1.80 MPa in accordance with ISO 75-1, 2. There is no particular upper limit for the load deflection temperature, but 280°C or lower is practical, and even 270°C or lower is sufficient to meet the required performance. The resin composition of this embodiment preferably has excellent flame retardancy. Specifically, it is preferable that the flame retardancy according to the UL-94 standard is V-0 when the resin composition of this embodiment is molded into a test piece with a thickness of 0.4 mm. The resin composition of this embodiment preferably has a low water absorption rate. Specifically, when the resin composition of this embodiment is molded into an ISO tensile test piece (4 mm thick), and the test piece is left standing for 72 hours in an atmosphere of 80°C and 95% relative humidity, the water absorption rate calculated from the mass before and after this period is preferably 1.6% or less, more preferably 1.5% or less, and even more preferably 1.4% or less. The lower limit of the water absorption rate is preferably 1.0% or more. The above-mentioned load deflection temperature, flame retardancy, and water absorption rate are measured according to the examples described below.

[0069] <Method for producing resin compositions> Any method can be used to manufacture the resin composition of this embodiment. For example, one method involves mixing (A) a semi-aromatic polyamide resin, (B) flake-shaped glass, (C) a phosphorus-based flame retardant, (D) an LDS additive, and (E) other additives using a mixing means such as a V-type blender to prepare a single blended product, which is then melt-kneaded in a vented extruder to form pellets. Alternatively, as a two-stage mixing method, components other than (B) flake-shaped glass are thoroughly mixed beforehand, then melt-kneaded in a vented extruder to produce pellets, and finally, these pellets are mixed with (B) flake-shaped glass, and then melt-kneaded in a vented extruder. Furthermore, one method involves preparing a mixture of components other than (B) flake-shaped glass in advance using a V-type blender or the like, supplying this mixture from the first chute of a twin-screw extruder with a vent, and supplying (B) flake-shaped glass from a second chute in the middle of the extruder for melting, kneading, and pelletizing.

[0070] In the screw configuration of the extruder's kneading zone, it is preferable to place the elements that promote kneading on the upstream side and the elements that have the ability to increase pressure on the downstream side. Elements that promote kneading include progressive kneading disc elements, orthogonal kneading disc elements, wide kneading disc elements, and progressive mixing screw elements.

[0071] The heating temperature during melt mixing can usually be appropriately selected from the range of 180 to 360°C. If the temperature is too high, decomposition gases are likely to be generated, which may cause extrusion defects such as strand breakage. Therefore, it is desirable to select a screw configuration that takes shear heating into consideration. To suppress decomposition during mixing and subsequent molding processes, it is desirable to use antioxidants and heat stabilizers.

[0072] <Molded products> The molded article of this embodiment is formed from the resin composition or pellets of the resin composition of this embodiment. The method for manufacturing the molded product in this embodiment is not particularly limited, and any molding method commonly used for resin compositions can be arbitrarily employed. Examples include injection molding, ultra-high-speed injection molding, injection compression molding, two-color molding, hollow molding methods such as gas-assisted molding, molding using a heat-insulating mold, molding using a rapidly heated mold, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating) molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding, and blow molding. Molding methods using a hot runner system can also be used.

[0073] The molded article obtained by molding the resin composition of this embodiment is preferably used as a plated molded article having a plating on its surface. In the molded article of this embodiment, it is preferable that the plating has the properties of an antenna.

[0074] <Method for manufacturing plated molded products> Next, a method for manufacturing a plated molded article is disclosed, which includes irradiating the surface of a molded article formed from the resin composition of this embodiment with a laser, and then applying a metal to form a plating. Figure 1 is a schematic diagram showing the process of forming a plating on the surface of a molded product 1 using laser direct structuring technology. In Figure 1, the molded product 1 is a flat substrate, but it does not necessarily have to be a flat substrate; it may be a molded product that is partially or entirely curved. Furthermore, the resulting plated molded product is not limited to the final product, but can also include various parts.

[0075] During the plating process, a laser 2 is irradiated onto the molded product 1, as shown in Figure 1. The laser referred to here is not specifically defined and can be appropriately selected from known lasers such as YAG lasers, excimer lasers, and electromagnetic beams, with YAG lasers being preferred. The wavelength of the laser is also not specifically defined. A preferred wavelength range is 200 nm to 1200 nm, and more preferably 800 nm to 1200 nm. When the laser is irradiated, only the portion 3 irradiated by the laser is activated in the molded product 1. In this activated state, the molded product 1 is applied to the plating solution 4. The plating solution 4 is not particularly specified, and a wide range of known plating solutions can be used. Preferably, the plating solution consists of one or more of the following metal components (especially electroless plating solutions), more preferably a plating solution consisting of one or more of the following metals (especially electroless plating solutions), and even more preferably a plating solution containing copper (especially electroless plating solutions). In other words, in this embodiment, it is preferable that the plating consists of at least one of the above metals as the metal component. There is no specific method for applying the molded product 1 to the plating solution 4, but one example is to immerse it in a solution containing the plating solution. After applying the plating solution, the molded product will have plating 5 formed only on the parts that have been irradiated with the laser. In the method of this embodiment, it is possible to form plating (circuits) with a width of 1 mm or less, and even 150 μm or less (the lower limit is not specifically defined, but for example, 30 μm or more). To suppress corrosion and deterioration of the formed plating (circuit), the plating can be further protected with nickel and gold after electroless plating, for example. Similarly, electrolytic plating can be used after electroless plating to form the required film thickness in a short time. Furthermore, the above-described method for manufacturing plated molded products is preferably used as a method for manufacturing portable electronic device components having an antenna, including the above-described method for manufacturing plated molded products.

[0076] The resin composition, pellets, and molded articles of this embodiment can be used in various applications, such as electronic components (especially portable electronic device components) including connectors, switches, relays, and conductive circuits. In particular, the resin composition, pellets, and molded articles of this embodiment can be preferably used in SMT (Surface Mount Technology) applications.

[0077] Furthermore, without departing from the spirit of this embodiment, reference may be given to the descriptions in Japanese Patent Publication No. 2011-219620, Japanese Patent Publication No. 2011-195820, Japanese Patent Publication No. 2011-178873, Japanese Patent Publication No. 2011-168705, and Japanese Patent Publication No. 2011-148267. [Examples]

[0078] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or other reasons, measurements can be taken using other instruments with equivalent performance.

[0079] 1. Raw materials The raw materials shown in Table 1 were used. [Table 1]

[0080] <Synthesis Example of PAMP6> Into a reaction vessel equipped with a stirrer, a partial condenser, a total condenser, a thermometer, a dropping funnel, a nitrogen inlet tube, and a strand die, 7220 g (49.4 mol) of adipic acid (manufactured by Roadia) and 11.66 g of sodium acetate / sodium hypophosphite monohydrate (molar ratio = 1 / 1.5) were charged. After sufficient nitrogen substitution, while stirring the system under a small amount of nitrogen flow, it was heated and melted to 170 °C. 6647 g of a mixed xylylenediamine in which the molar ratio of meta-xylylenediamine to para-xylylenediamine is 70 / 30 (34.16 mol of meta-xylylenediamine, 14.64 mol of para-xylylenediamine, manufactured by Mitsubishi Gas Chemical Company) was dropped into the melt in the reaction vessel under stirring. While discharging the generated condensed water out of the system, the internal temperature was continuously raised to 260 °C over 2.5 hours. After the dropping was completed, the internal temperature was raised. When it reached 270 °C, the inside of the reaction vessel was depressurized, and the internal temperature was further raised to continue the melt polycondensation reaction at 280 °C for 20 minutes. Then, the system was pressurized with nitrogen, and the obtained polymer was taken out from the strand die and pelletized to obtain a polyamide resin. The melting point was 256 °C.

[0081] 2. Examples 1, 2, Comparative Examples 1 to 3 <Compound> The components shown in Table 1 were weighed as shown in Table 2 (the unit of each component is parts by mass). The components other than the flaky glass were blended in a tumbler and charged from the root of a twin-screw extruder (manufactured by Shibaura Machine Co., Ltd., TEM26SS) and melted. Then, the flaky glass was side-fed to produce pellets of the resin composition. The temperature setting of the twin-screw extruder was 280 °C.

[0082] <Flexural Strength and Flexural Modulus> After drying the pellets obtained by the above manufacturing method at 80°C for 12 hours, an ISO tensile test piece (4 mm thick) was injection molded using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., "NEX140III") under the conditions of a cylinder temperature of 280°C, a mold temperature of 130°C, and a molding cycle of 50 seconds. In accordance with ISO 178, using the above ISO tensile test piece (4 mm thick), the flexural strength (unit: MPa) and flexural modulus (unit: GPa) were measured in an environment of a temperature of 23°C and a humidity of 50%. The results are shown in Table 2.

[0083] <Charpy impact strength> In accordance with ISO 179-1 and 2, using the above ISO tensile test piece (4 mm thick), a Charpy impact strength with notch (unit: kJ / m 2 ) and a Charpy impact strength without notch (unit: kJ / m 2 ) were measured using a 1J hammer in an environment of a temperature of 23°C and a humidity of 50%. The results are shown in Table 2.

[0084] <Water absorption rate> Using the ISO tensile test piece (4 mm thick) obtained above, the test piece was left standing in an atmosphere of 80°C and a relative humidity of 95% for 72 hours, and the mass before and after that was measured to calculate the water absorption rate (unit: %). Water absorption rate (%) = [(mass of the test piece after water absorption - mass of the test piece before water absorption) / mass of the test piece before water absorption] × 100

[0085] <DTUL (Heat deflection temperature under load)> Using the ISO tensile test piece (4 mm thick) obtained above, it was processed into a shape based on ISO 75-1 and ISO 75-2, and the heat deflection temperature under load (unit: °C) was measured at a load of 1.80 MPa based on ISO 75-1 and ISO 75-2. Also, the DTUL after leaving the test piece standing in an atmosphere of 80°C and a relative humidity of 95% for 72 hours was measured in the same manner. Furthermore, the retention rate of DTUL after water absorption with respect to before water absorption was calculated. DTUL retention rate (%) = (DTUL before water absorption / DTUL after water absorption) × 100

[0086] <Flame retardancy (UL94 test)> The polyamide resin pellets obtained by the manufacturing method described above were dried at 120°C for 4 hours, and then injection molded using an injection molding machine (Japan Steel Works, Ltd., "J55AD") to form UL test combustion pieces measuring 125 mm in length, 13 mm in width, and 0.4 mm in thickness. The cylinder temperature and mold temperature were set to 280°C and 130°C, respectively. The obtained test specimens were evaluated for flame retardancy in accordance with the UL94 test. After the test specimens were left to stand for 48 hours in an atmosphere of 23°C and 50% humidity, the total burning time (seconds) of the five test specimens and the burning time (seconds) of the test specimen with the longest burning time were measured and recorded in the UL94 column of Table 2. In addition, the test specimens were heat-treated by leaving them to stand for 168 hours in a hot air circulating dryer set at 70°C (heat treatment at 70°C), and the flame retardancy was evaluated in the same manner, and the results were recorded as numerical values ​​in parentheses in the UL94 column of Table 2. The results are shown in Table 2.

[0087] <Plating properties> The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours, and then injected using an injection molding machine (Nissei Plastic Industrial Co., Ltd., "NEX-140III") under the conditions of cylinder temperature 300°C, mold temperature 130°C, and molding cycle of 50 seconds to form a plate measuring 60 mm x 60 mm x 2 mm in thickness. The obtained plates were irradiated with a YAG laser with a wavelength of 1064 nm at an output of 10 W, a velocity of 80 m / s, and a frequency of 3 μs. Next, the plates were degreased with a 10 mass% ethanol aqueous solution and then plated for 10 minutes in a MacDermid Copper100XB electroless plating bath at 65°C (set temperature 68°C). The evaluation was as follows: A: Plating was formed. B: Plating could not be formed.

[0088] [Table 2]

[0089] As is clear from the above results, the molded articles formed from the resin composition of the present invention were resin compositions with excellent flame retardancy and a high load deflection temperature. In particular, the DTUL was maintained at a high temperature even after water absorption treatment (Examples 1 and 2). In contrast, when the thickness of the flake-shaped glass fibers was greater (Comparative Example 1), the temperature of deflection under load became lower. Furthermore, when glass fibers were used instead of flake glass (Comparative Example 2), the flame retardancy was inferior. Furthermore, when the LDS additive was not included (Comparative Example 3), there were no problems with either flame retardancy or load deflection temperature, but plating could not be formed.

[0090] Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications are possible without departing from the intent and scope of the invention. [Explanation of symbols]

[0091] 1 Resin molded products 2 lasers 3. Area irradiated by the laser 4 Plating solution 5 Plating

Claims

1. (A) 30 to 65% by mass of semi-aromatic polyamide resin, (B) Flake-like glass with a thickness of 0.1 to 2.0 μm in an amount of 10 to 50% by mass, (C) A phosphorus-based flame retardant comprising 5 to 15% by mass of at least one phosphinate and diphosphinate, (D) 1 to 20% by mass of a laser direct structuring additive, (E) Consists of 0 to 20% by mass of at least one other additive, A resin composition in which the sum of (A) to (E) is 100% by mass, wherein (A) the semi-aromatic polyamide resin contains constituent units having linear aliphatic chains with 4 to 7 carbon atoms, and the content of reinforcing fibers in the resin composition is less than 1% by mass.

2. The resin composition according to claim 1, wherein the thickness of the (B) flake-shaped glass is 0.35 μm or more.

3. The resin composition according to claim 1 or 2, wherein the content of halogen atoms in the resin composition is less than 0.001% by mass.

4. The resin composition according to claim 1 or 2, wherein the flame retardancy according to the UL-94 standard is V-0 when the resin composition is molded into a test piece with a thickness of 0.4 mm.

5. The resin composition according to claim 1 or 2, wherein the (A) semi-aromatic polyamide resin comprises a polyamide resin containing diamine units and dicarboxylic acid units, wherein 70 mol% or more of the diamine units are xylylenediamine units.

6. The resin composition according to claim 1 or 2, wherein the (C) phosphorus-based flame retardant comprises at least one compound represented by formula (I) and a compound represented by formula (II). 【Chemistry 1】 (In formula (I), R １ and R ２ Each of these independently represents a linear or branched alkyl group with 1 to 6 carbon atoms, or an aryl group with 6 to 10 carbon atoms. M represents a calcium ion, aluminum ion, magnesium ion, or zinc ion. m is a natural number representing the valency of M. 【Chemistry 2】 (In formula (II), R ４ and R ５ Each of these independently represents a linear or branched alkyl group with 1 to 6 carbon atoms, or an aryl group with 6 to 10 carbon atoms. ３ represents a linear or branched alkylene group with 1 to 10 carbon atoms, an arylene group with 6 to 10 carbon atoms, an alkylarylene group with 7 to 10 carbon atoms, or an arylalkylene group with 7 to 10 carbon atoms. M represents a calcium ion, aluminum ion, magnesium ion, or zinc ion. n is a natural number representing the valence of M. n, a, and b are natural numbers satisfying the relationship 2 × b = n × a.

7. The resin composition according to claim 1 or 2, wherein the (B) laser direct structuring additive comprises copper chromium oxide.

8. The resin composition according to claim 1 or 2, further comprising a nucleating agent.

9. The thickness of the (B) flake-shaped glass is 0.35 μm or more. The content of halogen atoms in the resin composition is less than 0.001% by mass. When the aforementioned resin composition is molded into a test piece with a thickness of 0.4 mm, its flame retardancy according to the UL-94 standard satisfies V-0. The (A) semi-aromatic polyamide resin includes a polyamide resin that contains diamine units and dicarboxylic acid units, wherein 70 mol% or more of the diamine units are xylylenediamine units. The (C) phosphorus-based flame retardant comprises at least one compound represented by formula (I) and one compound represented by formula (II), The (B) laser direct structuring additive contains copper-chromium oxide, The resin composition according to claim 1, further comprising a nucleating agent. 【Transformation 3】 (In formula (I), R １ and R ２ Each of these independently represents a linear or branched alkyl group with 1 to 6 carbon atoms, or an aryl group with 6 to 10 carbon atoms. M represents a calcium ion, aluminum ion, magnesium ion, or zinc ion. m is a natural number representing the valency of M. 【Chemistry 4】 (In formula (II), R ４ and R ５ each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. R ３ represents a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 10 carbon atoms, or an arylalkylene group having 7 to 10 carbon atoms. M represents a calcium ion, an aluminum ion, a magnesium ion, or a zinc ion. n represents a natural number representing the valence of M. n, a, and b are natural numbers that satisfy the relational expression 2 × b = n × a.)

10. Pellets of the resin composition according to claim 1.

11. A molded article formed from the resin composition described in claim 1.

12. A molded article formed from the pellets described in claim 10.

13. The molded article according to claim 11 or 12, wherein the surface of the molded article is plated.

14. The molded article according to claim 13, wherein the plating has the properties of an antenna.

15. A molded article according to claim 11 or 12, which is a component of a portable electronic device.

16. A method for manufacturing a plated molded article, comprising irradiating the surface of a molded article formed from a resin composition according to claim 1, 2, or 9 with a laser, and then applying a metal to form a plating.

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