Polycarbonate resin composition

Abstract

A polycarbonate resin composition that meets various regulations and is environmentally friendly, while possessing excellent flame retardancy and superior LDS performance. The polycarbonate resin composition is characterized by containing 0.5 to 50 parts by mass of a laser direct structuring additive (B), 0.01 to 1 part by mass of an organic sulfonic acid metal salt (C), and 0.1 to 5.5 parts by mass of a flame retardant aid (D) with a 10% weight loss temperature of 350 to 600°C per 100 parts by mass of polycarbonate resin (A).

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition, and more specifically, to a polycarbonate resin composition that is environmentally friendly, clears various regulations such as PFAS, and possesses excellent laser direct structuring performance and excellent flame retardancy. [Background technology]

[0002] Polycarbonate resin is a resin with excellent heat resistance, mechanical properties, and electrical properties, and is widely used as a material for manufacturing parts in various industrial fields, such as vehicle parts, electrical and electronic equipment components, housing components, and other industrial sectors. In particular, flame-retardant polycarbonate resin compositions are suitably used as parts for vehicle parts, electrical and electronic equipment components such as personal computers, mobile phones, and battery cases, and components for office automation and information equipment such as printers and photocopiers.

[0003] In recent years, there has been a growing demand for methods to manufacture antennas capable of 3D design for a wide range of applications, including smartphones, various 5G devices, in-vehicle communication systems, and base stations. Laser direct structuring (hereinafter sometimes referred to as "LDS") is one such technology that has attracted attention for forming these 3D antennas. LDS technology is a technique in which, for example, a laser is irradiated onto the surface of a molded product (resin molded product) containing an LDS additive to activate it, and a plating layer is formed by applying metal to the activated portion. 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 (for example, Patent Document 1).

[0004] Furthermore, in recent years, there has been a growing demand for flame retardancy, and polycarbonate resin molded products like these are now required to have a high degree of flame retardancy, with UL-94 V-0 certification becoming increasingly common. Halogenated and phosphorus-based flame retardants have been used to impart flame retardancy to polycarbonate resins. However, achieving V-0 flame retardancy with phosphorus-based flame retardants requires a relatively high additive ratio, which tends to degrade the mechanical properties of the polycarbonate resin material. Flame retardation using halogenated bromine-based or chlorine-based flame retardants is subject to stricter regulations prohibiting its use due to toxicity and environmental problems caused by the generation of harmful gases. Fluorine-based flame retardants, such as perfluoroalkane metal salts, enable high levels of flame retardancy with relatively small amounts. Furthermore, by combining such flame retardants with polyfluoroethylene as a drip-preventing agent, dripping can be suppressed and flame retardancy can be further improved. However, in recent years, fluorine compounds have become subject to international regulations, primarily in Japan, Europe, and the United States. PFAS regulations targeting perfluoroalkyl and polyfluoroalkyl compounds are progressing, mainly in the EU and the US, and polyfluoroethylenes are also included. PFAS regulations are being further strengthened internationally. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2009 / 141799 [Overview of the project] [Problems that the invention aims to solve]

[0006] Therefore, there is a strong demand for a highly functional, flame-retardant polycarbonate resin composition for LDS that does not generate toxic gases during combustion, clears various regulations, and is environmentally friendly. The present invention has been made in view of the above circumstances, and its objective (problem) is to provide a polycarbonate resin composition that is environmentally friendly, has excellent LDS performance, and has excellent flame retardancy. [Means for solving the problem]

[0007] The inventors of the present invention, after diligent research to achieve the above objectives, discovered that the above objectives could be solved by combining LDS additives, organic sulfonic acid metal salts, and specific flame retardant additives in specific amounts, and thus completed the present invention. This invention relates to the following polycarbonate resin compositions and molded articles.

[0008] 1. A polycarbonate resin composition characterized by containing, per 100 parts by mass of polycarbonate resin (A), 0.5 to 50 parts by mass of laser direct structuring additive (B), 0.01 to 1 part by mass of organic sulfonic acid metal salt (C), and 0.1 to 5.5 parts by mass of flame retardant aid (D) having a 10% weight loss temperature of 350 to 600°C. 2. The polycarbonate resin composition according to item 1 above, wherein the flame retardant additive (D) is a mineral containing aluminum or magnesium. 3. The polycarbonate resin composition according to 1 or 2 above, wherein the flame retardant additive (D) is a silicate mineral. 4. A polycarbonate resin composition according to any one of the above 1 to 3, wherein the flame retardant additive (D) is selected from boehmite, halloysite, sepiolite, hydromagnesite, kaolin, montmorillonite, pyrophyllite, attapulgite, and vermiculite. 5. A polycarbonate resin composition according to any one of 1 to 4 above, wherein the content of the flame retardant aid (D) is 0.1 to 1.0 parts by mass per 100 parts by mass of polycarbonate resin (A). 6. The polycarbonate resin composition according to any one of 1 to 5 above, wherein the organic sulfonic acid metal salt (C) is an organic sulfonic acid metal salt that does not contain phosphorus or halogen. 7. A polycarbonate resin composition according to any one of 1 to 6 above, wherein the organic sulfonic acid metal salt (C) is an aromatic sulfonic acid metal salt. 8. A polycarbonate resin composition according to any one of claims 1 to 7, further comprising 1 to 90 parts by mass of filler (E) per 100 parts by mass of polycarbonate resin (A). 9. The polycarbonate resin composition according to item 8 above, wherein the filler (E) is a glass-based filler. 10. The polycarbonate resin composition according to item 9 above, wherein the filler (E) is glass fiber. 11. A polycarbonate resin composition according to any one of the above 1 to 10, wherein the fluorine content measured by combustion ion chromatography is less than 500 ppm by mass. A polycarbonate resin composition according to any one of the above 1 to 11, having a thickness of 12.1.5 mm and an UL-94 rating of V-0. 13. Pellets of the polycarbonate resin composition described in any of items 1 to 12 above. 14. A molded article of the polycarbonate resin composition described in any of items 1 to 13 above. 15. Molded product of the pellets described in item 13 above. 16. A polycarbonate resin composition characterized by containing, per 100 parts by mass of polycarbonate resin (A), 0.5 to 50 parts by mass of laser direct structuring additive (B), 0.01 to 1 part by mass of organic sulfonic acid metal salt (C), and 0.1 to 5.5 parts by mass of a mineral (D) selected from one or more of boehmite, halloysite, sepiolite, hydromagnesite, kaolin, montmorillonite, pyrophyllite, attapulgite, and vermiculite. [Effects of the Invention]

[0009] The polycarbonate resin composition of the present invention is an environmentally friendly material that clears various regulations such as PFAS, does not generate toxic gases when burned, has high flame retardancy while being environmentally friendly, can achieve V-0 at a thickness of 1.5 mm, has excellent LDS performance, and also has excellent flexural modulus and heat resistance. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below with reference to embodiments and examples. In this specification, unless otherwise specified, "~" means that the numbers before and after it are included as the lower and upper limits, respectively.

[0011] The polycarbonate resin composition of the present invention is characterized by comprising, per 100 parts by mass of a polycarbonate resin (A), 0.5 to 50 parts by mass of a laser direct structuring additive (B), 0.01 to 1 part by mass of an organic sulfonic acid metal salt (C), and 0.1 to 5.5 parts by mass of a flame retardant auxiliary (D) having a 10% weight loss temperature of 350 to 600°C.

[0012] [Polycarbonate Resin (A)] The polycarbonate resin (A) used in the present invention is not particularly limited, and various types thereof can be used. Polycarbonate resins can be classified into aromatic polycarbonate resins, in which the carbons directly bonded to the carbonic acid linkages are each aromatic carbon, and aliphatic polycarbonate resins, in which the carbons directly bonded to the carbonic acid linkages are each aliphatic carbon; either type can be used. Among these, as the polycarbonate resin (A), aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical properties, and the like.

[0013] Among the monomers serving as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds are as follows: dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (i.e., resorcinol), and 1,4-dihydroxybenzene; dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, and 4,4'-dihydroxybiphenyl;

[0014] dihydroxynaphthalenes such as 2,2'-dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene;

[0015] Dihydroxydiaryl ethers such as 2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis(3-hydroxyphenoxy)benzene, and 1,3-bis(4-hydroxyphenoxy)benzene;

[0016] 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A), 1,1-Bis(4-hydroxyphenyl)propane, 2,2-Bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C), 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-methoxy-4-hydroxyphenyl)propane, 1,1-Bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-Bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-cyclohexyl-4-hydroxyphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, Bis(4-hydroxyphenyl)methane, Bis(4-hydroxyphenyl)cyclohexylmethane, Bis(4-hydroxyphenyl)phenylmethane, Bis(4-hydroxyphenyl)(4-propenylphenyl)methane, Bis(4-hydroxyphenyl)diphenylmethane, Bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-naphthylethane, 1,1-Bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-Bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)hexane, 1,1-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)octane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)nonane, 1,1-bis(4-hydroxyphenyl)decane, 1,1-Bis(4-hydroxyphenyl)dodecane, Bis(hydroxyaryl)alkanes such as;

[0017] 1,1-Bis(4-hydroxyphenyl)cyclopentane, 1,1-Bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,4-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-Bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane, 1,1-Bis(4-hydroxyphenyl)-3-propyl-5-methylcyclohexane, 1,1-Bis(4-hydroxyphenyl)-3-tert-butyl-cyclohexane, 1,1-Bis(4-hydroxyphenyl)-4-tert-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane, 1,1-Bis(4-hydroxyphenyl)-4-phenylcyclohexane, Bis(hydroxyaryl)cycloalkanes such as;

[0018] 9,9-Bis(4-hydroxyphenyl)fluorene, Bisphenols containing cardo structures, such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene;

[0019] 4,4'-Dihydroxydiphenyl sulfide, Dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; 4,4'-Dihydroxydiphenylsulfone, Dihydroxydiarylsulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone; These are some examples.

[0020] Among these, bis(hydroxyaryl)alkanes are preferred, and among them, bis(4-hydroxyphenyl)alkanes are preferred, and in particular, 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A) and 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C) are preferred from the viewpoint of impact resistance and heat resistance. Furthermore, one aromatic dihydroxy compound may be used, or two or more may be used in any combination and ratio.

[0021] Among the monomers used as raw materials for polycarbonate resin, examples of carbonate precursors include carbonyl halides and carbonate esters. Note that one type of carbonate precursor may be used, or two or more types may be used in any combination and ratio.

[0022] Examples of carbonyl halides include, for example, phosgene; bischloroformates of dihydroxy compounds; monochloroformates of dihydroxy compounds; and other haloformates.

[0023] Examples of carbonate esters include diaryl carbonates such as diphenyl carbonate and dityl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; and carbonates of dihydroxy compounds such as biscarbonates, monocarbonates, and cyclic carbonates of dihydroxy compounds.

[0024] The method for producing the polycarbonate resin (A) is not particularly limited, and any method can be used. Examples include interfacial polymerization, molten transesterification, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers. Among these, interfacial polymerization and molten transesterification are preferred because they offer a greater improvement in moisture and heat resistance, with interfacial polymerization being particularly preferred.

[0025] The molecular weight of the polycarbonate resin (A) is the viscosity-average molecular weight (Mv) calculated from the solution viscosity measured at 25°C using methylene chloride as the solvent, preferably 10,000 to 50,000, more preferably 11,000 to 40,000, and most preferably 12,000 to 35,000, and especially preferably 13,000 to 30,000. By setting the viscosity-average molecular weight to be above the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, and by setting the viscosity-average molecular weight to be below the upper limit of the above range, the decrease in fluidity of the polycarbonate resin composition of the present invention can be suppressed and improved, thereby enhancing moldability and facilitating molding. Furthermore, two or more polycarbonate resins with different viscosity-average molecular weights may be mixed and used. In this case, polycarbonate resins whose viscosity-average molecular weight is outside the preferred range described above may also be mixed.

[0026] The viscosity-average molecular weight [Mv] is calculated by using methylene chloride as the solvent, determining the intrinsic viscosity [η] (unit: dl / g) at 25°C using an Ubbelohde viscometer, and then using Schnell's viscosity formula, i.e., η = 1.23 × 10⁻⁶. -4 Mv 0.83 It refers to the value calculated from [the formula]. In addition, intrinsic viscosity [η] is the specific viscosity [η] at each solution concentration [C] (g / dl). sp This value was calculated by measuring [the value] and using the following formula.

number

[0027] Furthermore, in order to improve the appearance and fluidity of the molded product, the polycarbonate resin (A) may contain polycarbonate oligomers. The viscosity-average molecular weight [Mv] of these polycarbonate oligomers is usually 1500 or more, preferably 2000 or more, and usually 9500 or less, preferably 9000 or less. Moreover, it is preferable that the amount of polycarbonate oligomers contained be 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomers).

[0028] Furthermore, the polycarbonate resin (A) may be made not only from virgin raw materials but also from polycarbonate resin recycled from used products (so-called material-recycled polycarbonate resin), and it is also preferable to contain both virgin raw materials and recycled resin, or to consist solely of recycled polycarbonate resin. The proportion of recycled polycarbonate resin in the polycarbonate resin (A) is preferably 30% or more, and more preferably 40% or more, 50% or more, 60% or more, 70% or more, or 80% or more, and it is also preferable for the recycled polycarbonate resin to be 100%.

[0029] [LDS additive (B)] The polycarbonate resin composition of the present invention contains a laser direct structuring (LDS) additive (B). When the LDS additive is irradiated with a laser beam, metal atoms are activated and a metal layer is formed on the surface.

[0030] Examples of LDS additives (B) include heavy metal composite oxides such as copper-chromium oxide (CuCr2O4) and spinel; copper salts such as copper hydroxide phosphate, copper phosphate, copper sulfate, and copper thiocyanate; antimony-containing tin oxide such as antimony-doped tin oxide; and aluminum-doped zinc oxide. Of these, copper-chromium oxide or antimony-containing tin oxide are more preferred. Furthermore, copper-chromium oxide functions as a black pigment, making it suitable for obtaining black molded products. Antimony-containing tin oxide can be used as a white pigment, allowing it to be used for white molded products or in combination with other pigments to create desired color variations.

[0031] The particle size of the LDS additive (B) is preferably 0.01 to 50 μm, and more preferably 0.05 to 30 μm. This particle size tends to result in better uniformity of the plated surface when plating is applied.

[0032] The content of LDS additive (B) is 0.5 to 50 parts by mass per 100 parts by mass of polycarbonate resin (A), preferably 1 part by mass or more, more preferably 3 parts by mass or more, 5 parts by mass or more, 7 parts by mass or more, 8 parts by mass or more, 9 parts by mass or more, and especially preferably 10 parts by mass or more, and also preferably 45 parts by mass or less, more preferably 40 parts by mass or less, 35 parts by mass or less, 30 parts by mass or less, 25 parts by mass or less, and especially preferably 20 parts by mass or less.

[0033] A molded product made from a polycarbonate resin composition containing LDS additive (B) by injection molding or the like can be plated by irradiating its surface with a laser beam. For example, by irradiating it in a desired pattern such as an antenna circuit, an activated metal layer is formed only in the area where the circuit pattern is to be formed on the surface of the molded product, and a surface structure advantageous for subsequent metal plating is created. The molded product is then immersed in a plating solution and plated with copper, nickel, gold, etc. by electroplating (or electroplating) to form the circuit pattern.

[0034] [Organosulfonic acid metal salt (C)] The polycarbonate resin composition of the present invention contains an organic sulfonic acid metal salt (C). As the organic sulfonic acid metal salt (C), non-phosphorus and non-halogen organic sulfonic acid metal salt flame retardants that do not contain phosphorus and / or halogens in their molecules are preferred.

[0035] The metal in the metal salt is preferably an alkali metal or an alkaline earth metal, such as alkali metals like lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs); and alkaline earth metals like magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). Among these, sodium, potassium, and cesium are preferred, with sodium and potassium being particularly preferred.

[0036] Preferred examples of the organic sulfonic acid metal salt (C) include metal salts of aromatic sulfonic acids, metal salts of aromatic sulfonamides (or sulfonimides), and metal salts of polystyrene sulfonic acid.

[0037] Specific examples of these include alkali metal salts of aromatic sulfonic acids having at least one aromatic group in their molecule, such as potassium 3-(phenylsulfonyl)benzenesulfonate (i.e., potassium diphenylsulfon-3-sulfonate), dipotassium diphenylsulfon-3,3'-disulfonate, sodium benzenesulfonate, potassium benzenesulfonate, cesium benzenesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, cesium p-toluenesulfonate, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, cesium dodecylbenzenesulfonate, potassium styrenesulfonate, sodium polystyrenesulfonate, potassium polystyrenesulfonate, and cesium polystyrenesulfonate; Examples include alkaline earth metal salts of aromatic sulfonic acids having at least one aromatic group in their molecule, such as magnesium p-toluenesulfonate, calcium p-toluenesulfonate, strontium p-toluenesulfonate, barium p-toluenesulfonate, magnesium dodecylbenzenesulfonate, and calcium dodecylbenzenesulfonate.

[0038] Examples of metal salts of aromatic sulfonamides (or sulfonimides) include potassium salt of N-(p-tolylsulfonyl)-p-toluenesulfoimide, potassium salt of N-(N'-benzylaminocarbonyl)sulfanilimide, and potassium salt of N-(phenylcarboxyl)-sulfanilimide.

[0039] Among the above, preferred organic sulfonic acid metal salts (C) are metal salts of p-toluenesulfonic acid, metal salts of phenylsulfonylbenzenesulfonic acid, and metal salts of polystyrenesulfonic acid, and among these, alkali metal salts, and especially sodium salts or potassium salts are preferred. The organic sulfonic acid metal salt (C) may be used alone, or two or more may be used in any combination and ratio.

[0040] The content of the organic sulfonic acid metal salt (C) is 0.01 to 1 part by mass per 100 parts by mass of polycarbonate resin (A), preferably 0.02 parts by mass or more, more preferably 0.03 parts by mass or more, 0.05 parts by mass or more, 0.08 parts by mass or more, or 0.1 parts by mass or more, and more preferably less than 1.0 part by mass, more preferably 0.7 parts by mass or less, 0.5 parts by mass or less, 0.4 parts by mass or less, 0.3 parts by mass or less, and especially preferably 0.2 parts by mass or less.

[0041] Furthermore, it is preferable that the polycarbonate resin composition of the present invention substantially does not contain phosphorus-based flame retardants and / or halogen-based flame retardants. Here, "substantially contained" means that the amount of phosphorus-based flame retardants and / or halogen-based flame retardants, individually or in total, is preferably less than 0.05 parts by mass, more preferably less than 0.03 parts by mass, more preferably less than 0.01 parts by mass, less than 0.005 parts by mass, less than 0.001 parts by mass, and particularly preferably less than 0.0005 parts by mass, per 100 parts by mass of polycarbonate resin (A).

[0042] [Flame retardant additive (D) with a 10% weight loss temperature of 350-600°C] The polycarbonate resin composition of the present invention contains a flame retardant additive (D) with a 10% weight loss temperature of 350 to 600°C. The flame retardant additive is used in combination with an organic sulfonic acid metal salt (C), which is used to make the polycarbonate resin flame retardant, to produce a synergistic effect. The flame retardant additive (D) is selected to have a 10% weight loss temperature of 350-600°C, which further enhances the flame retardancy of the organic sulfonic acid metal salt (C) by releasing interlayer water and structural water under high heat such as flames, and by dehydrating through the cooling and diluting effect, while also achieving heat resistance under high-temperature conditions during extrusion and molding.

[0043] The 10% weight loss temperature of flame retardant additive (D) refers to the temperature at which the flame retardant additive decreases by 10% from its initial weight when heated from room temperature to 600°C at a heating rate of 20°C / min under a nitrogen atmosphere (200 mL / min) using a thermogravimetric analyzer. The 10% weight loss temperature of the flame retardant additive (D) is preferably 380°C or higher, more preferably 400°C or higher, even more preferably 430°C or higher, and particularly preferably 450°C or higher. By using a flame retardant additive with such a weight loss temperature, the flame retardant performance of the resin molded product can be improved without decomposition during extrusion or molding. The 10% weight loss temperature of the flame retardant additive (D) is preferably 590°C or lower, more preferably 580°C or lower, even more preferably 570°C or lower, and particularly preferably 560°C or lower. By using a flame retardant additive with such a weight loss temperature, structural water is released before the polycarbonate completely decomposes during combustion, thereby exhibiting a flame retardant effect.

[0044] As the flame retardant additive (D), minerals containing aluminum or magnesium are preferred, such as boehmite, halloysite, sepiolite, hydromagnesite, kaolin, montmorillonite, pyrophyllite, attapulgite, and vermiculite, with boehmite, halloysite, and sepiolite being particularly preferred.

[0045] Boehmite is an alumina monohydrate represented by the chemical formula Al2O3·1H2O, and is preferred because it has particularly high heat resistance and chemical stability. Halloysite is a type of clay mineral classified as a phyllosilicate mineral, and its typical chemical formula is Al2Si2O5(OH)4. Halloysite has a layered structure with weak bonds between unit layers and water molecules incorporated between layers, and it has a roll-like, tubular form. The mechanism by which halloysite exhibits flame retardancy as a flame retardant is that when exposed to high heat such as flames, interlayer water and structural water are released, and due to the cooling and diluting effect, as well as the aluminol surface (-Al-OH) inside the halloysite + This is thought to be because the acid sites act as acid sites, suppressing the formation of low molecular weight components through the cleavage reaction of polycarbonate resin, thereby facilitating the formation of crosslinked structures through isomerization reactions and promoting good char formation. Sepiolite is a type of clay mineral classified as a phyllosilicate mineral, and its chemical formula is Mg8Si 12 O30 represented by (OH)4(OH2)4·8H2O. Sepiolite is a fibrous mineral composed of discontinuous layers, is porous, has a large specific surface area, and features high adsorption properties for water and other substances. The mechanism by which sepiolite exhibits flame retardancy is considered to be that when exposed to high heat such as flame, interlayer water and structural water are released to produce a cooling and dilution effect, and the fiber structure of sepiolite reinforces the formed char.

[0046] Hydromagnesite is a hydrous basic carbonate mineral of magnesium, and is a mineral typically represented by Mg5(CO3)4(OH)2·4H2O. Kaolin, also called kaolinite, is a mineral typically represented by Al2Si2O5(OH)4. Montmorillonite is a type of silicate mineral, and is typically (Na,Ca) 0.33 (Al,Mg)2Si4O 10 (OH)2·nH2O. Pyrophyllite is a type of layered silicate mineral, and is typically Al2Si4O 10 (OH)2. Attapulgite is a natural silicate mineral mainly composed of hydrous magnesium and aluminum silicate, and is typically [Mg(Al (0.5-1) Fe (0-0.5) )]Si4O 10 (OH)·4H2O. Vermiculite is a type of silicate mineral formed by weathering of biotite, phlogopite and the like, and its chemical composition is Mg 1-x (Mg,Fe,Fe 3+ ,Al)3(Si,Al)4O 10 (OH)2·4H2O.

[0047] The aforementioned flame retardant auxiliary (D) having a 10% weight loss temperature of 350 to 600°C releases interlayer water and / or structural water, and through its cooling and dilution effect, as well as by promoting the promotion of robust char formation by the organic sulfonic acid metal salt (C), makes flame retardancy extremely favorable, and can provide an environmentally friendly material that complies with regulations such as those on PFAS. Furthermore, the aforementioned flame retardant additive (D), which has a 10% weight loss temperature of 350-600°C, remains stable and does not decompose at the molding temperature of the polycarbonate resin composition, and can decompose during combustion to release interlayer water and / or structural water.

[0048] The flame retardant additive (D) is preferably surface-treated. Specific examples of surface treatment agents include silicone compounds such as organopolysiloxanes, coupling agents such as silane-based coupling agents, titanate-based coupling agents, and aluminum-based coupling agents, alcohols such as trimethylolethane, trimethylolpropane, and pentaerythritol, alkanolamines such as triethylamine, higher fatty acids such as stearic acid, fatty acid metal salts such as calcium stearate and magnesium stearate, polyacrylates such as sodium polyacrylate and ammonium polyacrylate, hydrocarbon lubricants such as polyethylene wax and liquid paraffin, basic amino acids such as lysine and arginine, polyglycerin, and their derivatives. Among these, silicone compounds such as organopolysiloxanes are preferred because surface treatment with silicone compounds improves heat resistance and also improves dispersibility in polycarbonate resin, resulting in a significant improvement in flame retardancy.

[0049] The amount of flame retardant additive (D) is 0.1 to 5.5 parts by mass per 100 parts by mass of polycarbonate resin (A), and good flame retardancy is achieved with such a small amount. Below the lower limit, flame retardancy is insufficient, and if the amount exceeds the upper limit, the decomposition of the polycarbonate progresses, making it difficult to achieve good flame retardancy. The content of the flame retardant additive (D) is preferably 0.11 parts by mass or more, more preferably 0.12 parts by mass or more, and preferably 5.0 parts by mass or less, more preferably 4.0 parts by mass or less, 3.0 parts by mass or less, 2.5 parts by mass or less, 2.0 parts by mass or less, 1.8 parts by mass or less, 1.5 parts by mass or less, 1.3 parts by mass or less, 1.1 parts by mass or less, 1.0 part by mass or less, less than 1.0 part by mass, 0.9 parts by mass or less, 0.8 parts by mass or less, and especially less than 0.8 parts by mass. By keeping the content below the above upper limit, the decomposition of the polycarbonate resin is suppressed, and the load deflection temperature at a thickness of 4.0 mm tends to improve. When the flame retardant additive (D) is boehmite, the content is preferably 0.2 parts by mass or more, more preferably 0.4 parts by mass or more, and more preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and particularly preferably 1.0 part by mass or less, per 100 parts by mass of polycarbonate resin (A). When the flame retardant additive (D) is halloysite, its content is preferably 0.11 parts by mass or more, more preferably 0.12 parts by mass or more, and preferably 1.0 part by mass or less, more preferably 0.5 parts by mass or less, and particularly preferably 0.2 parts by mass or less, per 100 parts by mass of polycarbonate resin (A). When the flame retardant additive (D) is sepiolite, its content is preferably 0.11 parts by mass or more, more preferably 0.12 parts by mass or more, and preferably 3.0 parts by mass or less, more preferably 1.5 parts by mass or less, and particularly preferably 1.0 part by mass or less, per 100 parts by mass of polycarbonate resin (A). By using the flame retardant additive (D) described above, it is possible to achieve a good balance between flame retardancy and LDS performance by using it in combination with a small amount of organic sulfonic acid metal salt.

[0050] [Filler (E)] The polycarbonate resin composition of the present invention preferably further contains a filler (E), and the content of the filler is preferably 1 to 90 parts by mass per 100 parts by mass of polycarbonate resin (A). By including it in this way, the anti-sagging ability of the filler (E) can be balanced well, and an even higher level of flame retardancy can be achieved. The content of the filler (E) is more preferably 3 parts by mass or more, more preferably 5 parts by mass or more, 7 parts by mass or more, or 10 parts by mass or more, per 100 parts by mass of polycarbonate resin (A), and more preferably 80 parts by mass or less, more preferably 75 parts by mass or less, or 70 parts by mass or less. The filler (E) may contain only one type or two or more types.

[0051] As the filler (E), an inorganic filler is preferred, and the inorganic filler may be a needle-shaped inorganic filler, a fibrous inorganic filler, or a plate-shaped inorganic filler, but a glass-based filler is preferred. Furthermore, the aforementioned flame retardant additive (D) is excluded as a filler material (E).

[0052] The filler (E) is preferably a glass-based filler, with glass fibers, glass flakes, glass beads, and glass balloons being preferred examples, and glass fibers and glass flakes being particularly preferred. The raw material glass composition is preferably alkali-free, and examples include E glass, C glass, S glass, R glass, etc., but E glass is preferably used.

[0053] In addition to the common circular cross-sectional shape, various irregular cross-sectional shapes may be used for the glass fibers. The glass fibers preferably have a number-average fiber length (cut length) of 0.5 to 10 mm, and more preferably 1.0 to 5.0 mm. The number-average fiber diameter of the glass fibers is preferably 4.0 μm or more, more preferably 4.5 μm or more, and even more preferably 5.0 μm or more, with an upper limit of preferably 25 μm or less, and more preferably 20 μm or less. Glass fibers having a flattened cross-section are also preferred, with a flattening ratio of 1.5 to 8 being more preferred, and a flattening ratio of 2 to 6 being even more preferred. The average major axis (width) of the fiber cross-section of the flattened cross-section glass fibers is preferably 10 to 50 μm, more preferably 12 to 40 μm, even more preferably 15 to 35 μm, and particularly preferably 18 to 30 μm. The number-average fiber length of the flattened cross-section glass fibers is preferably 0.5 to 20 mm, more preferably 1 to 15 mm, and even more preferably 2 to 10 mm. Furthermore, the ratio of the average fiber length to the average fiber diameter (aspect ratio) of the flattened cross-section glass fibers is preferably 2 to 120, more preferably 2.5 to 70, and even more preferably 3 to 50. Examples of such flattened cross-section glass fibers include the CSG series manufactured by Nitto Boseki Co., Ltd., and particularly "CSG 3PA-830". Glass flakes are typically scaly flakes with a thickness of 1 to 20 μm and a side length of 0.05 to 1.0 mm. Alternatively, extremely thin glass flakes with an average thickness of 0.3 to 1 μm may be used. Examples of such extremely thin glass flakes include "Fine Flake" and "DURAFLAKE" from Nippon Sheet Glass Co., Ltd., with "MEG160 FY-M01" being a particularly noteworthy example. By using both the flattened cross-section glass fibers and ultra-thin glass flakes described above, a polycarbonate resin composition with superior dimensional stability and low anisotropy can be obtained.

[0054] The glass-based filler is preferably surface-treated with a surface treatment agent such as a silane coupling agent, such as γ-methacrylateoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, or γ-aminopropyltriethoxysilane. The amount of surface treatment agent applied is preferably 0.01 to 1% by mass of the glass-based filler. Furthermore, it is preferable to use materials that have been surface-treated with lubricants such as fatty acid amide compounds and silicone oils, or antistatic agents such as quaternary ammonium salts. It is also preferable to use materials that have been surface-treated with resins that have film-forming ability, such as epoxy resins or urethane resins, or with a mixture of resins that have film-forming ability and heat stabilizers or flame retardants. In particular, glass-based fillers are preferably those that have been surface-treated with a surface treatment agent such as a silane coupling agent, and then further treated with a resin (also called a binding agent) that has film-forming ability, such as epoxy resin or urethane resin.

[0055] [Release agent] The resin composition of the present invention preferably contains a mold release agent. Examples of release agents include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number average molecular weight of 200 to 15,000, and polysiloxane-based silicone oils.

[0056] Examples of aliphatic carboxylic acids include saturated or unsaturated aliphatic monovalent, divalent, or trivalent carboxylic acids. Here, aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and more preferably aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetrariacontanoic acid, montanic acid, adipic acid, and azelaic acid.

[0057] As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, for example, the same aliphatic carboxylic acid as described above can be used. On the other hand, as the alcohol, for example, saturated or unsaturated monohydric or polyhydric alcohols can be used. These alcohols may have substituents such as fluorine atoms or aryl groups. Among these, monohydric or polyhydric saturated alcohols having 30 or fewer carbon atoms are preferred, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or fewer carbon atoms are more preferred. Here, "aliphatic" is used as a term that also includes alicyclic compounds.

[0058] Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, and dipentaerythritol.

[0059] Furthermore, the above-mentioned esters may contain aliphatic carboxylic acids and / or alcohols as impurities. Also, the above-mentioned esters may be pure substances or mixtures of multiple compounds. Moreover, the aliphatic carboxylic acids and alcohols that combine to form a single ester may be used individually, or two or more may be used in any combination and ratio.

[0060] Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture mainly composed of myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

[0061] Aliphatic hydrocarbons with a number-average molecular weight of 200 to 15,000 include, for example, liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. Note that alicyclic hydrocarbons are also included in the definition of aliphatic hydrocarbons. Furthermore, these hydrocarbons may be partially oxidized. Among these, paraffin wax, polyethylene wax, or partially oxided polyethylene wax are preferred, and paraffin wax and polyethylene wax are more preferred. Furthermore, the number-average molecular weight of the aliphatic hydrocarbon is preferably 5000 or less. Furthermore, while aliphatic hydrocarbons may be single substances, mixtures of substances with varying constituent components and molecular weights can also be used as long as the main component falls within the above-mentioned range.

[0062] Examples of polysiloxane-based silicone oils include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

[0063] Furthermore, the above-mentioned release agent may contain one type, or two or more types in any combination and ratio.

[0064] The release agent content is preferably 0.1 to 2 parts by mass, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less, per 100 parts by mass of polycarbonate resin (A). If the release agent content is below the lower limit of the above range, the release effect is likely to be insufficient, and if it exceeds the upper limit of the above range, a decrease in hydrolysis resistance and mold contamination during injection molding may occur.

[0065] [Stabilizer] The polycarbonate resin composition of the present invention preferably contains a stabilizer, and phosphorus-based stabilizers or phenol-based stabilizers are preferred.

[0066] Any known phosphorus-based stabilizer can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphate; acidic pyrophosphate metal salts such as sodium acidic pyrophosphate, potassium acidic pyrophosphate, and calcium acidic pyrophosphate; phosphates of Group 1 or Group 2 metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; and organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds, with organic phosphate compounds and organic phosphite compounds being particularly preferred.

[0067] Examples of organic phosphate compounds include octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, octadecyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, and bisphenoxyethyl acid phosphate. Examples include A-acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, bisnonylphenyl acid phosphate, etc., or their metal salts. Examples of such organic phosphate compounds include "ADEKA Stab AX-71" manufactured by ADEKA Corporation and "JP-518Zn" manufactured by Johoku Chemical Industry Co., Ltd.

[0068] Examples of organic phosphite compounds include triphenyl phosphite, tris(mononylphenyl) phosphite, tris(mononyl / dinonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, monooctyldiphenyl phosphite, dioctylmonophenyl phosphite, monodecyldiphenyl phosphite, didecylmonophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite, distearylpentaerythritol diphosphite, and bis(2,4-dicumylphenyl)pentaerythritol phosphite. Examples of such organic phosphite compounds include ADEKA's "ADEKA Stab 1178," "ADEKA Stab 2112," "ADEKA Stab HP-10," "ADEKA Stab PEP-36," and "ADEKA Stab PEP-8," Johoku Chemical Industry's "JP-351," "JP-360," and "JP-3CP," and BASF's "Irgaphos 168." Furthermore, the product may contain one type of phosphorus-based stabilizer, or two or more types in any combination and ratio.

[0069] The phosphorus-based stabilizer content is typically 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and more preferably 0.03 parts by mass or more, per 100 parts by mass of polycarbonate resin (A), and typically 1 part by mass or less, preferably 0.7 parts by mass or less, and more preferably 0.5 parts by mass or less. If the phosphorus-based stabilizer content is below the lower limit of the above range, the thermal stabilization effect may be insufficient, and if the phosphorus-based stabilizer content exceeds the upper limit of the above range, the effect may plateau and become uneconomical.

[0070] Examples of phenolic stabilizers include hindered phenolic antioxidants. Specific examples include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3',3”,5,5',5”-hexa-tert-butyl-a,a',a”-(mesitylene-2,4,6- Examples include triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, and 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate.

[0071] Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred. Specific examples of such phenolic antioxidants include BASF's "Irganox 1010" and "Irganox 1076," and ADEKA's "ADEKA Stab AO-50" and "ADEKA Stab AO-60." Furthermore, the product may contain one type of phenolic stabilizer, or two or more types in any combination and ratio.

[0072] The content of the phenolic stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 1 part by mass or less, preferably 0.5 parts by mass or less, per 100 parts by mass of polycarbonate resin (A). By setting the content of the phenolic stabilizer to be above the lower limit of the above range, the effect of the phenolic stabilizer can be sufficiently obtained, and by setting it to be below the upper limit of the above range, the effect does not plateau, making it economical. It is preferable to include both phosphorus-based and phenol-based stabilizers, as this further improves stability.

[0073] [Additives, etc.] The polycarbonate resin composition of the present invention may contain other additives besides those mentioned above, such as ultraviolet absorbers, fluorescent whitening agents, pigments, dyes, plasticizers, and compatibilizers. These additives may be present in one or more types.

[0074] Furthermore, other resins besides polycarbonate resin (A) may be included. Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate; styrene-based resins such as polystyrene resin, high-impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-butadiene-styrene copolymer (ABS resin); polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; polyurethane resin; polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; and polymethacrylate resin. When other resins are included besides polycarbonate resin (A), the content is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, per 100 parts by mass of polycarbonate resin (A), and among these, 20 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, and especially 1 part by mass or less.

[0075] [Polycarbonate resin composition] The polycarbonate resin composition of the present invention has high flame retardancy and can achieve V-0 in UL-94 testing with a UL test specimen that is 1.5 mm thick.

[0076] The polycarbonate resin composition of the present invention is molded into a molded article. The manufacturing method for the molded product can be any molding method commonly used for polycarbonate resin compositions. 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 insulated molds, molding using rapidly heated molds, foam molding (including supercritical fluids), 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. Among these, injection molding methods such as injection molding, ultra-high-speed injection molding, and injection compression molding are preferred.

[0077] [Molded products] Examples of molded products include parts for electrical and electronic equipment, office automation equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building materials, various containers, leisure goods and miscellaneous items, and lighting equipment. In particular, it is suitable for use in parts for electrical and electronic equipment, office automation equipment, information terminal equipment, home appliances, and lighting equipment. For example, it is suitable for use in components for secondary battery devices used indoors or outdoors, battery packs, storage batteries for electric bicycles, and components for enclosures used outdoors.

[0078] Plating can be formed on the surface of a resin molded product by laser direct structuring. The shape of the resin molded product can be anything; it can be flat, partially or entirely curved, or have a complex three-dimensional shape. The resin molded product is irradiated with a laser. The laser is not particularly limited and can be appropriately selected from known lasers such as YAG lasers, FAYb lasers, carbon dioxide lasers, and excimer lasers, with YAG lasers and FAYb lasers being preferred. The wavelength of the laser is also not particularly specified. The preferred wavelength range is 200 nm to 1200 nm. Particularly preferred is 800 nm to 1200 nm. When the laser is irradiated, an activated metal layer is formed only in the irradiated area on the surface of the molded product, and surface roughening advantageous for subsequent metal plating is achieved. The molded product is immersed in a plating solution with or without a cleaning step, and plated with copper, nickel, gold, silver, palladium, preferably copper, by electroplating (or electroplating), so that a metal layer is formed only in the laser-irradiated area.

[0079] Furthermore, by applying laser direct structuring to the molded product of the present invention, it is possible to form circuits with a width of, for example, 1 mm or less, and even 150 μm or less (the lower limit is not specifically defined, but for example, 30 μm or more). Therefore, it is extremely effective for various mobile devices such as smartphones and tablet terminals, hearing aids, medical or dental treatment and surgical devices, various sensors, automotive devices such as steering wheel switches, or their components. [Examples]

[0080] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples. The components used in the examples and comparative examples are shown in Table 1 below.

[0081] [Table 1]

[0082] The 10% weight loss temperature was measured using a Hitachi High-Tech Science Corporation calorimeter "TG / DTA7200" under a nitrogen atmosphere. A 5 mg sample was heated from 40°C to 600°C at a heating rate of 20°C / min, and the temperature at which the weight loss reached 10% of the room temperature weight was measured. An aluminum pan was used as the sample pan.

[0083] (Examples 1-11, Comparative Examples 1-8) <Manufacturing of resin composition pellets> Of the components listed above, all except filler (E) were blended in the proportions (parts by mass) shown in Tables 2 and 3 below. After mixing in a tumbler for 20 minutes, the mixture was supplied to a twin-screw extruder "TEX30α" manufactured by Japan Steel Works, Ltd., which was equipped with one vent. Filler (E) was then added in the proportions (parts by mass) shown in Tables 2 and 3 below via a side feeder from the middle of the barrel. The mixture was kneaded under the conditions of a screw rotation speed of 200 rpm, a discharge rate of 25 kg / hr, and a barrel temperature of 280°C. The molten resin extruded in strand form was rapidly cooled in a water bath and pelletized using a pelletizer to obtain pellets of the polycarbonate resin composition.

[0084] <Measurement of fluorine content (unit: mass ppm)> The fluorine content in the resin composition was quantified by combustion ion chromatography. Specifically, the polycarbonate resin composition pellets obtained above were heated in an argon atmosphere at 270°C for 10 minutes using an automated sample combustion device, the "AQF-100" manufactured by Mitsubishi Chemical Analytec Co., Ltd., and the amount of fluorine ions generated was quantified using the "ICS-90" manufactured by Nippon Dionex Co., Ltd. To calculate the content, a calibration curve created from separately prepared standard substances was used. Substances that were difficult to measure by combustion ion chromatography because they were below the detection limit of 5 ppm by mass are marked as "ND" (not detected) in Table 2-3. Resin compositions that do not contain PFAS compounds are naturally marked as ND. The fluorine content is preferably less than 500 ppm by mass, more preferably 400 ppm by mass or less, 250 ppm by mass or less, 100 ppm by mass or less, and particularly preferably below the detection limit of 5 ppm by mass (ND).

[0085] <Flame retardancy rating: UL-94 (1.5mm thick)> The resin composition pellets obtained above were dried at 120°C for 4 hours, and then injection molded using a Sumitomo Heavy Industries SE100DU injection molding machine under the conditions of cylinder temperature 300°C, mold temperature 110°C, and molding cycle of 40 seconds to produce UL-94 test pieces with a length of 125 mm, a width of 13 mm, and a thickness of 1.5 mm. The obtained UL test specimens were tested in accordance with the UL-94 standard set by Underwriters Laboratories (UL) in the United States. Flammability results were classified as V-0, V-1, V-2, and HB from best to worst, with non-compliant specimens classified as NG.

[0086] [Evaluation of LDS properties] The resin composition pellets obtained above were dried at 120°C for 4 hours, and then 90mm x 60mm x 2mm thick flat test pieces were injection molded using an injection molding machine (Sumitomo Heavy Industries, Ltd. "SE100DU") under the conditions of a cylinder temperature of 280°C and a mold temperature of 100°C. The obtained flat test specimen was irradiated over a 55 mm x 40 mm area using a SUNX LP-Z SERIES laser irradiation device (FAYB laser with a wavelength of 1060 nm and a maximum output of 13 W) at output levels of 100, 80, 60, 40, and 20%, pulse periods of 50 microseconds, and speeds of 4 m / s and 2 m / s. The subsequent plating process was carried out in a MACDERMID COPPER100XB STRIKE electroless plating bath at 65°C (set temperature 68°C) for 20 minutes. The plating performance (LDS performance) was evaluated by visually measuring the thickness of the copper plated after 20 minutes, according to the following criteria. A: Excellent appearance (the copper color is dark and the plating is thick) B: The plating is present but slightly thin (though still usable). C: The plating doesn't adhere at all.

[0087] <Measurement of flexural modulus> The resin composition pellets obtained above were dried at 120°C for 4 hours. Then, injection molding was performed using a Nissei Plastic Industrial Co., Ltd. injection molding machine (NEX80III model) under the following conditions: cylinder setting temperature 280°C, mold temperature 80°C, injection time 2 seconds, and molding cycle 50 seconds, to injection mold an ISO multipurpose test specimen (4 mm thick). Using the obtained ISO multipurpose test specimen (4mm thick), the flexural modulus (unit: GPa) was measured in accordance with ISO 178.

[0088] [Measurement of heat resistance (temperature of deflection under load, DTUL)] Using the ISO multipurpose test specimen (4mmt) obtained above, the temperature of deflection under load (DTUL, unit: °C) was measured under a load of 1.80 MPa according to the ISO 75A method. A temperature of deflection of 135°C or higher is preferred, more preferably 136°C or higher, and among those, 137°C or higher, 140°C or higher, 142°C or higher, 143°C or higher, and especially 145°C or higher is preferred. The evaluation results are shown in Tables 2 and 3 below.

[0089] [Table 2]

[0090] [Table 3] [Industrial applicability]

[0091] The polycarbonate resin composition of the present invention is a polycarbonate resin material that meets various regulations such as PFAS, is environmentally friendly, possesses high flame retardancy, and has excellent LDS performance, making it suitable for use in various molded products.

Claims

1. A polycarbonate resin composition characterized by containing, per 100 parts by mass of polycarbonate resin (A), 0.5 to 50 parts by mass of laser direct structuring additive (B), 0.01 to 1 part by mass of an organic sulfonic acid metal salt (C) in which the metal of the metal salt is an alkali metal or alkaline earth metal, and 0.1 to 5.5 parts by mass of a mineral (D) selected from one or more of boehmite, halloysite, sepiolite, hydromagnesite, kaolin, montmorillonite, pyrophyllite, attapulgite, and vermiculite.

2. The polycarbonate resin composition according to Claim 1, wherein the content of the mineral (D) is 0.1 to 1.0 parts by mass per 100 parts by mass of the polycarbonate resin (A).

3. The polycarbonate resin composition according to claim 1 or 2, wherein the organic sulfonic acid metal salt (C) is an organic sulfonic acid metal salt that does not contain phosphorus or halogen.

4. The polycarbonate resin composition according to claim 3, wherein the organic sulfonic acid metal salt (C) is an aromatic sulfonic acid metal salt.

5. Furthermore, the polycarbonate resin composition according to claim 1 or 2, wherein the filler (E) is contained in an amount of 1 to 90 parts by mass per 100 parts by mass of polycarbonate resin (A).

6. The polycarbonate resin composition according to claim 5, wherein the filler (E) is a glass-based filler.

7. The polycarbonate resin composition according to claim 6, wherein the filler (E) is glass fiber.

8. The polycarbonate resin composition according to claim 1 or 2, wherein the fluorine content measured by combustion ion chromatography is less than 500 ppm by mass.

9. The polycarbonate resin composition according to claim 1 or 2, wherein the UL-94 layer with a thickness of 1.5 mm is V-0.

10. Pellets of the polycarbonate resin composition according to claim 1 or 2.

11. A molded article of the polycarbonate resin composition according to claim 1 or 2.

12. A molded article of pellets according to claim 10.

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