Thermoplastic resin composition and molded product thereof

Abstract

This thermoplastic resin composition comprises a thermoplastic resin (A), flat-cross-section glass fibers (B), and glass flakes (C). The thermoplastic resin (A) contains more than 10 mass% but not more than 80 mass% of a polycarbonate resin (A1) and not less than 20 mass% but less than 90 mass% of a thermoplastic polyester resin (A2). The sum of the contents of the flat-cross-section glass fibers (B) and the glass flakes (C) is 10 to 50 parts by mass inclusive with respect to 100 parts by mass of the sum of the contents of the thermoplastic resin (A), the flat-cross-section glass fibers (B), and the glass flakes (C). The average thickness of the glass flakes (C) is less than 0.45 μm.

Description

Thermoplastic resin composition and molded article thereof

[0001] The present invention relates to a thermoplastic resin composition and a molded article thereof.

[0002] BACKGROUND ART Thermoplastic resins, particularly polycarbonate resins, have been used in a wide range of fields, such as electrical and electronic equipment parts, office automation equipment parts, machine parts, and vehicle parts, because they are excellent in transparency, impact resistance, heat resistance, and the like, and the molded articles obtained from them also have excellent dimensional stability.

[0003] Furthermore, resin compositions containing polyester resins such as polyethylene terephthalate (PET) are widely used to improve the chemical resistance, solvent resistance, and flowability of polycarbonate resins. Furthermore, glass fillers are sometimes added to improve rigidity, heat resistance, and dimensional stability (low shrinkage and low linear expansion) (see, for example, Patent Document 1).

[0004] Japanese Patent Application Laid-Open No. 2023-112342

[0005] As described above, resin compositions containing a polycarbonate resin and a polyester resin have excellent fluidity and chemical resistance in addition to the excellent properties of polycarbonate resin. Adding a glass-based filler to such a resin composition can increase mechanical strength and rigidity. However, resin compositions containing a glass-based filler have the disadvantage that they do not achieve isotropic dimensional stability due to anisotropic molding shrinkage caused by the orientation of the glass-based filler. Meanwhile, when producing large molded articles such as automotive exterior components by injection molding, it is highly desirable to achieve as isotropic dimensional stability as possible, and suppressing dimensional anisotropy during molding is a challenge. Furthermore, to ensure the rigidity required for automotive exterior components, an improvement in elastic modulus is also strongly required, and moldability is also required to achieve a good molded appearance.

[0006] The present invention solves these problems and aims to provide a thermoplastic resin composition having sufficient rigidity and yield strength and reduced anisotropy in the linear expansion coefficient and shrinkage rate, and a molded article thereof.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by using a thermoplastic resin composition containing specific amounts of a specific thermoplastic resin, flat cross-section glass fibers, and glass flakes, and have completed the present invention. That is, the present invention includes at least the following embodiments. The present invention also includes embodiments in which the features of the following embodiments are combined in any desired manner.

[0008] [1] A thermoplastic resin composition containing a thermoplastic resin (A), a flat cross section glass fiber (B), and glass flakes (C), wherein the thermoplastic resin (A) contains more than 10 mass% and 80 mass% or less of a polycarbonate resin (A1) and 20 mass% or more and less than 90 mass% of a thermoplastic polyester resin (A2), wherein the total content of the flat cross section glass fiber (B) and the glass flakes (C) is 10 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the total content of the thermoplastic resin (A), the flat cross section glass fiber (B), and the glass flakes (C), and wherein the average thickness of the glass flakes (C) is less than 0.45 μm.

[0009] [2] The thermoplastic resin composition according to [1], wherein the thermoplastic resin (A) contains 50% by mass or more and 80% by mass or less of a polycarbonate resin (A1) and 20% by mass or more and 50% by mass or less of a thermoplastic polyester resin (A2).

[0010] [3] The thermoplastic resin composition according to [1] or [2], wherein the polyester resin (A2) is a crystalline thermoplastic polyester resin.

[0011] [4] The thermoplastic resin composition according to any one of [1] to [3], wherein the glass transition temperature of the polyester resin (A2) is 80°C or higher.

[0012] [5] The thermoplastic resin composition according to any one of [1] to [4], wherein the thermoplastic polyester resin (A2) is one or more selected from the group consisting of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.

[0013] [6] The thermoplastic resin composition according to [5], wherein the thermoplastic polyester resin (A2) contains at least polyethylene naphthalate.

[0014] [7] The thermoplastic resin composition according to [5], wherein the thermoplastic polyester resin (A2) contains at least polyethylene terephthalate, and the intrinsic viscosity of the polyethylene terephthalate is 0.50 dL / g or more and 2.0 dL / g or less.

[0015] [8] The thermoplastic resin composition according to any one of [1] to [7], wherein the viscosity average molecular weight of the polycarbonate resin (A1) is 16,000 to 50,000.

[0016] [9] The thermoplastic resin composition according to any one of [1] to [8], wherein the content mass ratio of the flat cross section glass fiber (B) to the glass flake (C) (flat cross section glass fiber (B) / glass flake (C)) is in the range of 0.2 to 4.0.

[0017]

[10] The thermoplastic resin composition according to any one of [1] to [9], wherein the average minor axis of the fiber cross section of the flat cross section glass fiber (B) is 3 to 20 μm.

[0018]

[11] The thermoplastic resin composition according to any one of [1] to

[10] , wherein the average value of the flatness (long axis / short axis of the fiber cross section) of the flat cross section glass fiber (B) is greater than 1.5 and less than or equal to 8.

[0019]

[12] The linear expansion coefficient in the MD and TD directions measured according to ISO 11359-2 is 2.1 × 10 －５ / K ~ 3.2 × 10 －５ / K, and the ratio of the linear expansion coefficients of MD and TD is in the range of 0.8 to 1.1.

[0020]

[13] A thermoplastic resin composition containing a thermoplastic resin (A), a flat cross section glass fiber (B), and glass flakes (C), wherein the thermoplastic resin (A) contains 50% by mass or more and 80% by mass or less of a polycarbonate resin (A1) and 20% by mass or more and 50% by mass or less of a thermoplastic polyester resin (A2), the thermoplastic polyester resin (A2) is a crystalline polyester resin, the total content of the flat cross section glass fiber (B) and the glass flakes (C) is 10 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the total content of the thermoplastic resin (A), the flat cross section glass fiber (B), and the glass flakes (C), and the thermoplastic resin composition wherein the average thickness of the glass flakes (C) is 0.65 μm or less.

[0021]

[14] A thermoplastic resin composition containing a thermoplastic resin (A), a flat cross section glass fiber (B), and glass flakes (C), wherein the thermoplastic resin (A) contains 50% by mass or more and 80% by mass or less of a polycarbonate resin (A1) and 20% by mass or more and 50% by mass or less of a thermoplastic polyester resin (A2), wherein the thermoplastic polyester resin (A2) has a glass transition temperature of 80°C or more, wherein the total content of the flat cross section glass fiber (B) and the glass flakes (C) is 10 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the total content of the thermoplastic resin (A), the flat cross section glass fiber (B), and the glass flakes (C), and wherein the average thickness of the glass flakes (C) is 0.65 μm or less.

[0022]

[15] The thermoplastic resin composition according to

[14] , wherein the polyester resin (A2) has a glass transition temperature of 90°C or higher.

[0023]

[16] A molded article obtained from the thermoplastic resin composition according to any one of [1] to

[15] .

[0024]

[17] The molded article according to

[16] , which is a molded article selected from the group consisting of housing parts and lens barrels thereof for cameras, telescopes, microscopes, projection exposure devices, or optical measuring devices; housing parts and mechanical parts thereof for smartphone cameras, in-vehicle cameras, drive recorders, surveillance cameras, or small cameras mounted on drones; housings and mechanical parts thereof for car collision prevention sensors, rear monitor sensors, vehicle speed sensors, temperature sensors, or security sensors; frame members and outer panel members thereof for automobiles, motorcycles, bicycles, or wheelchairs; panel members and mechanical parts thereof for home televisions, personal computer displays, in-vehicle monitors, smartphones, or head-mounted displays; and housings and mechanical parts thereof for barcode readers or scanners.

[0025] According to the present invention, it is possible to provide a thermoplastic resin composition having sufficient rigidity and yield strength, an excellent molded appearance, and reduced anisotropy of the linear expansion coefficient and shrinkage rate, and a molded article thereof.

[0026] Hereinafter, an embodiment of the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Note that the following present embodiment is an example for explaining the present invention, and the present invention is not limited to this embodiment. In this specification, the term "to" is used to mean that the numerical values ​​before and after it are included as lower and upper limits. In this specification, various physical property values ​​and characteristic values ​​are those at 23°C unless otherwise specified. In this specification, weight average molecular weights and number average molecular weights are polystyrene-equivalent values ​​measured by GPC (gel permeation chromatography) unless otherwise specified. In this specification, ppm means mass ppm.

[0027] [Summary] A thermoplastic resin composition according to a first embodiment of the present invention is a thermoplastic resin composition containing a thermoplastic resin (A), a flat cross section glass fiber (B), and glass flakes (C), wherein the thermoplastic resin (A) contains more than 10% by mass and 80% by mass or less of a polycarbonate resin (A1) and 20% by mass or more and less than 90% by mass of a thermoplastic polyester resin (A2), and the total content of the flat cross section glass fiber (B) and the glass flakes (C) is 10 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the total content of the thermoplastic resin (A), the flat cross section glass fiber (B), and the glass flakes (C), and the average thickness of the glass flakes (C) is less than 0.45 μm.

[0028] A thermoplastic resin composition according to a second embodiment of the present invention is a thermoplastic resin composition containing a thermoplastic resin (A), a flat cross section glass fiber (B), and glass flakes (C), wherein the thermoplastic resin (A) contains 50% by mass or more and 80% by mass or less of a polycarbonate resin (A1) and 20% by mass or more and 50% by mass or less of a thermoplastic polyester resin (A2), and the thermoplastic polyester resin (A2) is a crystalline polyester resin, and the total content of the flat cross section glass fiber (B) and the glass flakes (C) is 10 parts by mass or more and 50 parts by mass or less relative to a total content of the thermoplastic resin (A), the flat cross section glass fiber (B), and the glass flakes (C) of 100 parts by mass, and the average thickness of the glass flakes (C) is 0.65 μm or less.

[0029] A thermoplastic resin composition according to a third embodiment of the present invention is a thermoplastic resin composition containing a thermoplastic resin (A), a flat cross section glass fiber (B), and glass flakes (C), wherein the thermoplastic resin (A) contains 50% by mass or more and 80% by mass or less of a polycarbonate resin (A1) and 20% by mass or more and 50% by mass or less of a thermoplastic polyester resin (A2), the thermoplastic polyester resin (A2) having a glass transition temperature of 80°C or more, the total content of the flat cross section glass fiber (B) and the glass flakes (C) being 10 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the total content of the thermoplastic resin (A), the flat cross section glass fiber (B), and the glass flakes (C), and the average thickness of the glass flakes (C) is 0.65 μm or less.

[0030] Hereinafter, the thermoplastic resin composition according to the first embodiment of the present invention, the thermoplastic resin composition according to the second embodiment, and the thermoplastic resin composition according to the third embodiment of the present invention will be collectively referred to as the "thermoplastic resin composition of the present invention."

[0031] [Mechanism] In the thermoplastic resin composition of the present invention, by using a combination of flat cross section glass fiber (B) and glass flake (C) as a glass-based filler, it is possible to obtain a thermoplastic resin composition having excellent strength and low anisotropy of dimensional accuracy and a linear expansion coefficient at the same level as that of metals such as aluminum and magnesium metal. In particular, by using thin glass flakes (C) with an average thickness of less than 0.45 μm or 0.65 μm or less, the number of glass flakes per unit mass of the glass flakes (C) blended into the thermoplastic resin composition can be increased, thereby further improving dimensional stability, reducing dimensional accuracy and its anisotropy, and increasing mechanical strength such as rigidity. In addition, the extremely thin glass flakes (C) improve the fluidity of the thermoplastic resin composition and promote the formation of a skin layer when filling a mold during molding, so that the flat cross section glass fiber (B) and glass flakes (C) blended into the resin composition are embedded inside the molded article, improving the appearance of the resulting molded article.

[0032] [Thermoplastic Resin (A)] The thermoplastic resin composition of the present invention contains a thermoplastic resin (A). The thermoplastic resin (A) of the present invention contains a polycarbonate resin (A1) and a thermoplastic polyester resin (A2) described below in predetermined proportions. That is, the thermoplastic resin (A) is used because it is excellent in transparency, impact resistance, heat resistance, etc., and the resulting molded article also has excellent dimensional stability, etc., and therefore, the thermoplastic resin (A1) is used in combination with the polycarbonate resin (A1) to improve the chemical resistance, solvent resistance, and flowability of the polycarbonate resin (A1).

[0033] The thermoplastic resin (A) of the present invention may contain, in addition to the polycarbonate resin (A1) and the thermoplastic polyester resin (A2), one or more of polyolefin resins such as polyethylene resins and polypropylene resins; styrene-based resins; polyamide resins; polyimide resins; polyetherimide resins; polyphenylene ether resins; polyphenylene sulfide resins; polysulfone resins, etc., in any combination and ratio.

[0034] <Polycarbonate Resin (A1)> There is no limitation on the type of polycarbonate resin (A1) used as the thermoplastic resin (A), and one type may be used alone, or two or more types may be used in any combination and in any ratio. Polycarbonate resins are polymers having a basic structure with a carbonate bond represented by the general formula -(-O-X-O-C(=O)-)-. In the formula, X is a hydrocarbon group, but X having a heteroatom or heterobond introduced therein may also be used to impart various properties.

[0035] As the polycarbonate resin (A1), an aromatic polycarbonate resin in which X in the above general formula is an aromatic hydrocarbon group is particularly preferred. The aromatic polycarbonate resin refers to a polycarbonate resin in which each carbon atom directly bonded to a carbonate bond is an aromatic carbon group. Among various polycarbonate resins, the aromatic polycarbonate resin is superior in terms of heat resistance, mechanical properties, electrical properties, etc.

[0036] There are no specific limitations on the type of polycarbonate resin, such as an aromatic polycarbonate resin. Examples include polycarbonate polymers, such as an aromatic polycarbonate polymer obtained by reacting a dihydroxy compound with a carbonate precursor. In this case, a polyhydroxy compound or the like may be reacted in addition to the dihydroxy compound and carbonate precursor. Alternatively, a method of reacting carbon dioxide as a carbonate precursor with a cyclic ether may be used. Polycarbonate polymers, such as an aromatic polycarbonate polymer, may be linear or branched. Furthermore, polycarbonate polymers, such as an aromatic polycarbonate polymer, may be homopolymers composed of one type of repeating unit, or may be copolymers having two or more types of repeating units. Various copolymerization forms, such as random copolymers and block copolymers, may be selected for the copolymer. Typically, such polycarbonate polymers, such as an aromatic polycarbonate polymer, are thermoplastic resins.

[0037] <Raw Materials for Polycarbonate Resin> Among the monomers that serve as raw materials for polycarbonate resin, examples of aromatic dihydroxy compounds are as follows.

[0038] 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; 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;

[0039] 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;

[0040] 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A), 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 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(4-hydroxy-3,5-dimethylphenyl)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, 1,2-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-naphthylethan, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)hexane, 1,1-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)octane, 4,4-bis(4-hydroxyphenyl)heptane, bis(hydroxyaryl)alkanes such as 2,2-bis(4-hydroxyphenyl)nonane, 1,10-bis(4-hydroxyphenyl)decane, and 1,1-bis(4-hydroxyphenyl)dodecane;

[0041] 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,4-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)-3-tert-butyl-cyclohexane, bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane, 1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexane, etc.;

[0042] Cardo structure-containing bisphenols such as 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene; dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone; etc.

[0043] Of these, bis(hydroxyaryl)alkanes are preferred, and bis(4-hydroxyphenyl)alkanes are particularly preferred, with 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A) being particularly preferred from the standpoints of impact resistance and heat resistance. The aromatic dihydroxy compounds may be used alone or in any combination and ratio of two or more.

[0044] Among the monomers that serve as raw materials for aliphatic polycarbonate resins, examples of aliphatic dihydroxy compounds include the following:

[0045] Alkanediols such as ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, and decane-1,10-diol;

[0046] cycloalkanediols such as cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4-(2-hydroxyethyl)cyclohexanol, and 2,2,4,4-tetramethyl-cyclobutane-1,3-diol;

[0047] Glycols such as ethylene glycol, 2,2'-oxydiethanol (i.e., diethylene glycol), triethylene glycol, propylene glycol, and spiroglycol;

[0048] aralkyldiols such as 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,3-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene, 2,3-bis(hydroxymethyl)naphthalene, 1,6-bis(hydroxyethoxy)naphthalene, 4,4'-biphenyldimethanol, 4,4'-biphenyldiethanol, 1,4-bis(2-hydroxyethoxy)biphenyl, bisphenol A bis(2-hydroxyethyl)ether, and bisphenol S bis(2-hydroxyethyl)ether;

[0049] Cyclic ethers such as 1,2-epoxyethane (i.e., ethylene oxide), 1,2-epoxypropane (i.e., propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1-methyl-1,2-epoxycyclohexane, 2,3-epoxynorbornane, and 1,3-epoxypropane; etc.

[0050] The aliphatic dihydroxy compounds may be used alone or in any combination of two or more in any ratio.

[0051] Among the monomers serving as raw materials for polycarbonate resins, examples of carbonate precursors include carbonyl halides, carbonate esters, etc. The carbonate precursors may be used alone or in any combination and ratio of two or more.

[0052] Specific examples of carbonyl halides include phosgene, and haloformates such as bischloroformates of dihydroxy compounds and monochloroformates of dihydroxy compounds. Specific examples of carbonate esters include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, and carbonates of dihydroxy compounds such as cyclic carbonates.

[0053] <<Method for producing polycarbonate resin (A1)>> The method for producing the polycarbonate resin (A1) is not particularly limited, and any method can be used. Examples thereof include interfacial polymerization, melt transesterification, pyridine method, ring-opening polymerization of a cyclic carbonate compound, and solid-phase transesterification of a prepolymer. Below, particularly preferred methods among these methods will be specifically described.

[0054] (Interfacial Polymerization Method) First, the production of a polycarbonate resin by interfacial polymerization method will be described. In the interfacial polymerization method, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually maintaining the pH at 9 or higher, and then interfacial polymerization is carried out in the presence of a polymerization catalyst to obtain a polycarbonate resin. Note that a molecular weight modifier (end terminator) may be present in the reaction system as needed, and an antioxidant may be present to prevent oxidation of the dihydroxy compound. The dihydroxy compound and carbonate precursor are as described above. Note that, among carbonate precursors, phosgene is preferably used, and the method using phosgene is particularly called the phosgene method.

[0055] Examples of organic solvents inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene, and xylene; etc. One type of organic solvent may be used, or two or more types may be used in any combination and ratio.

[0056] Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium bicarbonate, with sodium hydroxide and potassium hydroxide being preferred. The alkali compounds may be used alone or in any combination and ratio of two or more. There is no limitation on the concentration of the alkali compound in the alkaline aqueous solution, but it is typically used at 5 to 10% by mass in order to control the pH of the alkaline aqueous solution in the reaction to 10 to 12. Furthermore, when blowing in phosgene, for example, the molar ratio of the bisphenol compound to the alkali compound is preferably 1:1.9 or greater, more preferably 1:2.0 or greater, and more preferably 1:3.2 or less, more preferably 1:2.5 or less, in order to control the pH of the aqueous phase to 10 to 12, preferably 10 to 11.

[0057] Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic tertiary amines such as N,N'-dimethylcyclohexylamine and N,N'-diethylcyclohexylamine; aromatic tertiary amines such as N,N'-dimethylaniline and N,N'-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, and triethylbenzylammonium chloride; pyridine; and salts of guanidine. One type of polymerization catalyst may be used, or two or more types may be used in any combination and ratio.

[0058] Examples of molecular weight regulators include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; and phthalimides, with aromatic phenols being preferred. Specific examples of such aromatic phenols include alkyl-substituted phenols such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long-chain alkyl-substituted phenols; vinyl-containing phenols such as isopropanylphenol; epoxy-containing phenols; and carboxyl-containing phenols such as 2-methyl-6-hydroxyphenylacetic acid. One type of molecular weight regulator may be used, or two or more types may be used in any combination and ratio. The amount of molecular weight regulator used is typically 0.5 mol or more, preferably 1 mol or more, per 100 mol of dihydroxy compound, and typically 50 mol or less, preferably 30 mol or less. By using the molecular weight regulator in this range, the thermal stability and hydrolysis resistance of the resulting polycarbonate resin can be improved.

[0059] During the reaction, the order in which the reaction substrate, reaction solvent, catalyst, additives, etc. are mixed may be any order as long as the desired polycarbonate resin is obtained, and any appropriate order may be selected. For example, when phosgene is used as the carbonate precursor, the molecular weight modifier may be mixed at any time between the reaction of the dihydroxy compound with phosgene (phosgenation) and the start of the polymerization reaction. The reaction temperature is typically 0 to 40°C, and the reaction time is typically several minutes (e.g., 10 minutes) to several hours (e.g., 6 hours).

[0060] (Melt transesterification method) Next, a case where a polycarbonate resin is produced by a melt transesterification method will be described. In the melt transesterification method, for example, a transesterification reaction between a carbonate diester and a dihydroxy compound is carried out.

[0061] The dihydroxy compound is as described above. On the other hand, examples of the carbonate diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; and substituted diphenyl carbonates such as ditolyl carbonate. Among these, diphenyl carbonate and substituted diphenyl carbonates are preferred, with diphenyl carbonate being particularly preferred. Note that one type of carbonate diester may be used, or two or more types may be used in any combination and ratio.

[0062] The ratio of the dihydroxy compound to the carbonic acid diester may be any ratio as long as the desired polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester per mole of the dihydroxy compound, and more preferably 1.01 moles or more. The upper limit of this molar ratio is usually 1.30 moles or less. By adjusting the molar ratio within this range, the terminal hydroxyl group concentration of the resulting polycarbonate resin can be adjusted to a suitable range.

[0063] In polycarbonate resins, the concentration of terminal hydroxyl groups tends to have a significant effect on thermal stability, hydrolysis stability, color tone, etc. Therefore, the amount of terminal hydroxyl groups may be adjusted as needed by any known method. In the transesterification reaction, a polycarbonate resin with an adjusted amount of terminal hydroxyl groups can usually be obtained by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the degree of reduced pressure during the transesterification reaction, etc. This operation can also adjust the molecular weight of the resulting polycarbonate resin.

[0064] When the amount of terminal hydroxyl groups is adjusted by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the mixing ratio is as described above. In addition, a more proactive adjustment method is a method in which a terminal terminator is separately added during the reaction. In this case, examples of the terminal terminator include monohydric phenols, monocarboxylic acids, and carbonic acid diesters. The terminal terminator may be used alone or in any combination and ratio of two or more.

[0065] When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination as an auxiliary. Note that the transesterification catalyst may be used alone or in any combination and ratio of two or more.

[0066] In the melt transesterification method, the reaction temperature is usually 100 to 320°C. The pressure during the reaction is usually reduced to 2 mmHg or less. As a specific operation, the melt polycondensation reaction may be carried out under the above-mentioned conditions while removing by-products such as hydroxy compounds. The melt polycondensation reaction may be carried out either batchwise or continuously. When carried out batchwise, the order in which the reaction substrates, reaction solvent, catalyst, additives, etc. are mixed may be any order as long as the desired polycarbonate resin is obtained, and any appropriate order may be set. However, in consideration of the stability of the polycarbonate resin, etc., it is preferable to carry out the melt polycondensation reaction continuously.

[0067] In the melt transesterification method, a catalyst deactivator may be used as needed. Any compound that neutralizes the transesterification catalyst can be used as the catalyst deactivator. Examples include sulfur-containing acidic compounds and their derivatives. One catalyst deactivator may be used, or two or more catalyst deactivators may be used in any combination and ratio. The amount of catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, preferably 5 equivalents or less, relative to the alkali metal element or alkaline earth metal element contained in the transesterification catalyst. Furthermore, the amount is usually 1 ppm or more, and usually 100 ppm or less, preferably 20 ppm or less, relative to the polycarbonate resin.

[0068] <<Structural Viscosity Index N of Polycarbonate Resin (A1)>> The polycarbonate resin (A1) preferably contains a certain proportion or more of a polycarbonate resin having a structural viscosity index N within a predetermined range. As described in detail in the literature "Rheology for Chemists" (Kagaku Dojin, 1982, pp. 15-16), the structural viscosity index N is an index for evaluating the flow characteristics of a melt. Typically, the melting characteristics of a polycarbonate resin can be expressed by the mathematical formula: γ = a σN. In the formula, γ is the shear rate, a is a constant, σ is the stress, and N is the structural viscosity index.

[0069] In the above formula, when N = 1, Newtonian fluidity is indicated, and the larger the value of N, the greater the non-Newtonian fluidity. In other words, the flow characteristics of a melt are evaluated based on the magnitude of the structural viscosity index N. In general, polycarbonate resins with a large structural viscosity index N tend to have high melt viscosity in the low shear region. Therefore, when a polycarbonate resin with a large structural viscosity index N is mixed with another polycarbonate resin, dripping during combustion of the resulting molded article can be suppressed, improving flame retardancy. However, in order to maintain the moldability of the resulting polycarbonate resin composition within a good range, it is preferable that the structural viscosity index N of this polycarbonate resin is not excessively large.

[0070] Therefore, it is preferable that the polycarbonate resin (A1) contains at least a certain proportion of polycarbonate resins having a structural viscosity index N of usually 1.2 or more, preferably 1.25 or more, more preferably 1.28 or more, and usually 1.8 or less, preferably 1.7 or less. A high structural viscosity index N means that the polycarbonate resin has a branched structure, and by containing a polycarbonate resin having such a high structural viscosity index N, dripping of the obtained molded article during combustion can be suppressed, and flame retardancy can be improved.

[0071] The structural viscosity index N can also be expressed by the above-mentioned formula derived from Log ηa = [(1-N) / N] × Log γ + C, as described in, for example, JP 2005-232442 A. In the formula, N: structural viscosity index, γ: shear rate, C: constant, and ηa: apparent viscosity. As can be seen from this formula, the N value can also be evaluated from γ and ηa in the low shear region where viscosity behavior differs significantly. For example, the N value can be determined from ηa at γ = 12.16 sec-1 and γ = 24.32 sec-1.

[0072] As described in, for example, JP-A-8-259687 and JP-A-8-245782, polycarbonate resins having a structural viscosity index N of 1.2 or more can be obtained by selecting catalyst conditions or production conditions when reacting a dihydroxy compound with a carbonate diester by a melting method (ester interchange method), without adding a branching agent, to obtain polycarbonate resins having a high structural viscosity index N and excellent hydrolysis stability.

[0073] Polycarbonate resins having a structural viscosity index N of 1.2 or greater can also be produced by using a branching agent in the production process using a conventional phosgene method or melting method (transesterification method). Specific examples of branching agents include polyhydroxy compounds such as phloroglucin, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, and 2,6-dimethyl-2,4,6-tris(4-hydroxyphenylheptene-3,1,3,5-tris(4-hydroxyphenyl)ethane, as well as 3,3-bis(4-hydroxyaryl)oxindole (=isatin bisphenol), 5-chloroisatin bisphenol, 5,7-dichloroisatin bisphenol, and 5-bromoisatin bisphenol. The amount used is in the range of 0.01 to 10 mol % relative to the dihydroxy compound, and particularly preferably in the range of 0.1 to 3 mol %.

[0074] In the polycarbonate resin composition of the present invention, the polycarbonate resin (A1) preferably contains a polycarbonate resin having a structural viscosity index N falling within the specified range (hereinafter, this polycarbonate resin may be referred to as a "predetermined N polycarbonate resin"). The polycarbonate resin (A1) preferably contains at least 20% by mass, preferably at least 50% by mass, and more preferably at least 60% by mass of the polycarbonate resin. By combining the polycarbonate resin with the predetermining N polycarbonate resin in this manner, an unnecessary increase in torque during extrusion is prevented, which makes it less likely to result in a decrease in productivity. In other words, both moldability and productivity can be significantly improved. There is no upper limit to the content of the predetermining N polycarbonate resin in the polycarbonate resin (A1). It is usually 100% by mass or less, but preferably 90% by mass or less, and more preferably 85% by mass or less. The predetermining N polycarbonate resin may be used alone, or two or more may be used in any combination and ratio. Furthermore, the polycarbonate resin (A1) may contain, in addition to the above-mentioned specified N polycarbonate resin, a polycarbonate resin whose structural viscosity index N is outside the above-mentioned specified range. There is no limitation on the type of polycarbonate resin, but linear polycarbonate resins are particularly preferred. By combining a specified N polycarbonate resin with a linear polycarbonate resin, the resulting polycarbonate resin composition can be advantageously balanced between flame retardancy (anti-dripping property) and moldability (fluidity). From this perspective, the polycarbonate resin (A1) may be composed of a specified N polycarbonate resin and a linear polycarbonate resin. The structural viscosity index N of this linear polycarbonate resin is usually about 1 to 1.15.

[0075] <<Viscosity Average Molecular Weight of Polycarbonate Resin (A1)>> The molecular weight of the polycarbonate resin (A1) used in the present invention is preferably a viscosity average molecular weight (Mv) of 16,000 to 50,000. A viscosity average molecular weight of 16,000 or more can provide sufficient mechanical strength, while a viscosity average molecular weight of 50,000 or less provides excellent fluidity and moldability. The viscosity average molecular weight is preferably 18,000 or more, more preferably 19,000 or more, even more preferably 20,000 or more, particularly preferably 21,000 or more, and especially preferably 22,000 or more, while preferably 45,000 or less, more preferably 40,000 or less, even more preferably 36,000 or less, and particularly preferably 33,000 or less. Methods for adjusting the molecular weight within these ranges include known methods such as controlling the amount of the molecular weight regulator described above.

[0076] In this specification, the viscosity average molecular weight (Mv) of a polycarbonate resin is determined by measuring the intrinsic viscosity [η] (unit: dl / g) at a temperature of 20°C using methylene chloride as a solvent with an Ubbelohde viscometer, and calculating the viscosity average molecular weight (Mv) using the Schnell viscosity formula, i.e., η = 1.23 × 10 －４ Mv ０．８３ The intrinsic viscosity [η] is a value calculated from the following formula after measuring the specific viscosity [ηsp] at each solution concentration [C] (g / dl).

[0077]

[0078] <<Terminal Hydroxyl Group Concentration of Polycarbonate Resin (A1)>> The terminal hydroxyl group concentration of the polycarbonate resin (A1) is arbitrary and may be appropriately selected and determined, but is typically 1,000 ppm by mass or less, preferably 800 ppm by mass or less, and more preferably 600 ppm by mass or less. This can further improve the residence heat stability and color tone of the polycarbonate resin composition of the present invention. The lower limit, particularly for polycarbonate resin (A1) produced by a melt transesterification method, is typically 10 ppm by mass or more, preferably 30 ppm by mass or more, and more preferably 40 ppm by mass or more. This can suppress a decrease in molecular weight and further improve the mechanical properties of the polycarbonate resin composition of the present invention. When two or more polycarbonate resins having different terminal hydrogen group concentrations are mixed and used, the terminal hydroxyl group concentration is the actual value measured using the mixed polycarbonate resin by the method described below. The terminal hydroxyl group concentration is expressed in ppm by mass as the mass of the terminal hydroxyl groups relative to the mass of the polycarbonate resin. The terminal hydroxyl group concentration can be measured by colorimetric determination using the titanium tetrachloride / acetic acid method (the method described in Macromol. Chem. 88 215 (1965)).

[0079] <Form of Polycarbonate Resin (A1)> The polycarbonate resin (A1) is not limited to an embodiment containing only one type of polycarbonate resin, and a mixture of two or more types of polycarbonate resins differing in monomer composition, molecular weight, terminal hydroxyl group concentration, etc. may be used.

[0080] Furthermore, for example, polycarbonate resin may be constituted as a copolymer mainly composed of polycarbonate resin, such as a copolymer with an oligomer or polymer having a siloxane structure for the purpose of further enhancing flame retardancy and impact resistance; a copolymer with a monomer, oligomer, or polymer having a phosphorus atom for the purpose of further improving thermal oxidation stability and flame retardancy; a copolymer with a monomer, oligomer, or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; a copolymer with an oligomer or polymer having an olefin structure such as polystyrene for improving optical properties; or a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance.

[0081] In order to improve the appearance and flowability of molded articles, the polycarbonate resin (A1) may contain a polycarbonate oligomer. The viscosity-average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. In this case, the polycarbonate oligomer contained in the polycarbonate resin (A1) is preferably 30 mass% or less of the polycarbonate resin (A1) (including the polycarbonate oligomer).

[0082] Furthermore, the polycarbonate resin (A1) may be not only a virgin raw material but also a polycarbonate resin regenerated from used products (so-called material-recycled polycarbonate resin). Examples of the used products include optical recording media such as optical disks; light guide plates; transparent vehicle components such as automobile window glass, automobile headlamp lenses, and windshields; containers such as water bottles; eyeglass lenses; soundproof walls, glass windows, corrugated sheets, and other building components. In addition, crushed products obtained from non-conforming products, sprues, runners, etc., or pellets obtained by melting these may also be used.

[0083] When using such recycled polycarbonate resins, it is preferable to use polycarbonate resins with minimal amounts of foreign matter, such as metal powder and coloring components, mixed in during the recycling process so as not to impair the quality of the resulting molded articles. For example, pellets containing no foreign matter greater than 0.3 mm in size per 100 g of pellets are preferred, with no more than 5 particles greater than 0.2 mm and no more than 0.3 mm being more preferred, and no more than 50 particles greater than 0.1 mm and no more than 0.2 mm being particularly preferred. However, the recycled polycarbonate resin preferably accounts for no more than 80% by mass, and more preferably no more than 50% by mass, of the polycarbonate resin (A1) contained in the thermoplastic resin composition of the present invention. This is because recycled polycarbonate resins are likely to have been subjected to degradation such as thermal degradation and aging, and using such polycarbonate resins in amounts greater than the above ranges may result in a deterioration in hue and mechanical properties.

[0084] Commercially available recycled polycarbonate resins include "PC 2010A" manufactured by Ausell, "PC-116X" manufactured by Hongyu, and "MJ-311A" manufactured by MJ Material.

[0085] <Thermoplastic polyester resin (A2)> The thermoplastic polyester resin (A2) is a polymer or copolymer obtained by a condensation reaction of a dicarboxylic acid component consisting of dicarboxylic acids or their reactive derivatives and a diol component consisting of diols or their ester derivatives as the main components. From the viewpoint of industrial productivity, it is particularly preferable to use a polyester resin obtained by polycondensing an aromatic dicarboxylic acid as the main acid component with an alcohol mainly consisting of an aliphatic diol as the main acid component as the thermoplastic polyester resin (A2). Only one type of thermoplastic polyester resin (A2) may be used, or two or more types may be used in any combination and in any ratio.

[0086] From the viewpoint of obtaining a thermoplastic resin composition having excellent heat resistance and chemical resistance, the thermoplastic polyester resin (A2) is preferably a crystalline polyester resin, such as crystalline polyethylene terephthalate (C-PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN).

[0087] Furthermore, from the viewpoint of obtaining a thermoplastic resin composition having excellent heat resistance, the glass transition temperature (Tg) of the thermoplastic polyester resin is preferably 70° C. or higher, more preferably 80° C. or higher, even more preferably 90° C. or higher, and particularly preferably 100° C. or higher. In this specification, the glass transition temperature (Tg) of the resin is a value determined by differential scanning calorimetry (DSC) based on ISO-11357-2.

[0088] Examples of the aromatic dicarboxylic acid component used in the production of the thermoplastic polyester resin (A2) include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 4,4'-biphenylmethanedicarboxylic acid, 4,4'-biphenylsulfonedicarboxylic acid, 4,4'-biphenylisopropylidenedicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4'-p-terphenylenedicarboxylic acid, and 2,5-pyridinedicarboxylic acid. Substituted products thereof (e.g., alkyl group-substituted products such as 5-methylisophthalic acid) and reactive derivatives thereof (e.g., alkyl ester derivatives such as dimethyl terephthalate and diethyl terephthalate) can also be used.

[0089] Among these, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and alkyl ester derivatives thereof are more preferred, and terephthalic acid and alkyl ester derivatives thereof are particularly preferred. These aromatic dicarboxylic acids may be used alone or in combination of two or more, and may also be used in combination with one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, or alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

[0090] Examples of the diols used in producing the thermoplastic polyester resin (A2) include aliphatic diols such as ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, triethylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, and 2,2-dimethyl-1,3-propanediol; alicyclic diols such as 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanediol, and trans- or cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol; and aromatic diols such as p-xylenediol, bisphenol A, tetrabromobisphenol A, and tetrabromobisphenol A-bis(2-hydroxyethyl ether), and substituted versions of these can also be used.

[0091] Of these, from the viewpoints of heat resistance, dimensional stability, etc., aliphatic diols are preferred, ethylene glycol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are more preferred, and ethylene glycol is particularly preferred.

[0092] The diol may be used alone or in combination of two or more. As the diol component, one or more long-chain diols having a molecular weight of 400 to 6,000, such as polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol, may be copolymerized in combination with the above diols.

[0093] In addition, the thermoplastic polyester resin (A2) can be copolymerized with hydroxycarboxylic acids such as parahydroxybenzoic acid, other carboxylic acids, and alcohols other than the above diols, and such copolymer resins can also be used in the present invention. However, it is preferable that such copolymerization components are small in amount, and it is preferable that 80% by mass or more, and even 90% by mass or more of the thermoplastic polyester resin (A2) are components derived from aromatic dicarboxylic acids and aliphatic diols. It is also preferable that 80 mol% or more, and even 90 mol% or more of the aromatic dicarboxylic acids and aliphatic diols are each composed of one compound.

[0094] From the viewpoints of high processing versatility and heat resistance, cold resistance, and chemical resistance, the thermoplastic polyester resin (A2) is preferably polyalkylene terephthalate or polyalkylene naphthalate. Here, polyalkylene terephthalate refers to a resin containing an alkylene terephthalate structural unit, and may be a copolymer of an alkylene terephthalate structural unit and another structural unit. Furthermore, polyalkylene naphthalate refers to a resin containing an alkylene naphthalate structural unit, and may be a copolymer of an alkylene naphthalate structural unit and another structural unit.

[0095] Examples of polyalkylene terephthalates or polyalkylene naphthalates include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), poly(cyclohexane-1,4-dimethylene terephthalate), polytrimethylene terephthalate, etc. Among these, polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) are preferred, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) are more preferred, and polyethylene naphthalate (PEN) is even more preferred.

[0096] In addition to the above, examples of polyalkylene terephthalate or polyalkylene naphthalate include alkylene terephthalate or polyalkylene naphthalate copolymers having alkylene terephthalate or polyalkylene naphthalate structural units as the main structural unit, and polyalkylene terephthalate or polyalkylene naphthalate mixtures having polyalkylene terephthalate or polyalkylene naphthalate as the main component.Furthermore, those containing or copolymerized with an elastomer component such as polyoxytetramethylene glycol (PTMG) can also be used.

[0097] Examples of alkylene terephthalate copolyesters include copolyesters composed of two or more diol components and terephthalic acid, and copolyesters composed of a diol component, terephthalic acid, and a dicarboxylic acid other than terephthalic acid. When two or more diol components are used, they may be appropriately selected from the diol components described above, but it is preferable to keep the monomer unit copolymerized with the alkylene terephthalate main structural unit within 25 mass% because this will improve heat resistance.

[0098] Examples of the alkylene terephthalate copolymer include alkylene terephthalate copolyesters having alkylene terephthalate structural units as the main structural unit, such as ethylene glycol / isophthalic acid / terephthalic acid copolymer (isophthalic acid-copolymerized polyethylene terephthalate) and 1,4-butanediol / isophthalic acid / terephthalic acid copolymer (isophthalic acid-copolymerized polybutylene terephthalate), as well as 1,4-butanediol / isophthalic acid / decanedicarboxylic acid copolymers, and among these, alkylene terephthalate copolyesters are preferred.

[0099] When an alkylene terephthalate copolyester is used as the thermoplastic polyester resin (A2), the above-mentioned isophthalic acid copolymerized polyethylene terephthalate and isophthalic acid copolymerized polybutylene terephthalate are preferred, and among these, those containing an isophthalic acid component of 25 mass% or less are particularly preferred from the viewpoint of heat resistance.

[0100] As the thermoplastic polyester resin (A2), polyethylene terephthalate is particularly preferred in terms of compatibility with the polycarbonate resin (A1) and mechanical properties. Here, polyethylene terephthalate refers to a polyester resin having a structure in which terephthalic acid units and ethylene glycol units are ester-bonded, and includes, in addition to polyethylene terephthalate (homopolymer), polyethylene terephthalate copolymers containing other copolymerization components other than terephthalic acid units and ethylene glycol units, and mixtures of homopolymers and polyethylene terephthalate copolymers.

[0101] The polyethylene terephthalate may contain one or more dicarboxylic acid units other than terephthalic acid. Specific examples of other dicarboxylic acids include aromatic dicarboxylic acids such as isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, bis(4,4'-carboxyphenyl)methane, anthracenedicarboxylic acid, and 4,4'-diphenyletherdicarboxylic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 4,4'-dicyclohexyldicarboxylic acid; and aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, and dimer acid. In the polyethylene terephthalate used in the present embodiment, terephthalic acid units preferably account for 80 mol % or more of all dicarboxylic acid units, more preferably 90 mol % or more, even more preferably 95 mol % or more, and may even account for 99 mol % or more.

[0102] The polyethylene terephthalate may contain one or more other diol units in addition to ethylene glycol as the diol units. Specific examples of the other diol units include aliphatic glycols such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, and neopentyl glycol; alicyclic glycols such as cyclohexanedimethanol; and aromatic dihydroxy compound derivatives such as bisphenol A and bisphenol S. In the polyethylene terephthalate used in this embodiment, ethylene glycol units preferably account for 80 mol % or more of all diol units, more preferably 90 mol % or more, and even more preferably 95 mol % or more, and may even account for 99 mol % or more.

[0103] Furthermore, the polyethylene terephthalate may be copolymerized with a branched component, for example, a trifunctional acid such as tricarballylic acid, trimellitic acid, trimellitic acid, etc., or a tetrafunctional acid such as pyromellitic acid, capable of forming an ester, or a trifunctional or tetrafunctional alcohol such as glycerin, trimethylolpropane, pentaerythritol, etc., in a proportion of, for example, 1.0 mol % or less, preferably 0.5 mol % or less, and more preferably 0.3 mol % or less.

[0104] The polyethylene terephthalate used in this embodiment is preferably a polyethylene terephthalate homopolymer in which terephthalic acid units and ethylene glycol units are ester-bonded. Alternatively, it may be a polyethylene terephthalate copolymer containing, as the carboxylic acid units, one or more dicarboxylic acids other than the terephthalic acid and / or, as the diol units, one or more diols other than the ethylene glycol. In the polyethylene terephthalate, the terephthalic acid units and ethylene glycol units preferably account for 85 mol % or more, more preferably 90 mol % or more, even more preferably 95 mol % or more, even more preferably 98 mol % or more, and even more preferably 99 mol % or more of all units excluding terminal groups.

[0105] When the polyethylene terephthalate is a polyethylene terephthalate modified by copolymerization, isophthalic acid copolymerized polyethylene terephthalate is preferred. Among these, isophthalic acid copolymerized polyethylene terephthalate in which units derived from isophthalic acid (hereinafter, sometimes referred to as "isophthalic acid units") account for 0.5 mol% to 15 mol% of all units derived from dicarboxylic acid components is preferred. By using such a specific polyethylene terephthalate, the nominal tensile strain at break of the resulting molded article tends to be further improved.

[0106] The proportion of the isophthalic acid units in all units derived from the dicarboxylic acid component is preferably 0.7 mol% or more, more preferably 0.9 mol% or more, even more preferably 1.1 mol% or more, still more preferably 1.3 mol% or more, and even more preferably 1.5 mol% or more. The proportion of the isophthalic acid units in all units derived from the dicarboxylic acid component is, in order, 10.0 mol% or less, 8.0 mol% or less, 5.0 mol% or less, 4.0 mol% or less, preferably 3.5 mol% or less, more preferably 3.0 mol% or less, even more preferably 2.5 mol% or less, still more preferably 2.3 mol% or less, and even more preferably 2.0 mol% or less.

[0107] The intrinsic viscosity [η] of the polyethylene terephthalate used in this embodiment is preferably 0.50 dL / g or more, more preferably 0.60 dL / g or more, even more preferably 0.65 dL / g or more, even more preferably 0.70 dL / g or more, even more preferably 0.73 dL / g or more, particularly preferably more than 0.76 dL / g, particularly preferably 0.78 dL / g or more, and the intrinsic viscosity may be 0.80 dL / g or more. When the intrinsic viscosity of the polyethylene terephthalate is equal to or greater than the above lower limit, the nominal tensile strain at break of the resulting molded article tends to be further improved. Furthermore, the intrinsic viscosity of the polyethylene terephthalate is preferably 2.0 dL / g or less, more preferably 1.5 dL / g or less, even more preferably 1.2 dL / g or less, even more preferably 0.95 dL / g or less, and even more preferably 0.85 dL / g or less. When the intrinsic viscosity of the polyethylene terephthalate is not more than the above upper limit, the melt viscosity during melt-kneading or molding does not become too high, and the load on the extruder or molding machine tends to be reduced. When the thermoplastic polyester resin (A2) contains two or more polyethylene terephthalates, the intrinsic viscosity is the intrinsic viscosity of the mixture.

[0108] In the present invention, the intrinsic viscosity of polyethylene terephthalate is a value obtained by measuring the number of seconds it takes for a polymer solution having a concentration of 1.0 g / dL and the solvent alone to fall at 30°C using a mixed solvent of phenol / tetrachloroethane (1 / 1 by mass), and then calculating the value from the following formula. For commercially available products, the catalog value can be used: IV = ((1 + 4K Ｈ η ｓｐ ) ０．５ -1) / (2K Ｈ ・C) (However, η ｓｐ =η ０ -1, η is the number of seconds the polymer solution falls, η ０ is the number of seconds the solvent falls, C is the polymer solution concentration (g / dL), K Ｈ is Huggins' constant, which is set to 0.33.)

[0109] The amount of terminal carboxyl groups in the polyethylene terephthalate used in this embodiment may be appropriately selected and determined, but is typically 60 eq / ton or less, preferably 50 eq / ton or less, and more preferably 30 eq / ton or less. The terminal carboxyl group concentration of polyethylene terephthalate is a value determined by dissolving 0.5 g of polyethylene terephthalate in 25 mL of benzyl alcohol and titrating with a 0.01 mol / L benzyl alcohol solution of sodium hydroxide. The amount of terminal carboxyl groups can be adjusted by any conventionally known method, such as adjusting polymerization conditions such as the raw material charging ratio, polymerization temperature, and pressure reduction method during polymerization, or by reacting a terminal blocking agent.

[0110] The polyethylene terephthalate used in this embodiment preferably contains 0.50% by mass or less of cyclic trimer, more preferably 0.40% by mass or less, and even more preferably 0.30% by mass or less. By setting the content below the upper limit, the occurrence of silver smearing during retention tends to be further reduced. While the lower limit is not particularly specified, 0.1% by mass or more is practical. The amount of cyclic trimer was measured by dissolving 0.1 g of polyethylene terephthalate in a solvent such as chloroform, dissolving and reprecipitation, filtering the supernatant, and then measuring it by high-performance liquid chromatography (HPLC). Quantitation was performed using a single-point absolute calibration curve method, and the value was expressed in terms of DMT (dimethyl terephthalate).

[0111] As such polyethylene terephthalate (PET), virgin products (hereinafter sometimes referred to as "virgin PET"), recycled products (hereinafter sometimes referred to as "recycled PET"), bio-derived products (hereinafter sometimes referred to as "bio-PET"), and mixtures thereof can be used. Note that bio-PET refers to polyethylene terephthalate in which at least a portion of the raw materials is derived from biological resources (biomass). The polyethylene terephthalate used in this embodiment may be any one of virgin products, recycled products, and bio-derived products, or a combination of these, but recycled products are preferred in terms of reducing the environmental load.

[0112] Examples of recycled PET include those obtained through material recycling, in which collected used PET bottles and films are crushed and alkaline-cleaned for reuse as fibers, etc.; those obtained through chemical recycling (chemical decomposition); and those obtained through mechanical recycling. Chemical recycling involves chemically decomposing collected used PET bottles and films, returning them to their raw material level and resynthesizing polyethylene terephthalate. Mechanical recycling, on the other hand, is a method that more reliably removes dirt from polyethylene terephthalate than material recycling by performing alkaline cleaning more rigorously than in the material recycling described above or by vacuum drying at high temperatures. For example, after removing foreign matter from used PET bottles, they are crushed and washed, then pelletized in an extruder, crystallized at approximately 120-150°C, and then solid-phase polymerized at approximately 210°C under a nitrogen stream or high vacuum to produce recycled PET. Bio-PET is PET produced by replacing the monoethylene glycol (a PET raw material) with a bio-based material derived from sugarcane.

[0113] Bio-PET and recycled PET that contain a low content of foreign matter and reaction residues (such as isophthalic acid) that may have been mixed in during processing, etc., are preferred from the viewpoint of improving the quality of the resulting molded products. For example, it is preferable that the purity, expressed as the ratio of isophthalic acid to terephthalic acid, be 2.0% or less, particularly 1.4% or less, and especially 1.0% or less.

[0114] Commercially available bio-PET products include "RAMAPET N1B" manufactured by INDORAMA and "Bio-Clapet KS710B-8B" manufactured by Kuraray Co., Ltd. Commercially available recycled PET products include "RAMAPET N1-100" manufactured by INDORAMA, "RP-772w" manufactured by INTCO, and "CF-80" manufactured by EcoBlue.

[0115] <Contents of Polycarbonate Resin (A1) and Thermoplastic Polyester Resin (A2)> The content of polycarbonate resin (A1) in the thermoplastic resin (A) according to the first embodiment of the present invention is more than 10% by mass and not more than 80% by mass, and the content of thermoplastic polyester resin (A2) is 20% by mass or more and less than 90% by mass. When the content of polycarbonate resin (A1) in the thermoplastic resin (A) is greater than the lower limit and the content of thermoplastic polyester resin (A2) is less than the upper limit, the transparency, impact resistance, heat resistance, dimensional stability of molded articles, and the like tend to be excellent due to the polycarbonate resin (A1). When the content of polycarbonate resin (A1) is not more than the upper limit and the content of thermoplastic polyester resin (A2) is not less than the lower limit, the effect of improving chemical resistance, solvent resistance, and flowability due to the thermoplastic polyester resin (A2) tends to be excellent. From this viewpoint, it is more preferable that the content of polycarbonate resin (A1) in the thermoplastic resin (A) is 30 to 75 mass% and the content of thermoplastic polyester resin (A2) is 25 to 75 mass%, and it is even more preferable that the content of polycarbonate resin (A1) is 50 to 70 mass% and the content of thermoplastic polyester resin (A2) is 30 to 50 mass%.

[0116] The content of polycarbonate resin (A1) in the thermoplastic resin (A) according to the second and third embodiments of the present invention is 50% by mass or more and 80% by mass or less, and the content of thermoplastic polyester resin (A2) is 20% by mass or more and 50% by mass or less. When the content of polycarbonate resin (A1) in the thermoplastic resin (A) is greater than the above lower limit and the content of thermoplastic polyester resin (A2) is less than the above upper limit, the transparency, impact resistance, heat resistance, dimensional stability of molded articles, etc. tend to be superior due to the polycarbonate resin (A1). When the content of polycarbonate resin (A1) is less than the above upper limit and the content of thermoplastic polyester resin (A2) is greater than the above lower limit, the effect of improving chemical resistance, solvent resistance, and flowability due to the thermoplastic polyester resin (A2) tends to be superior. From this viewpoint, it is more preferable that the content of polycarbonate resin (A1) in the thermoplastic resin (A) is 50 to 75 mass% and the content of thermoplastic polyester resin (A2) is 25 to 50 mass%, and it is even more preferable that the content of polycarbonate resin (A1) is 50 to 70 mass% and the content of thermoplastic polyester resin (A2) is 30 to 50 mass%.

[0117] In any embodiment, when the thermoplastic resin (A) contains the above-mentioned other thermoplastic resins other than the polycarbonate resin (A1) and the thermoplastic polyester resin (A2), from the viewpoint of more effectively obtaining the above-mentioned effects provided by containing the polycarbonate resin (A1) and the thermoplastic polyester resin (A2), the content of the other thermoplastic resins in the thermoplastic resin (A) is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 0 to 10% by mass.

[0118] [Flat Cross Section Glass Fiber (B)] The thermoplastic resin composition of the present invention contains a flat cross section glass fiber (B). By using the flat cross section glass fiber (B) in combination with the glass flakes (C) described below, it is possible to obtain a thermoplastic resin composition that is excellent in strength and low anisotropy of dimensional accuracy, and has a linear expansion coefficient at the same level as that of metals such as aluminum and magnesium metal.

[0119] The flat cross section glass fiber (B) used in the present invention has a ratio of the major axis (width) to the minor axis (thickness) (major axis / minor axis (width / thickness), hereinafter referred to as "flatness") in a cross section (hereinafter simply referred to as "fiber cross section") perpendicular to the fiber length direction of the glass fiber, on average, of preferably more than 1.5, more preferably 1.6 or more, even more preferably 1.8 or more, particularly preferably 2 or more, and preferably 8 or less, more preferably 7 or less, even more preferably 6 or less, particularly preferably 5 or less. If the flatness of the flat cross section glass fiber (B) is more than 1.5, the dimensional anisotropy of the resin composition can be desirably reduced, and if it is 8 or less, it can be used without impairing the appearance of a molded article made from the resin composition.

[0120] The average value of the major axis (width) of the fiber cross section of the flat cross section glass fiber (B) 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 average value of the minor axis (thickness) of the fiber cross section of the flat cross section glass fiber (B) is preferably 3 to 20 μm, more preferably 4 to 15 μm, and even more preferably 5 to 12 μm. If the average values ​​of the major axis and minor axis of the flat cross section glass fiber (B) are equal to or greater than the above lower limit, they contribute to the dimensional accuracy and rigidity-imparting effect of the resin composition, and if they are equal to or less than the above upper limit, the fluidity of the resin composition can be kept within an appropriate range, and a good appearance can be obtained.

[0121] The number average fiber length of the flat cross section glass fiber (B) is preferably 0.5 to 20 mm, more preferably 1 to 15 mm, and even more preferably 2 to 10 mm. If the number average fiber length is equal to or greater than the lower limit, the material rigidity and mechanical strength are desirable, and if it is equal to or less than the upper limit, the handleability during kneading processing is good. Furthermore, the ratio of the average fiber length to the average fiber diameter (aspect ratio) of the flat cross section glass fiber (B) is preferably 2 to 120, more preferably 2.5 to 70, and even more preferably 3 to 50. If the aspect ratio is less than 2, the mechanical strength tends to decrease, and conversely, if it exceeds 120, warpage and anisotropy increase, and the appearance of the molded product tends to deteriorate significantly.

[0122] The major axis, minor axis, fiber length, and fiber diameter (the fiber diameter corresponds to the major axis) of the flat cross section glass fiber (B) are values ​​measured by scanning electron microscope (SEM) observation, and these average values ​​are obtained by averaging the respective measurement values ​​of 3,000 to 10,000 pieces.

[0123] The glass composition of the flat cross section glass fiber (B) may be any glass composition that is generally used in thermoplastic resins, and alkali-resistant glass compositions containing A glass, E glass, and zirconia components may also be used.Among these, the glass composition of the flat cross section glass fiber (B) used in the present invention is preferably alkali-free glass (E glass) in order to improve the thermal stability of the polycarbonate resin composition.

[0124] The flat cross section glass fiber (B) used in the present invention can be surface treated with a silane coupling agent such as aminosilane or epoxysilane in order to improve adhesion to the polycarbonate resin.

[0125] The flat cross section glass fiber (B) is also preferably used as chopped strands obtained by bundling a large number of these fibers and cutting them to a predetermined length, and in this case, it is preferable to blend a sizing agent into the flat cross section glass fiber. By blending the sizing agent, good mechanical properties can be obtained in addition to the advantage of improving the production stability of the polycarbonate resin composition. There are no particular restrictions on the sizing agent, but examples include urethane-based, epoxy-based, and acrylic-based sizing agents.

[0126] As such flat cross section glass fiber (B), "CSG 3PA830S" (flatness: 4.0) manufactured by Nitto Boseki Co., Ltd., "ECS 03 T-187-FGF" (flatness: 4.0) manufactured by Nippon Electric Glass Co., Ltd., and "ECS307AT-3-M4" manufactured by CPIC are commercially available.

[0127] [Glass Flakes (C)] The thermoplastic resin composition according to the first embodiment of the present invention contains glass flakes (C) having an average thickness of less than 0.45 μm. The glass flakes (C) according to the first embodiment of the present invention have an average thickness of less than 0.45 μm, which is extremely thin compared to the thickness of ordinary glass flakes, which is about 5 μm. The average thickness of the glass flakes (C) is particularly preferably 0.3 to 0.4 μm. If the average thickness is 0.45 μm or more, the aforementioned effects of the present invention achieved by using ultrathin glass flakes (C) cannot be obtained. Furthermore, if the average thickness is below the lower limit of the above range, the glass flakes may become extremely susceptible to cracking, resulting in reduced rigidity and impact resistance.

[0128] The thermoplastic resin compositions according to the second and third embodiments of the present invention contain glass flakes (C) having an average thickness of 0.65 μm or less. The average thickness of the glass flakes (C) according to the second and third embodiments of the present invention is preferably 0.05 to 0.65 μm, more preferably 0.10 to 0.5 μm, even more preferably 0.20 μm or more but less than 0.45 μm, and particularly preferably 0.30 to 0.40 μm. That is, in the thermoplastic resin compositions according to the second and third embodiments, by using a crystalline polyester resin or a thermoplastic polyester resin (A2) having a glass transition temperature of 80° C. or higher as the thermoplastic polyester resin (A2), the effects of the present invention can be effectively achieved using glass flakes (C) having an average thickness of 6.5 μm or less. If the average thickness of the glass flakes (C) exceeds 6.5 μm, the effects of the present invention cannot be achieved. Furthermore, if the average thickness is below the lower limit of the above range, the glass flakes may become extremely susceptible to cracking, which may result in reduced rigidity and impact resistance.

[0129] The average thickness of the glass flakes is a value measured by the following method. That is, the thickness of 100 or more glass flakes is measured using a scanning electron microscope (SEM) and the measured values ​​are averaged. In this case, the glass flakes may be observed individually with the scanning electron microscope, or the glass flakes may be filled into a resin to be molded, and the resin may be broken and the fracture surface may be observed and measured.

[0130] The average particle size (length) of the glass flakes (C) is preferably 5 to 1000 μm, more preferably 20 to 700 μm, and even more preferably 50 to 200 μm. The average particle size here is the major axis of the glass flakes, and is calculated as the median diameter D50 of the weight-average distribution.

[0131] The glass composition of the glass flakes (C) is not particularly limited, and various glass compositions such as A-glass, C-glass, and E-glass can be appropriately selected and used.

[0132] The glass flakes (C) are preferably surface-treated with a known surface treatment agent, such as a silane coupling agent, methylhydrogensiloxane, titanate coupling agent, or aluminate coupling agent, from the viewpoint of improving mechanical strength. Furthermore, the glass flakes (C) are preferably granulated or bundled with a binder such as an acrylic resin, a urethane resin, an epoxy resin, or an unsaturated polyester resin, from the viewpoint of handling. However, the above-mentioned average particle size range and thickness range of the glass flakes (C) do not apply to the granules or bundles obtained by such granulation or bundling.

[0133] As the glass flakes (C) having an average thickness of less than 0.45 μm used in the present invention, "MEC140FY-D01" (average thickness: 0.35 μm) manufactured by Nippon Sheet Glass Co., Ltd. is commercially available.

[0134] [Content of each component in the thermoplastic resin composition] The total content of the flat cross section glass fiber (B) and the glass flake (C) in the thermoplastic resin composition of the present invention is 10 to 50 parts by mass, preferably 15 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, particularly preferably more than 30 parts by mass, and preferably 45 parts by mass or less, relative to 100 parts by mass of the total content of the thermoplastic resin (A), the flat cross section glass fiber (B), and the glass flake (C). If the total content of the flat cross section glass fiber (B) and the glass flake (C) is less than the above lower limit, the effects of improving the dimensional accuracy, low anisotropy, reduction in the linear expansion coefficient, etc., due to their inclusion are insufficient. On the other hand, if the content exceeds the above upper limit, the fluidity decreases, and the moldability and the appearance of the resulting molded product become inferior.

[0135] In addition, from the viewpoint of obtaining a good balance between the effects of low anisotropy and imparting rigidity by using the flat cross section glass fiber (B) and the effects of reducing the linear expansion coefficient and imparting a good appearance by using the glass flakes (C), the content of the flat cross section glass fiber (B) per 100 parts by mass of the total content of the polycarbonate resin (A1) and the thermoplastic polyester resin (A2) is preferably 8 to 20 parts by mass, particularly 10 to 15 parts by mass, the content of the glass flakes (C) is preferably 15 to 30 parts by mass, particularly 20 to 25 parts by mass, and the content ratio of the flat cross section glass fiber (B) to the glass flakes (C) (flat cross section glass fiber (B) / glass flakes (C)) is preferably in the range of 0.2 to 4.0, particularly 0.5 to 2.0.

[0136] The total content of the thermoplastic resin (A), the flat cross section glass fiber (B), and the glass flake (C) in the thermoplastic resin composition of the present invention is preferably 98% by mass or more, from the viewpoint of fully obtaining the respective effects of containing these components.

[0137] [Phosphorus-Based Transesterification Inhibitor] Since the thermoplastic resin composition of the present invention contains the polycarbonate resin (A1) and the thermoplastic polyester resin (A2) as the thermoplastic resin (A), it is preferable to contain a phosphorus-based transesterification inhibitor in order to inhibit the transesterification reaction between the polycarbonate resin (A1) and the thermoplastic polyester resin (A2).

[0138] Examples of phosphorus-based transesterification inhibitors include organic phosphate compounds. Examples of organic phosphate compounds include alkyl acid phosphate, alkenyl acid phosphate, and metal salts thereof. The alkyl acid phosphate or alkenyl acid phosphate of the phosphate compound is preferably represented by the following formula (I). That is, the alkyl acid phosphate or alkenyl acid phosphate is preferably represented by the following formula (I), and the alkyl acid phosphate metal salt or alkenyl acid phosphate metal salt is preferably a metal salt such as a zinc salt or aluminum salt of the alkyl acid phosphate or alkenyl acid phosphate represented by the following formula (I). O=P(OH) ｎ (OR) ３－ｎ ...(I) (In formula (I), R represents an alkyl group having 8 to 30 carbon atoms or an alkenyl group having 8 to 30 carbon atoms, and n represents an integer of 1 or 2. When n is 1, the two Rs may be the same or different.)

[0139] The alkyl group represented by R in the above formula (I) may be a linear alkyl group or a branched alkyl group. Specific examples of the alkyl group represented by R include octyl, nonyl, isononyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl (stearyl), eicosyl, and tetracosyl groups. The alkenyl group represented by R may also be a linear alkenyl group or a branched alkenyl group. Specific examples of the alkenyl group represented by R include oleyl. n is 1 or 2, and the phosphate compound represented by formula (I) may be a mixture of a phosphate compound with n=1 and a phosphate compound with n=2.

[0140] The number of carbon atoms in the alkyl or alkenyl group represented by R in the above formula (I) is more preferably 12 to 24, and even more preferably 18. The alkyl acid phosphate is particularly preferably a mixture of distearyl acid phosphate in which n=1 and monostearyl acid phosphate in which n=2 in formula (II) below, where O=P(OH). ｎ (OC １８ H ３７ ) ３－ｎ ...(II) Furthermore, as the metal salt of alkyl acid phosphate, a mixture of distearyl acid phosphate zinc salt represented by the following formula (IIIa) and monostearyl acid phosphate zinc salt represented by the following formula (IIIb) is preferred.

[0141]

[0142] These phosphate compounds may be used alone or in combination of two or more. Specific examples of commercially available phosphate compounds include "JP-518Zn" manufactured by Johoku Chemical Industry Co., Ltd. and "AX-71" manufactured by ADEKA Corporation.

[0143] When the thermoplastic resin composition of this embodiment contains a phosphorus-based transesterification inhibitor, the content thereof is preferably 0.001 to 4 parts by mass per 100 parts by mass of the thermoplastic resin (A). By setting the content of the phosphorus-based transesterification inhibitor at or above the above-mentioned lower limit, the effect of suppressing the transesterification reaction between the polycarbonate resin (A1) and the thermoplastic polyester resin (A2) due to the incorporation of the phosphorus-based transesterification inhibitor can be sufficiently obtained. On the other hand, by setting the content of the phosphorus-based transesterification inhibitor at or below the above-mentioned upper limit, it is possible to prevent deterioration of the appearance of the molded article obtained by the incorporation of an excessive amount of the phosphorus-based transesterification inhibitor. From this viewpoint, the content of the phosphorus-based transesterification inhibitor is more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, particularly preferably 0.05 parts by mass or more, even more preferably 0.075 parts by mass or more, and even more preferably 0.1 parts by mass or more, per 100 parts by mass of the thermoplastic resin (A). The content of the phosphorus-based transesterification inhibitor (D) is more preferably 3 parts by mass or less, even more preferably 2 parts by mass or less, particularly preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less, per 100 parts by mass of the thermoplastic resin (A). The thermoplastic resin composition of this embodiment may contain only one type of phosphorus-based transesterification inhibitor, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably within the above range.

[0144] [Other Components] The thermoplastic resin composition of this embodiment may contain other components in addition to those described above, as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include various resins other than thermoplastic resins and resin additives. The other components may be contained alone or in any combination and ratio of two or more. Specific examples of other components include elastomers, mold release agents, stabilizers other than phosphorus-based transesterification inhibitors (heat stabilizers, light stabilizers), colorants (pigments, dyes), reactive compounds, nucleating agents, flame retardants, flame retardant assistants, fillers other than the flat cross-section glass fiber (B) and the glass flakes (C), antistatic agents, antifogging agents, antiblocking agents, flow improvers, plasticizers, dispersants, antibacterial agents, etc.

[0145] <Stabilizer> The thermoplastic resin composition of this embodiment may contain a stabilizer (light stabilizer and / or heat stabilizer) other than the phosphorus-based transesterification inhibitor. Examples of stabilizers include phosphorus-based compounds other than the phosphorus-based transesterification inhibitor, phenol-based compounds, hindered amine-based compounds, sulfur-based stabilizers, etc. Among these, phosphorus-based compounds other than the phosphorus-based transesterification inhibitor and phenol-based compounds are preferred.

[0146] Examples of phosphorus-based compounds other than the phosphorus-based transesterification inhibitor include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; metal acid pyrophosphates such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; phosphates such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphite compounds; and organic phosphonite compounds. Among these, organic phosphite compounds are preferred. The phosphorus-based compounds other than the phosphorus-based transesterification inhibitor may be contained alone or in combination.

[0147] The phenolic compound is preferably a hindered phenolic stabilizer, for example, 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-hydroxyphenylpropionamide], 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-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, etc. The phenolic compound may contain only one type, or two or more types.

[0148] Specific examples of stabilizers include the following: the descriptions in paragraphs 0066 to 0075 of JP-A-2021-063196, the descriptions in paragraphs 0047 to 0057 of JP-A-2018-070722, the descriptions in paragraphs 0030 to 0036 of JP-A-2019-056035, and the descriptions in paragraphs 0053 to 59 of JP-A-2020-045419. These contents are incorporated herein by reference.

[0149] When the thermoplastic resin composition of this embodiment contains a stabilizer, the content thereof is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, and even more preferably 0.05 parts by mass or more, per 100 parts by mass of the thermoplastic resin composition containing the thermoplastic resin (A), the flat cross-section glass fiber (B), and the glass flakes (C). By setting the stabilizer content at or above the lower limit, the effect of suppressing thermal degradation and oxidative degradation of the resin during melt-kneading, molding, and use as a molded product tends to be further improved. Furthermore, the upper limit of the stabilizer content is preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less, per 100 parts by mass of the thermoplastic resin composition. By setting the stabilizer content at or below the upper limit, adverse effects on the appearance and physical properties of molded products due to aggregation of additives such as stabilizers can be effectively suppressed. The thermoplastic resin composition of this embodiment may contain only one stabilizer, or may contain two or more stabilizers. When two or more types are contained, the total amount thereof is preferably within the above range.

[0150] <Release Agent> The thermoplastic resin composition of this embodiment may contain a release agent. Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane-based silicone oils. Specific examples of the release agent can be found in paragraphs 0083 to 0092 of JP 2015-199852 A, the contents of which are incorporated herein by reference.

[0151] When the thermoplastic resin composition of this embodiment contains a release agent, the amount is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the thermoplastic resin composition containing the thermoplastic resin (A), the flat cross section glass fiber (B), and the glass flakes (C). When the content of the release agent is equal to or greater than the lower limit, moldability tends to be further improved. Furthermore, the upper limit of the content of the release agent is preferably 5.0 parts by mass or less, more preferably 1.0 part by mass or less, relative to 100 parts by mass of the thermoplastic resin composition. By keeping the content of the release agent equal to or less than the upper limit, the occurrence of silver streaks tends to be further suppressed. The thermoplastic resin composition of this embodiment may contain only one type of release agent, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably within the above range.

[0152] [Method of Manufacturing Thermoplastic Resin Composition] The method of manufacturing the thermoplastic resin composition of the present invention is not limited, and a wide variety of known methods for manufacturing thermoplastic resin compositions can be used. For example, the thermoplastic resin (A), flat cross-section glass fiber (B), and glass flake (C), as well as the other components described above, may be premixed using a mixer such as a tumbler, Henschel mixer, supermixer, or ribbon blender, and then melt-kneaded using a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, or kneader. Alternatively, the thermoplastic resin composition may be produced without premixing the components, or by premixing only some of the components and feeding them into an extruder using a feeder to melt-knead them. A masterbatch may also be prepared by melt-kneading some of the components, such as a colorant, with the thermoplastic resin (A) to prepare a masterbatch, and then blending the remaining components with this to melt-knead them. It is also preferable to feed inorganic fillers such as flat cross-section glass fiber (B) and glass flake (C) from a side feeder midway through the extruder cylinder.

[0153] The heating temperature during melt-kneading can usually be selected appropriately from the range of 240 to 330°C. If the temperature is too high, it may cause decomposition gases or a decrease in strength due to a decrease in molecular weight. Therefore, it is desirable to select a screw configuration that takes into account shear heat generation, etc. To suppress decomposition during kneading and subsequent molding processes, it is desirable to use antioxidants and heat stabilizers.

[0154] [Physical properties of thermoplastic resin composition] <Molding shrinkage> The molding shrinkage of the thermoplastic resin composition of the present invention, measured by the method described in the Examples section below, is preferably 0.4% or less, more preferably 0.35% or less, and even more preferably 0.3% or less. When the molding shrinkage is below the upper limit, excellent dimensional accuracy is achieved. The smaller this molding shrinkage, the better.

[0155] <Linear expansion coefficient> The linear expansion coefficient of the thermoplastic resin composition of the present invention, measured by the method described in the Examples section below, is 2.1 × 10 in both the MD and TD directions, from the viewpoint of having a linear expansion coefficient at the same level as that of metals and controlling the dimensional accuracy of the molded product to the same level as that of different materials (glass or metal materials). －５ / K ~ 3.2 × 10 －５ / K, and is preferably in the range of 2.2 × 10 －５ / K ~ 2.8 x 10 －５ It is more preferable that the range is .beta. / K.

[0156] <Anisotropy of Dimensional Accuracy> The ratio of the linear expansion coefficients in MD and TD (MD / TD) of the thermoplastic resin composition of the present invention, measured by the method described in the Examples section below, is preferably in the range of 0.8 to 1.1, and more preferably in the range of 0.9 to 1.0, from the viewpoint of low anisotropy of dimensional accuracy.

[0157] <Flexural Modulus> The flexural modulus of the thermoplastic resin composition of the present invention, measured by the method described in the Examples section below, is preferably 7,500 MPa or more, more preferably 9,000 MPa or more, from the viewpoint of rigidity. The higher the flexural modulus, the better, and there is no particular upper limit, but it is usually 15,000 MPa or less.

[0158] [Method for Molding Thermoplastic Resin Composition] The thermoplastic resin composition of the present invention can be pelletized and molded into molded articles by various molding methods. Alternatively, the resin melt-kneaded in an extruder can be directly molded into a sheet, film, profile extrusion molded article, blow molded article, injection molded article, etc. without going through pelletization.

[0159] Examples of molding methods include injection molding, ultra-high speed injection molding, injection compression molding, two-color molding, gas-assisted and other blow molding methods, molding methods using a heat-insulating mold, molding methods using a rapidly heated mold, foam molding (including supercritical fluids), insert molding, IMC (in-mold coating molding), extrusion molding, sheet molding, thermoforming, rotational molding, laminate molding, press molding, etc. Molding methods using a hot runner system can also be used.

[0160] There are no restrictions on the shape, pattern, color, size, etc. of the molded product, and these may be set arbitrarily depending on the application of the molded product.

[0161] [Molded Articles] The thermoplastic resin composition of the present invention has excellent rigidity, dimensional stability, dimensional accuracy and its low anisotropy, moldability, fluidity, and molded article appearance, and is therefore suitable for various molded articles requiring toughness, strength, and appearance while being thin-walled. Specifically, the molded article of the present invention obtained by molding the thermoplastic resin composition of the present invention can be used as, for example, housing parts and lens barrels for cameras, telescopes, microscopes, projection exposure devices, and optical measuring devices; housing parts and mechanical parts for smartphone cameras, in-vehicle cameras, drive recorders, surveillance cameras, and small cameras mounted on drones; housings and mechanical parts for car collision prevention sensors, back monitor sensors, vehicle speed sensors, temperature sensors, and security sensors; frame members and outer panel members for automobiles, motorcycles, bicycles, and wheelchairs; panel members and mechanical parts for home televisions, personal computer displays, in-vehicle monitors, smartphones, and head-mounted displays; and barcode readers and scanner housings and mechanical parts.

[0162] The present invention will be explained in more detail below by showing examples, but the present invention should not be construed as being limited to the following examples.

[0163] [Materials Used] The materials used in the examples and comparative examples are as shown in Tables 1 and 2 below.

[0164]

[0165]

[0166]

[0167]

[0168] [Examples 1 to 7, Comparative Examples 1 to 4] <Production of Thermoplastic Resin Composition> The materials shown in Tables 1A, 1B, 2A, and 2B above were mixed in a tumbler in the amounts (all parts by mass) shown in Tables 3 and 4 below for 20 minutes, and then the mixture was supplied to a twin-screw extruder (TEX25αIII) equipped with one vent, manufactured by The Japan Steel Works, Ltd., and kneaded under conditions of a screw rotation speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 290°C. The molten resin composition extruded in the form of a strand was quenched in a water tank and pelletized using a pelletizer to obtain pellets of the thermoplastic resin composition.

[0169] <Molding of Test Piece I> The obtained pellets were dried at 120°C for 5 hours or more, and then injection molded in an injection molding machine ("SE100EV-A-SHR" manufactured by Sumitomo Heavy Industries, Ltd.) under conditions of a cylinder temperature of 280°C, a mold temperature of 80°C, and a molding cycle of 40 seconds, to prepare test pieces I having a thickness of 2 mm and a length of 100 mm.

[0170] <Molding of Test Piece II> The obtained pellets were dried at 120°C for 5 hours, and then molded into ISO dumbbell test pieces II having a thickness of 4 mm using an injection molding machine ("NEX80" manufactured by Nissei Plastic Industrial Co., Ltd.) under the conditions of a cylinder temperature of 300°C, a mold temperature of 100°C, an injection speed of 100 mm / s, and a holding pressure of 80 MPa.

[0171] [Measurement and Evaluation Methods] <Molding Shrinkage> The 100 mm square test piece I obtained above was conditioned for 24 hours or more at a room temperature of 23° C. and a humidity of 50% RH. Thereafter, the dimensions of the obtained test piece in the MD (Machine Direction, also referred to as the flow direction) and TD (Transverse Direction, also referred to as the transverse direction) directions were measured, and the molding shrinkage (unit: %) was calculated based on the dimensions of the injection molding die.

[0172] <Linear expansion coefficient> A test specimen was obtained by cutting the center of the 100 mm square test specimen I obtained above into a length of 10 mm, width of 10 mm, and thickness of 2 mm in the MD / TD directions, and used to measure the linear expansion coefficient based on ISO 11359-2. The measuring device used was a Hitachi High-Tech Science "TMA7100," and the length of the test specimen was measured. The temperature was raised from -40 to +80°C at a rate of 20°C / min, and the linear expansion coefficient (unit: / K) was calculated from the slope of the dimensional change with respect to the temperature change.

[0173] <Anisotropy of Dimensional Accuracy> The ratio of the linear expansion coefficients in the MD and TD calculated above (MD / TD) was calculated.

[0174] <Flexural Modulus> Using the ISO dumbbell test piece II (thickness: 4 mm) obtained above, the flexural modulus (unit: MPa) was measured at room temperature (23°C) or 80°C in accordance with ISO178.

[0175] <Appearance> The surface appearance of the 100 mm square test piece I obtained above was observed and evaluated according to the following criteria: A: No lifting of the glass-based filler was observed on the molded surface, and it was extremely good. B: Slight lifting of the glass-based filler was observed. C: The lifting of the glass-based filler was noticeable and it was whitened. D: The lifting of the glass-based filler was so great that it was not suitable for practical use.

[0176] <Chemical resistance> A 0.1N aqueous solution of sodium peroxide was applied to the 100 mm square test piece I obtained above, and the test piece was then left in an environment of 23°C and 50% RH for 10 minutes. The surface appearance of the test piece was then observed and evaluated according to the following criteria: A: No change B: Minor change C: Obvious change D: Attacked

[0177] The evaluation results are shown in Tables 3 and 4.

[0178]

[0179]

[0180] Table 3 shows that the thermoplastic resin composition of the present invention can be used to mold molded articles with excellent rigidity, dimensional accuracy, low anisotropy, and appearance. Furthermore, the combined use of polycarbonate resin (A1) and thermoplastic polyester resin (A2) also provides excellent chemical resistance. In contrast, as shown in Table 4, Comparative Examples 1 and 2, which used glass flakes with a large average thickness, produced molded articles with poor appearance. Comparative Example 3, which contained a small total content of flat cross-section glass fiber (C) and glass flake (D), had high molding shrinkage and linear expansion coefficients, resulting in poor dimensional accuracy.

[0181] [Examples 8 to 11] Pellets of thermoplastic resin compositions were obtained in the same manner as in Example 1, except that the blending ratios of the raw materials were changed as shown in Table 5. The obtained pellets were subjected to various evaluations in the same manner as in Example 1. The flexural modulus test was performed at room temperature (23°C) as well as at a temperature of 80°C. The results are shown in Table 5.

[0182]

[0183] A comparison between Example 8 and Example 10 and a comparison between Example 9 and Example 11 in Table 5 shows that by using a resin with a high glass transition temperature such as polyethylene naphthalate as the thermoplastic polyester resin (A2), a thermoplastic resin composition can be obtained that not only has properties equivalent to those obtained when polyethylene terephthalate or the like is used, but also exhibits high rigidity even at high temperatures such as 80°C.

[0184] 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 within the scope of the effects of the invention. This application is based on Japanese Patent Application No. 2024-117877, filed on July 23, 2024, and is incorporated by reference in its entirety.

[0185] The thermoplastic resin composition of the present invention is suitable for various molded articles that require thin wall thickness, low anisotropy in dimensional accuracy, and good appearance, and can be used in a wide range of fields such as interior and exterior parts for automobiles, etc., and housings for electric and electronic devices, office automation equipment, etc., and has very high industrial applicability.

Claims

1. A thermoplastic resin composition containing a thermoplastic resin (A), a flat cross section glass fiber (B), and glass flakes (C), wherein the thermoplastic resin (A) contains more than 10% by mass and not more than 80% by mass of a polycarbonate resin (A1) and 20% by mass or more and less than 90% by mass of a thermoplastic polyester resin (A2), wherein the total content of the flat cross section glass fiber (B) and the glass flakes (C) is 10 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the total content of the thermoplastic resin (A), the flat cross section glass fiber (B), and the glass flakes (C), and wherein the average thickness of the glass flakes (C) is less than 0.45 μm.

2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) contains 50% by mass or more and 80% by mass or less of a polycarbonate resin (A1) and 20% by mass or more and 50% by mass or less of a thermoplastic polyester resin (A2).

3. The thermoplastic resin composition according to claim 1, wherein the polyester resin (A2) is a crystalline thermoplastic polyester resin.

4. The thermoplastic resin composition according to claim 1, wherein the glass transition temperature of the polyester resin (A2) is 80°C or higher.

5. The thermoplastic resin composition according to claim 1, wherein the thermoplastic polyester resin (A2) is one or more selected from the group consisting of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.

6. The thermoplastic resin composition according to claim 5, wherein the thermoplastic polyester resin (A2) contains at least polyethylene naphthalate.

7. The thermoplastic resin composition according to claim 5, wherein the thermoplastic polyester resin (A2) contains at least polyethylene terephthalate, and the intrinsic viscosity of the polyethylene terephthalate is 0.50 dL / g or more and 2.0 dL / g or less.

8. The thermoplastic resin composition according to claim 1, wherein the viscosity average molecular weight of the polycarbonate resin (A1) is 16,000 to 50,000.

9. The thermoplastic resin composition according to claim 1, wherein the mass ratio of the flat cross section glass fiber (B) to the glass flake (C) (flat cross section glass fiber (B) / glass flake (C)) is in the range of 0.2 to 4.

0.

10. The thermoplastic resin composition according to claim 1, wherein the average minor axis of the fiber cross section of said flat cross section glass fiber (B) is 3 to 20 μm.

11. The thermoplastic resin composition according to claim 1, wherein the average flatness (long diameter / short diameter of fiber cross section) of the flat cross section glass fiber (B) is greater than 1.5 and less than 8.

12. The linear expansion coefficient in the MD and TD directions measured based on ISO11359-2 is 2.1 x 10 －５ / K ~ 3.2 × 10 －５ / K, and the ratio of the linear expansion coefficients in MD and TD is in the range of 0.8 to 1.

1.

13. A thermoplastic resin composition containing a thermoplastic resin (A), flat cross section glass fibers (B), and glass flakes (C), wherein the thermoplastic resin (A) contains 50% by mass or more and 80% by mass or less of a polycarbonate resin (A1) and 20% by mass or more and 50% by mass or less of a thermoplastic polyester resin (A2), the thermoplastic polyester resin (A2) is a crystalline polyester resin, the total content of the flat cross section glass fibers (B) and the glass flakes (C) is 10 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the total content of the thermoplastic resin (A), the flat cross section glass fibers (B), and the glass flakes (C), and the average thickness of the glass flakes (C) is 0.65 μm or less.

14. A thermoplastic resin composition containing a thermoplastic resin (A), a flat cross section glass fiber (B), and glass flakes (C), wherein the thermoplastic resin (A) contains 50% by mass or more and 80% by mass or less of a polycarbonate resin (A1) and 20% by mass or more and 50% by mass or less of a thermoplastic polyester resin (A2), wherein the glass transition temperature of the thermoplastic polyester resin (A2) is 80°C or higher, wherein the total content of the flat cross section glass fiber (B) and the glass flakes (C) is 10 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the total content of the thermoplastic resin (A), the flat cross section glass fiber (B), and the glass flakes (C), and wherein the average thickness of the glass flakes (C) is 0.65 μm or less.

15. The thermoplastic resin composition according to claim 14, wherein the glass transition temperature of the polyester resin (A2) is 90°C or higher.

16. A molded article obtained from the thermoplastic resin composition according to any one of claims 1 to 15.

17. The molded article according to claim 16, which is selected from the group consisting of housing parts and lens barrels for cameras, telescopes, microscopes, projection exposure devices, or optical measuring devices; housing parts and mechanical parts for smartphone cameras, in-vehicle cameras, drive recorders, surveillance cameras, or small cameras mounted on drones; housings and mechanical parts for automobile collision prevention sensors, rear monitor sensors, vehicle speed sensors, temperature sensors, or security sensors; frame members and outer panel members for automobiles, motorcycles, bicycles, or wheelchairs; panel members and mechanical parts for home televisions, personal computer displays, in-vehicle monitors, smartphones, or head-mounted displays; and housings and mechanical parts for barcode readers or scanners.

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