Polycarbonate resin coated molded products

Abstract

Polycarbonate resin coated molded product with excellent jet black and gloss. [Solution] A polycarbonate resin coated molded article having a black coating layer on the surface of a molded article of a resin composition containing 100 parts by mass of polycarbonate resin (A), 8 to 60 parts by mass of at least one flow modifier (B) selected from the group consisting of acrylonitrile-styrene copolymer (B1), polycaprolactone polymer (B2), and polycarbonate oligomer (B3), 10 to 85 parts by mass of flaky glass filler (C) having an average thickness of 0.45 to 1 μm, and 10 to 60 parts by mass of flat cross section glass fiber (D) having an aspect ratio of more than 1.5 and not more than 5, wherein the mass ratio (D) / (C) of the contents of the flat cross section glass fiber (D) to the contents of the flaky glass filler (C) is 0.1 to 2.5, and the mass ratio (C) / (B) of the contents of the flaky glass filler (C) to the contents of the flow modifier (B) is 0.8 to 7.

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin coated molded article, and more particularly to a polycarbonate resin coated molded article having excellent jet blackness and gloss, which has a black coating layer on the surface of a polycarbonate resin composition molded article that has a small molding shrinkage rate, a linear expansion coefficient at the same level as that of metal, extremely small anisotropy, high rigidity, excellent impact resistance, and excellent flowability and appearance of the molded article. [Background technology]

[0002] Polycarbonate resins have excellent mechanical properties and are widely used as engineering plastics. Depending on the field of use, various reinforcing agents and additives have been blended into them to improve their properties, particularly their mechanical properties. In fields requiring high mechanical strength and rigidity, fibrous reinforcing materials such as glass fiber have been used. However, resin compositions containing polycarbonate resins blended with glass fiber have excellent mechanical strength and rigidity, but suffer from the drawback of anisotropic molding shrinkage due to the orientation of the fibers. In recent years, in imaging or optical devices equipped with lenses, such as cameras, efforts have been made to use resin for the lens barrel cylindrical body (lens barrel) in order to reduce weight and cost, and materials such as polycarbonate resin reinforced with glass fiber are also being used. In lens barrels, the material must have sufficient rigidity and high dimensional accuracy to prevent the optical axis of the optical system from shifting during focusing or zooming.

[0003] Glass fibers having specific cross-sectional shapes have also been used to improve dimensional accuracy. Patent Document 1 proposes an aromatic polycarbonate resin composition with improved mechanical strength and flame retardancy, which is composed of a polycarbonate resin, flat cross-section glass fibers having a specific cross-sectional shape, and a phosphate ester-based flame retardant. In its examples, the polycarbonate resin composition is described, which contains a specific ratio of flat cross-section glass fibers and a 5 μm-thick flake glass filler, and further contains a phosphate ester-based flame retardant and polytetrafluoroethylene. However, its low anisotropy is not fully satisfactory, and the use of a phosphorus-based flame retardant tends to cause a decrease in impact strength and heat resistance due to plasticization of the polycarbonate resin. Therefore, the impact strength, heat resistance, and low anisotropy are insufficient and unsatisfactory. Furthermore, since the lens barrel is a composite of resin material and metals (or alloys) such as aluminum or magnesium, it is necessary to prevent misalignment of the optical axis due to differences in thermal expansion even over a wide range of operating temperatures, and the resin material is required to have a linear expansion coefficient similar to that of these metals. Furthermore, molded articles made from these polycarbonate resin compositions may be surface-painted depending on their applications. In some applications, such as interior and exterior components of automobiles and housings and frames of home appliances, a black paint (sometimes called "piano black") with excellent jet blackness and gloss has been preferred from the standpoint of design. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5021918 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above circumstances, and an object (problem) of the present invention is to provide a polycarbonate resin coated molded article having excellent jet blackness and gloss, which has a black coating layer on the surface of a molded article made from a polycarbonate resin composition that has a small molding shrinkage rate, a linear expansion coefficient at the same level as that of metal, extremely small anisotropy, high rigidity, excellent impact resistance, and excellent flowability and appearance of the molded article. [Means for solving the problem]

[0006] As a result of extensive research conducted by the present inventors in order to achieve the above-mentioned objects, they have found that a polycarbonate resin coated molded article that solves the above-mentioned problems can be obtained by providing a black coating layer on the surface of a molded article made of a polycarbonate resin composition that contains, in specific amounts, polycarbonate resin (A), a flow modifier (B) selected from an acrylonitrile-styrene copolymer (B1), a polycaprolactone polymer (B2), and a polycarbonate oligomer (B3), scaly glass filler (C) having an average thickness of 0.45 to 1 μm, flat cross-section glass fiber (D) having an aspect ratio of more than 1.5 and not more than 8, and a fatty acid ester (E), each in a specific amount, and thereby completing the present invention. The present invention relates to the following polycarbonate resin coated molded article.

[0007] 1. A polycarbonate resin coated molded article having a black coating layer on the surface of a molded article of a resin composition containing, relative to 100 parts by mass of polycarbonate resin (A), 8 to 60 parts by mass of at least one flow modifier (B) selected from the group consisting of acrylonitrile-styrene copolymer (B1), polycaprolactone polymer (B2), and polycarbonate oligomer (B3), 10 to 85 parts by mass of flaky glass filler (C) having an average thickness of 0.45 to 1 μm, and 10 to 60 parts by mass of flat cross section glass fiber (D) having an aspect ratio of more than 1.5 and not more than 5, wherein the mass ratio (D) / (C) of the contents of the flat cross section glass fiber (D) to the contents of the flaky glass filler (C) is 0.1 to 2.5, and the mass ratio (C) / (B) of the contents of the flaky glass filler (C) to the contents of the flow modifier (B) is 0.8 to 7. 2. A polycarbonate resin coated molded product as described in 1 above that is integrated with a metal plate. 3. A polycarbonate resin coated molded product according to 1 or 2 above, wherein the thickness of the black coating layer is 5 to 50 μm. 4. The linear expansion coefficient of the resin composition in the MD and TD directions measured in accordance with ISO 11359-2 is 2.1 x 10 -5 / K~2.8×10 -5 4. The coated molded polycarbonate resin article according to any one of 1 to 3 above, wherein the linear expansion coefficient ratio in MD to TD is 0.9 to 1.1. 5. A polycarbonate resin coated molded product according to any one of 1 to 4 above, wherein the resin composition does not contain a phosphorus-based flame retardant, or if it contains one, the content thereof is 1 part by mass or less per 100 parts by mass of the polycarbonate resin (A). 6. A polycarbonate resin coated molded article according to any one of 1 to 5 above, wherein the resin composition does not contain a fibril-forming fluororesin, or if it contains one, the content thereof is 1 part by mass or less per 100 parts by mass of the polycarbonate resin (A). 7. A polycarbonate resin coated molded product according to any one of 1 to 6 above, which is a molded product selected from the group consisting of 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, rear 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 reader and scanner housings and mechanical parts. [Effects of the Invention]

[0008] The polycarbonate resin coated molded article of the present invention has excellent jet blackness and gloss. [Brief explanation of the drawings]

[0009] [Figure 1] 1A and 1B are diagrams showing insert-molded articles produced in examples and comparative examples of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below with reference to embodiments and examples. In this specification, unless otherwise specified, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0011] [Polycarbonate resin (A)] The polycarbonate resin (A) used in the polycarbonate resin composition is not particularly limited, and various types can be used. Polycarbonate resins can be classified into aromatic polycarbonate resins in which the carbons directly bonded to the carbonate bonds are aromatic carbons, and aliphatic polycarbonate resins in which the carbons directly bonded to the carbonate bonds are aliphatic carbons, and either can be used. Among these, aromatic polycarbonate resins are preferred as the polycarbonate resin (A) from the viewpoints of heat resistance, mechanical properties, electrical properties, etc.

[0012] Among the monomers that are raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include: 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; 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;

[0013] 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A), 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C), 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-methoxy-4-hydroxyphenyl)propane, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-cyclohexyl-4-hydroxyphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)(4-propenylphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-naphthylethane, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)hexane, 1,1-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)octane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)nonane, 1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(4-hydroxyphenyl)dodecane, Bis(hydroxyaryl)alkanes such as;

[0014] 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,4-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-propyl-5-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-tert-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-tert-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane, 1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexane, Bis(hydroxyaryl)cycloalkanes such as;

[0015] 9,9-bis(4-hydroxyphenyl)fluorene, Cardo structure-containing bisphenols such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene;

[0016] 4,4'-dihydroxydiphenyl sulfide, Dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; 4,4'-dihydroxydiphenyl sulfone, dihydroxydiarylsulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone; etc.

[0017] Of these, bis(hydroxyaryl)alkanes are preferred, and bis(4-hydroxyphenyl)alkanes are particularly preferred. In particular, from the standpoints of impact resistance and heat resistance, 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A) and 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C) are preferred. The aromatic dihydroxy compounds may be used alone or in any combination of two or more in any ratio.

[0018] Among the monomers that serve 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.

[0019] Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformates of dihydroxy compounds and monochloroformates of dihydroxy compounds; and the like.

[0020] 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.

[0021] The method for producing the polycarbonate resin (A) is not particularly limited, and any method can be used. Examples include interfacial polymerization, melt transesterification, ring-opening polymerization of a cyclic carbonate compound, and solid-phase transesterification of a prepolymer. Among these, the interfacial polymerization and melt transesterification methods are preferred because they have a greater effect of improving moist heat resistance, and the interfacial polymerization method is particularly preferred.

[0022] The molecular weight of the polycarbonate resin (A), expressed as a viscosity average molecular weight (Mv) calculated from the solution viscosity measured at 25°C using methylene chloride as a solvent, is preferably 10,000 to 50,000, more preferably 11,000 to 40,000, and even more preferably 12,000 to 35,000, and particularly preferably 13,000 to 30,000. By setting the viscosity average molecular weight to at least the lower limit of the above range, the mechanical strength of the polycarbonate resin composition can be further improved, and by setting the viscosity average molecular weight to at most the upper limit of the above range, the decrease in fluidity of the polycarbonate resin composition can be further suppressed and improved, and molding processability can be improved, making molding process easier. Two or more polycarbonate resins having different viscosity average molecular weights may be mixed together, and in this case, polycarbonate resins having viscosity average molecular weights outside the above-mentioned preferred range may be mixed.

[0023] In the present invention, the viscosity average molecular weight [Mv] of the polycarbonate resin (A) and the polycarbonate oligomer (B3) is determined by measuring the intrinsic viscosity [η] (unit: dl / g) at a temperature of 25°C using methylene chloride as a solvent with an Ubbelohde viscometer, and then 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 the specific viscosity [η] at each solution concentration [C] (g / dl). sp ] was measured and the value was calculated according to the following formula.

number

[0024] The polycarbonate resin (A) may be not only virgin raw materials but also polycarbonate resin recycled from used products (so-called material-recycled polycarbonate resin), and it is also preferable to contain both virgin polycarbonate resin and recycled polycarbonate resin, or it may consist of recycled polycarbonate resin. When recycled polycarbonate resin is contained, the proportion of recycled polycarbonate resin in polycarbonate resin (A) is preferably 30 mass% or more, 40 mass% or more, 50 mass% or more, 60 mass% or more, or 80 mass% or more, and it is also preferable that the recycled polycarbonate resin is 100 mass%.

[0025] Furthermore, in the polycarbonate resin composition, the polycarbonate resin may be further 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.

[0026] [Flow modifier (B)] The polycarbonate resin composition contains at least one flow modifier (B) selected from the group consisting of an acrylonitrile-styrene copolymer (B1), a polycaprolactone polymer (B2), and a polycarbonate oligomer (B3). The content of the flow modifier (B) is 5 to 60 parts by mass relative to 100 parts by mass of the polycarbonate resin (A).

[0027] [Acrylonitrile-styrene copolymer (B1)] The acrylonitrile-styrene copolymer is a copolymer of acrylonitrile and a styrene monomer, and may further be a copolymer with other copolymerizable monomers.

[0028] Examples of the styrene monomer constituting the acrylonitrile-styrene copolymer include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene, and styrene and α-methylstyrene are more preferred, with styrene being particularly preferred.

[0029] Examples of copolymerizable monomers other than styrene-based monomers and acrylonitrile include (meth)acrylic acid ester-based monomers, maleimide-based monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide, and α,β-unsaturated carboxylic acids and anhydrides thereof such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid. Of these, (meth)acrylic acid ester monomers are preferred, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate, with methyl methacrylate being particularly preferred.

[0030] The term "(meth)acrylate" includes both methacrylate and acrylate, and the term "(meth)acrylic acid ester" includes both methacrylic acid ester and acrylic acid ester.

[0031] The method for producing the acrylonitrile-styrene copolymer is not limited, and known methods can be used, such as bulk polymerization, emulsion polymerization, solution polymerization, and suspension polymerization.

[0032] The content of acrylonitrile-derived monomer units in the acrylonitrile-styrene copolymer is preferably 5 to 50 mass%, more preferably 8 to 45 mass%, and the content of styrene-derived units is preferably 50 to 95 mass%, more preferably 55 to 92 mass%.

[0033] The melt volume rate (MVR) of acrylonitrile-styrene copolymer is 5 to 100 cm at 220°C and a load of 10 kg. 3 / 10 minutes range is preferable, 10 to 80 cm 3 / 10 minutes is more preferable. The mass average molecular weight (Mw) of the acrylonitrile-styrene copolymer is preferably 60,000 to 220,000, and more preferably 80,000 to 200,000. In the present invention, the mass average molecular weight (Mw) of the acrylonitrile-styrene copolymer is a mass average molecular weight measured by gel permeation chromatography (GPC) and converted into polystyrene.

[0034] Examples of the acrylonitrile-styrene copolymer include an acrylonitrile-styrene copolymer (AS resin) and an acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), with an acrylonitrile-styrene copolymer (AS resin) being particularly preferred.

[0035] When the acrylonitrile-styrene copolymer (B1) is contained, the content thereof is preferably 10 to 50 parts by mass relative to 100 parts by mass of the polycarbonate resin (A).

[0036] [Polycaprolactone polymer (B2)] Examples of the polycaprolactone polymer (B2) include polycaprolactone, polycaprolactone polyols such as polycaprolactone diol and polycaprolactone triol, and among these, polycaprolactone is preferred.

[0037] Polycaprolactone is a polymer of caprolactone, particularly ε-caprolactone, that is, a polymer or copolymer having a repeating unit of [-CH-CH-CH-CH-CH-CO-O-], and the polymer contains at least 70% by mass, preferably 75% by mass or more, and more preferably 80% by mass or more of such a structural unit.

[0038] When polycaprolactone is a copolymer of ε-caprolactone and another monomer, examples of the monomer copolymerizable with ε-caprolactone include lactone monomers such as β-propiolactone, pivalolactone, and butyrolactone; alkylene oxides such as ethylene oxide, 1,2-propionoxide, 1,3-propylene oxide, and tetrahydrofuran; unsaturated monomers such as styrene, methyl methacrylate, and butadiene; and coupling agents such as dimethyl terephthalate and diphenyl carbonate. These may be used alone or in combination of two or more. Some of the hydrogen atoms in the methylene chain of the polycaprolactone may be substituted with halogen atoms or hydrocarbon groups, and the polycaprolactone may be end-treated by esterification, etherification, or the like.

[0039] The number average molecular weight of polycaprolactone is preferably 200 to 10,000, more preferably 300 to 5,000, and even more preferably 400 to 3,000, as determined by gel permeation chromatography (GPC) and converted into polystyrene. The method for producing polycaprolactone is not particularly limited, but may be a method of ring-opening polymerization of ε-caprolactone using a suitable initiator such as alcohol, glycol, or water and a catalyst such as titanium tetrabutoxide or tin chloride.

[0040] When the polycaprolactone polymer (B2) is contained, the content thereof is preferably 10 to 50 parts by mass relative to 100 parts by mass of the polycarbonate resin (A).

[0041] [Polycarbonate oligomer (B3)] The polycarbonate oligomer (B3) is preferably one obtained by the reaction of an aromatic dihydroxy compound with a carbonate precursor such as phosgene, or by the transesterification reaction of an aromatic dihydroxy compound with diphenyl carbonate or the like.

[0042] Examples of aromatic dihydroxy compounds include those described as raw materials for the polycarbonate resin (A). Among these, bis(hydroxyaryl)alkanes are preferred, and bis(4-hydroxyphenyl)alkanes are particularly preferred, with 2,2-bis(4-hydroxyphenyl)propane and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane being particularly preferred, and 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A) being most preferred.

[0043] The viscosity average molecular weight [Mv] of the polycarbonate oligomer is preferably 1500 or more, more preferably 2000 or more, and is preferably 9500 or less, more preferably 9000 or less. The method for determining the viscosity average molecular weight [Mv] of the polycarbonate oligomer is as described above.

[0044] In the interfacial polymerization method using phosgene, the degree of polymerization of the polycarbonate oligomer can be adjusted by adding a molecular weight modifier, preferably a monohydric phenol or an alkyl-substituted phenol, to the polymerization system to block the terminals. Specific preferred examples of the monohydric phenol or alkyl-substituted phenol include long-chain alkyl-substituted phenols such as butylphenol, octylphenol, nonylphenol, decanylphenol, tetradecanylphenol, heptadecanylphenol, and octadecanylphenol. The amount of the molecular weight modifier added is preferably 3 to 70 mol % based on the aromatic dihydroxy compound.

[0045] When the polycarbonate oligomer (B3) is contained, the content thereof is preferably 10 to 50 parts by mass per 100 parts by mass of the polycarbonate resin (A).

[0046] [Flake-like glass filler (C)] The polycarbonate resin composition contains flaky glass filler (C) having an average thickness of 0.45 to 1 μm. The glass flake filler (C) has an average thickness of 0.45 to 1 μm, which is thinner than the approximately 5 μm thickness of ordinary glass flake fillers. The average thickness of the glass flake filler (C) is preferably 0.5 to 0.9 μm, more preferably 0.55 to 0.85 μm, and particularly preferably 0.6 to 0.8 μm. If the average thickness exceeds the upper limit of the above range, the elastic modulus of the polycarbonate resin composition tends to decrease. If the average thickness is below the lower limit of the above range, the glass flake filler becomes extremely susceptible to cracking, reducing rigidity and impact resistance, which are undesirable.

[0047] The average thickness of the glass flake filler is a value measured by the following method: using a scanning electron microscope (SEM), the thickness of 100 or more glass flake fillers is measured and the measured values ​​are averaged.

[0048] The average particle size (length) of the scaly glass filler (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 scaly glass filler, and is calculated as the median diameter of the weight-average distribution.

[0049] The glass flake filler (C) is 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 flake filler is 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 average particle size range and thickness range of the glass flake filler described above do not apply to the granules or bundles obtained by such granulation or bundling. Furthermore, the glass composition of the glass flake filler is not particularly limited, and various glass compositions, such as A-glass, C-glass, and E-glass, can be appropriately selected and used.

[0050] The content of the flaky glass filler (C) is 10 to 85 parts by mass, and preferably 15 to 80 parts by mass, per 100 parts by mass of the polycarbonate resin (A).

[0051] [Flat cross-section glass fiber (D)] The polycarbonate resin composition contains flat cross section glass fibers (D) having an aspect ratio of more than 1.5 and not more than 6 in combination with the above-mentioned thin-walled scaly glass filler (C). By using such flat cross section glass fibers (D) in combination with the scaly glass filler (C), it becomes possible to obtain a polycarbonate resin composition that is excellent in strength and low anisotropy and has a linear expansion coefficient at the same level as that of aluminum, magnesium metal, etc.

[0052] The flatness of the flat cross section glass fibers (D) is preferably 1.6 to 5 in average, i.e., the ratio of the major axis (width) to the minor axis (thickness) in the cross section in the fiber direction of the glass fibers (width / thickness, hereinafter referred to as "flatness"). The aspect ratio of a flat cross-section glass fiber is a value measured by the following method: using a scanning electron microscope (SEM), the major axis (width) and minor axis (thickness) of 10 or more flat cross-section glass fibers in the cross section in the fiber direction are measured and averaged.

[0053] The average major axis (width) of the fiber cross section of the flat cross section glass fiber (D) 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 minor axis (thickness) of the fiber cross section of the flat cross section glass fiber (D) is preferably 3 to 20 μm, more preferably 4 to 15 μm, and even more preferably 5 to 12 μm.

[0054] The average fiber length of the flat cross section glass fibers (D) is preferably 0.5 to 20 mm, more preferably 1 to 15 mm, and even more preferably 2 to 10 mm. The average fiber length of the flat cross section glass fibers is determined by measuring the fiber lengths of 100 or more flat cross section glass fibers using a scanning electron microscope (SEM) and averaging them. The ratio of the average fiber length to the average fiber diameter (aspect ratio) of the flat cross section glass fibers (D) is preferably 2 to 120, more preferably 2.5 to 70, and even more preferably 3 to 50. If the ratio of the average fiber length to the average fiber diameter (aspect ratio) of the flat cross section glass fibers is less than 2, the mechanical strength tends to decrease, and conversely, if it exceeds 120, warpage and anisotropy tend to increase and the appearance of the molded article tends to deteriorate significantly. The average fiber diameter of flat cross-section glass fibers is determined by measuring the cross-sectional areas of 10 or more flat cross-section glass fibers using an electron microscope photograph or the like, and calculating the average of the converted fiber diameters, which are the diameters of circular cross-section glass fibers having the same cross-sectional area as each of the measured cross-sectional areas.

[0055] As the flat cross section glass fiber (D), any glass fiber commonly used in thermoplastic resins, such as A-glass, E-glass, or alkali-resistant glass containing a zirconia component, can be used. Among these, the flat cross section glass fiber (D) used in the present invention is preferably alkali-free glass (E-glass) for the purpose of improving the thermal stability of the polycarbonate resin composition.

[0056] The flat cross section glass fiber (D) can be surface treated with a silane coupling agent such as aminosilane or epoxysilane in order to improve adhesion to the polycarbonate resin.

[0057] The flat cross section glass fiber (D) 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. The sizing agent is not particularly limited, but examples thereof include urethane-based, epoxy-based, and acrylic-based sizing agents.

[0058] The content of the flat cross section glass fiber (D) is 10 to 60 parts by mass relative to 100 parts by mass of the polycarbonate resin (A). If the content of the flat cross section glass fiber (D) is low, the elastic modulus and impact resistance will be insufficient, and conversely, if it is too high, the impact resistance and fluidity will be insufficient. The content of the flat cross section glass fiber (D) is preferably 15 to 55 parts by mass.

[0059] The total content of the scaly glass filler (C) and the flat cross section glass fiber (D) is preferably 30 to 100 parts by mass per 100 parts by mass of the polycarbonate resin (A).

[0060] [Mass ratio (D) / (C) of the flat cross-section glass fiber (D) and the scaly glass filler (C)] The mass ratio (D) / (C) of the flat cross section glass fiber (D) to the scaly glass filler (C) is 0.1 to 2.5.

[0061] [Mass ratio of the contents of the flaky glass filler (C) and the flow modifier (B): (C) / (B)] The mass ratio (C) / (B) of the contents of the flaky glass filler (C) and the flow improver (B) is 0.8-7. It is preferable that (C) / (B) is 0.9-6.

[0062] [Additives, etc.] The polycarbonate resin composition may contain additives other than those described above, such as stabilizers, release agents, flame retardants, fluorescent whitening agents, pigments, dyes, impact resistance improvers, antistatic agents, plasticizers, compatibilizers, etc. These additives may be blended singly or in combination of two or more.

[0063] As the release agent, a wide variety of known release agents can be used, including, for example, aliphatic carboxylic acid amide compounds, 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 silicone oils.

[0064] Examples of the aliphatic carboxylic acid amide compounds include compounds obtained by a dehydration reaction between a higher aliphatic monocarboxylic acid and / or a polybasic acid and a diamine. As the higher aliphatic monocarboxylic acid, saturated aliphatic monocarboxylic acids and hydroxycarboxylic acids having 16 or more carbon atoms are preferred, and examples thereof include palmitic acid, stearic acid, behenic acid, montanic acid, and 12-hydroxystearic acid. Examples of polybasic acids include aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, pimelic acid, and azelaic acid; aromatic dicarboxylic acids such as phthalic acid and terephthalic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and cyclohexylsuccinic acid. Examples of diamines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, metaxylylenediamine, tolylenediamine, paraxylylenediamine, phenylenediamine, and isophoronediamine. The aliphatic carboxylic acid amide compound is preferably a compound obtained by polycondensation of stearic acid, sebacic acid, and ethylenediamine, and more preferably a compound obtained by polycondensation of 2 moles of stearic acid, 1 mole of sebacic acid, and 2 moles of ethylenediamine. In addition to bisamide compounds obtained by reacting diamines with aliphatic carboxylic acids, such as N,N'-methylenebisstearamide and N,N'-ethylenebisstearamide, dicarboxylic acid amide compounds such as N,N'-dioctadecylterephthalamide can also be suitably used.

[0065] Examples of aliphatic carboxylic acids include saturated or unsaturated aliphatic mono-, di-, or tri-carboxylic acids. Aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are mono- or di-carboxylic acids having 6 to 36 carbon atoms, with saturated aliphatic mono-carboxylic acids having 6 to 36 carbon atoms being more preferred. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetralinic acid, montanic acid, adipic acid, and azelaic acid.

[0066] The aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol can be, for example, the same as the aliphatic carboxylic acid. On the other hand, the alcohol can be, for example, a saturated or unsaturated monohydric or polyhydric alcohol. These alcohols may have a substituent such as a fluorine atom or an aryl group. Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, and dipentaerythritol. Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, and esters of montanic acid and polyfunctional alcohols.

[0067] Examples of aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. Note that the aliphatic hydrocarbon compounds also include alicyclic hydrocarbon compounds. The number average molecular weight of the aliphatic hydrocarbon compounds is preferably 5,000 or less.

[0068] Examples of polyolefin waxes include polyethylene wax, polypropylene wax, and polyethylene propylene wax. The polyolefin wax may be unmodified or modified. Examples of modified polyolefin waxes include vinyl ester-modified polyolefin wax, acid-modified polyolefin wax, and oxidized polyolefin wax.

[0069] The polycarbonate resin composition preferably contains 0.05 to 1.3 parts by mass of a release agent relative to 100 parts by mass of the polycarbonate resin. The release agent may be contained in one kind or in two or more kinds.

[0070] A preferred example of the pigment is carbon black, which can be used to color molded articles of polycarbonate resin compositions black.

[0071] The carbon black is not particularly limited, and various carbon blacks can be used, such as oil furnace black, channel black, acetylene black, and ketjen black.

[0072] The average particle size of carbon black is not limited, but is preferably 5 to 60 nm, and more preferably 7 to 55 nm. The average particle size of carbon black can be determined using a transmission electron microscope.

[0073] The carbon black content is preferably 0.1 to 2.0 parts by mass per 100 parts by mass of the polycarbonate resin (A). If the carbon black content is less than the lower limit, it is difficult to obtain the desired coloring (jet blackness), and if it is more than the upper limit, the jet blackness and impact resistance are likely to be impaired due to poor dispersion of the carbon black.

[0074] It is preferable to compound carbon black in advance as a masterbatch containing carbon black at a high concentration in order to improve the handleability during production of the resin composition and the uniform dispersibility in the resin composition. In this case, the resin used for the carbon black masterbatch may be a polycarbonate resin or a resin other than a polycarbonate resin. It is also preferable to use a styrene-based resin, which makes it easy to disperse high-concentration carbon black and to prepare a masterbatch. The carbon black concentration in the carbon black masterbatch is usually about 20 to 50 mass %.

[0075] It is preferable that the polycarbonate resin composition does not contain a phosphorus-based flame retardant. That is, the polycarbonate resin composition does not contain a phosphorus-based flame retardant, or if it does contain one, the content thereof is preferably 1 part by mass or less, more preferably 0.7 parts by mass or less, and particularly preferably 0.5 parts by mass or less, per 100 parts by mass of the polycarbonate resin (A). If the phosphorus-based flame retardant is contained in an amount exceeding this range, the impact resistance and thermal stability of the polycarbonate resin composition tend to deteriorate, which is undesirable.

[0076] Furthermore, it is preferable that the polycarbonate resin composition does not contain a fibril-forming fluororesin, which is an anti-dripping agent. That is, it is preferable that the polycarbonate resin composition does not contain a fibril-forming fluororesin, or if it does contain one, that the content thereof is 1 part by mass or less, preferably 0.7 parts by mass or less, and particularly preferably 0.5 parts by mass or less, per 100 parts by mass of the polycarbonate resin (A). If the polycarbonate resin composition contains a fibril-forming fluororesin in an amount exceeding this range, the viscosity of the polycarbonate resin composition tends to increase, which deteriorates moldability, and this is not preferable.

[0077] The polycarbonate resin composition may also contain other resins in addition to the polycarbonate resin (A) and the flow modifier (B). Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; polyphenylene ether resin; polyphenylene sulfide resin; and polysulfone resin. One type of other resin may be contained, or two or more types may be contained in any combination and ratio. However, when other resins are contained, the content thereof is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, per 100 parts by mass of the polycarbonate resin (A).

[0078] [Method for producing polycarbonate resin composition] There are no limitations on the method for producing the polycarbonate resin composition, and a wide variety of known methods for producing polycarbonate resin compositions can be used, including a method in which the above-mentioned essential components and other components added as needed are premixed using various mixers such as a tumbler or a Henschel mixer, and then melt-kneaded using a mixer such as a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader, etc. The scaly glass filler (C) and the flat cross section glass fibers (D) are preferably side-fed. The melt-kneading temperature is not particularly limited, but is usually 260 to 320°C.

[0079] The polycarbonate resin composition can be pelletized and molded into various molded articles by various molding methods. Alternatively, the resin can be melt-kneaded in an extruder and directly molded into molded articles without going through pelletization.

[0080] The polycarbonate resin composition preferably has a linear expansion coefficient in the MD direction and the TD direction measured in accordance with ISO 11359-2 of 2.1 × 10 -5 / K~2.8×10 -5 / K, and the ratio of the linear expansion coefficients in MD and TD is 0.9 to 1.1. The polycarbonate resin composition preferably has a linear expansion coefficient in this range, so that when it is combined with a metal (or alloy) such as aluminum or magnesium to form a lens barrel or the like, the linear expansion coefficient is similar to that of these metals, making it possible to prevent deviations in circularity and optical axis due to differences in thermal expansion even over a wide range of ambient temperatures.

[0081] Molded articles obtained from polycarbonate resin compositions have low molding shrinkage, a linear expansion coefficient at the same level as that of aluminum or magnesium metal, highly low anisotropy, high rigidity, excellent impact resistance, and excellent fluidity (moldability) and appearance of molded articles.

[0082] [Paint layer] The coated molded article of the present invention has a black coating layer on the surface of the above-mentioned molded article. This coating layer is a layer that provides high designability in areas where a deep, intensely black color with excellent jet black color and gloss, known as piano black, is required. The paint used to form the coating layer is a commonly used paint, and examples include two-component and one-component heat-curing types, ultraviolet-curing types, etc. Examples of binder resins include urethane-based and acrylic-based polymers, and may also contain various additives such as carbon black and rheology control materials. The thickness of the black coating layer is preferably 5 to 50 μm, more preferably 10 to 40 μm, and most preferably 15 to 25 μm. If the thickness is less than this range, it is difficult to achieve a high level of design, and if it is more than this range, problems such as dripping of the coating on the edge surfaces of the molded product are likely to occur. The black coating layer of the molded article may be formed in multiple layers, or may be preferably coated with a primer, although in this case, multiple coatings increase costs and reduce the jet blackness and gloss.

[0083] [Method for forming black coating layer] Known methods can be used to apply the black coating layer to the molded article, and specific examples include comma coating, gravure coating, reverse coating, roll coating, lip coating, and spray coating. Spray coating is preferred to obtain high designability.

[0084] [Applications for painted molded products] Preferred uses of the coated molded article of the present invention include, 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, rear 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 housings and mechanical parts for barcode readers and scanners.

[0085] [sheet metal] The coated molded article of the present invention may be integrated with a metal sheet. There are no particular limitations on the metal sheet, but examples include aluminum, magnesium, iron, copper, stainless steel, and SECC (electro-galvanized steel sheet), with SECC being particularly preferred. Integration methods include TOM molding, insert molding, outsert molding (welding of products), and gluing, with insert molding being particularly preferred. Molded articles integrated with metal sheets are used for the applications described above, but since metal sheets have excellent electrical properties and electromagnetic wave shielding properties, properties that resin compositions do not have, they are particularly preferably used in electronic devices and the like. [Example]

[0086] The present invention will be explained in more detail below with reference to examples, but the present invention should not be construed as being limited to the following examples. The raw materials used in the following Examples 1 to 7 and Comparative Examples 1 to 3 are as follows.

[0087] [Table 1]

[0088] (Examples 1 to 7, Comparative Examples 1 to 3) [Production of polycarbonate resin composition pellets] Of the components listed in Table 1, all except the scaly glass fillers (C) and (CX), the flat cross section glass fiber (D), and the circular cross section glass fiber (DX) were uniformly mixed in the amounts (all parts by mass) listed in Table 2 below in a tumbler mixer, and then fed from a hopper to an extruder for melt-kneading. The scaly glass fillers (C) and (CX), the flat cross section glass fiber (D), and the circular cross section glass fiber (DX) were side-fed from a downstream position 2 / 3 of the way down the barrel length L from the upstream of the extruder. The extruder used was a twin-screw extruder (TEX25αIII, L / D=52.5) ​​manufactured by The Japan Steel Works, Ltd., and melt extrusion was carried out under conditions of a screw rotation speed of 200 rpm, a cylinder temperature of 300°C, and a discharge rate of 25 kg / hr. The extruded strands were quenched in a water bath and pelletized using a pelletizer.

[0089] The pellets obtained by the above manufacturing method were dried at 120°C for 5 hours, and then molded into 4 mm thick ISO multipurpose test specimens using an NEX80 injection molding machine manufactured by Nissei Plastic Industrial Co., Ltd. under the following conditions: cylinder temperature 290°C, mold temperature 100°C, injection speed 30 mm / s, and holding pressure 80 MPa. In addition, using the same model, a flat plate-shaped molded product measuring 100 mm in length, 100 mm in width, and 2 mm in thickness was molded under the following conditions: cylinder temperature 300°C, mold temperature 100°C, injection speed 100 mm / s, and holding pressure 80 MPa.

[0090] [Measurement of bending strength and bending modulus] The 4 mm thick ISO multipurpose test piece obtained above was used to measure the flexural strength (unit: MPa) and flexural modulus (unit: MPa) in accordance with ISO178.

[0091] [Charpy impact strength measurement] Using the 4mm thick ISO multipurpose test piece obtained above, the notched Charpy strength (unit: kJ / m) was measured based on ISO179. 2 ) was measured.

[0092] [Measurement of deflection temperature under load (DTUL)] Based on ISO75-1 and ISO75-2, a test piece measuring 10 mm in length, 4 mm in width, and 4 mm in thickness was prepared from the 4 mm thick ISO multipurpose test piece obtained above, and a constant bending load (1.80 MPa) was applied to the center of the piece in the flatwise direction. The temperature was then raised at a uniform rate, and the temperature (unit: °C) was measured when the strain at the center reached 0.34 mm.

[0093] [Measurement of linear expansion coefficient] The linear expansion coefficients in the MD and TD directions were determined based on ISO 11359-2. The center of the obtained flat plate-shaped molded product having a length of 100 mm, a width of 100 mm, and a thickness of 2 mm was cut out in the MD / TD direction to prepare a test piece having a length of 15 mm, a width of 10 mm, and a thickness of 2 mm, which was used to measure the linear expansion coefficient. The measuring device used was a Hitachi High-Tech Science TMA / SS6100. The length of the test piece was measured, and the temperature was raised from -30 to +120°C at a rate of 20°C / min. The linear expansion coefficient (unit: / K) was calculated from the slope of the dimensional change relative to the temperature change.

[0094] [Evaluation of linear expansion coefficient ratio (anisotropy)] The ratio of the linear expansion coefficients in the MD and TD calculated above (MD / TD) was calculated.

[0095] [Fluidity: Bar flow length] The pellets obtained above were dried at 120°C for 5 hours, and then the flow length (unit: mm) was measured using an NEX80 injection molding machine manufactured by Nissei Plastic Industrial Co., Ltd., using a bar flow mold (thickness 1 mm, width 20 mm, diameter 1.5 mm pin gate) under the following conditions: cylinder temperature 300°C, mold temperature 100°C, injection pressure 150 MPa, injection time 5 seconds, and molding cycle 45 seconds.

[0096] [Appearance evaluation of molded polycarbonate resin compositions] The pellets obtained above were dried at 120°C for 5 hours, and then a Nissei Plastic Industrial NEX80 injection molding machine was used to mold three-layer plates of 60 mm x 90 mm and thicknesses of 1 mm, 2 mm, and 3 mm at a cylinder temperature of 300°C, a mold temperature of 120°C, and an injection speed of 100 mm / s.The appearance of the plates was visually observed and evaluated according to the following criteria. A: Less surface roughness B: Partially rough surface C: Overall surface roughness

[0097] [Paint layer appearance evaluation] The 4 mm thick ISO multipurpose test pieces obtained above were painted using a Kawasaki Heavy Industries KJ194JB0 sprayer equipped with a Carlisle DeVILBISS T-AGPV spray gun. The paint used was Eco Sunshine Super MH EC-MH62-1806SG (piano black) manufactured by Musashi Paint Co., Ltd. as the base agent, Z-EC-H760 manufactured by Musashi Paint Co., Ltd. as the hardener, and thinner Z-K139 manufactured by Musashi Paint Co., Ltd. as the thinner, in a ratio of 100:40:100. During spray coating, the paint flow rate was set to 200 ml / min, the atomization pressure to 0.4 KPa, the spray pattern pressure to 0.2 KPa, and the distance from the spray gun to 150 mm. After coating, the test pieces were placed in an infrared drying oven at 80°C for 30 minutes, then removed and allowed to cool naturally. In addition, a tinplate was placed on a 4 mm ISO multipurpose test piece, and the above paint was applied in the same manner, and the thickness of the applied film was measured with a film thickness measuring instrument (L-300J, manufactured by Kett Electric Laboratory Co., Ltd.). The film thickness of the paint applied to the tinplate was 20 μm. Therefore, it is considered that the film thickness of the paint applied to the 4 mm ISO multipurpose test piece was also 20 μm.

[0098] After painting, the test pieces were visually inspected from a distance of 30 cm and the appearance was evaluated according to the following criteria. A: No problems with jet black or gloss on the surface B: There are some problems with jet black and gloss. C: Overall problems with jet black and gloss The evaluation results are shown in Table 2 below.

[0099] [Table 2]

[0100] (Example 8, Comparative Example 4) [Production of sheet metal insert molding 1 Example 8] The pellets used in Example 7 were dried at 120°C for 5 hours. Next, a rectangular metal plate described below was placed in a mold attached to an injection molding machine, and an insert-molded product of the metal plate and resin was molded under the following conditions: cylinder temperature 300°C, mold temperature 90°C, injection speed 60 mm / s, holding pressure 100 MPa, and cooling time 30 seconds. The injection molding machine used was an SE280HD injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. Figure 1 shows the shape of the obtained insert-molded product. In Figure 1, (c) is a top view, (a) is a cross-sectional view of A in (c) along line AA, (b) is a cross-sectional view of B in (c) along line BB, and (d) is a bottom view, with 1 being the resin part and 2 being the sheet metal. The insert-molded product has a box-like shape with an opening 3 at the bottom, and sheet metal 2 measuring 325 mm in length, 205 mm in width, and 1.2 mm in thickness is inserted above opening 3. The length and width of each part are as shown in the figure. SECC (electro-galvanized steel sheet) was used as sheet metal 2. The linear expansion coefficient of SECC is 1.2 x 10 -5 / K.

[0101] [Production of Sheet Metal Insert Molding 2 Comparative Example 4] For 100 parts by mass of aromatic polycarbonate resin (Mitsubishi Engineering Plastics Corporation's "Iupilon H-2000"), 42 parts by mass of ABS resin (Nippon A&L Corporation's "Clarastic UT-61"), 0.04 parts by mass of phosphorus-based antioxidant (ADEKA Corporation's "ADK STAB 2112"), 0.07 parts by mass of phenol-based antioxidant (BASF Corporation's "Irganox 1010"), 0.01 parts by mass of phosphate ester-based additive (ADEKA Corporation's "ADK STAB AX-71"), 0.01 parts by mass of mold release agent (NOF Corporation's stearic acid "NAA-180") ), 0.11 parts by mass of a release agent (pentaerythritol distearate "Unistar M-476D" manufactured by NOF Corporation), and 0.72 parts by mass of a carbon black masterbatch ("RB948G" manufactured by Koshigaya Chemical Co., Ltd.). The mixture was uniformly mixed in a tumbler mixer, and then fed from a hopper to an extruder where it was melt-kneaded to prepare pellets. The extruder and extrusion conditions were the same as those used to prepare pellets in Examples 1 to 7 and Comparative Examples 1 to 3. The linear expansion coefficient of these pellets was measured by the method described above, and it was found to be 7.0 × 10 in the MD direction. -5 / K, TD direction: 7.0×10 -5 The ratio of the linear expansion coefficient in the MD to the linear expansion coefficient in the TD (MD / TD) was 1.0.

[0102] Using the pellets obtained above, a sheet metal insert molding was produced under the same conditions as in Example 8.

[0103] [Appearance evaluation of painted products] The sheet metal insert molded products produced in Example 8 or Comparative Example 4 were painted on the resin portion of the molded product using a Kawasaki Heavy Industries KJ194JB0 sprayer and a Carlisle DeVILBISS T-AGPV spray gun to produce painted products. The paint and painting conditions were the same as those used in the ISO multipurpose test for Examples 1 to 7 and Comparative Examples 1 to 3. A tinplate was placed on the sheet metal insert molded product, and the paint was applied in the same manner. The applied film thickness was measured using a film thickness measuring instrument (Kett Electric Laboratory L-300J). The film thickness of the paint applied to the tinplate was 20 μm. Therefore, it is believed that the paint film thickness applied to the sheet metal insert molded products of Example 8 or Comparative Example 4 was also 20 μm.

[0104] The appearance of the painted products was evaluated visually from a distance of 30 cm, and there were no problems with the jet black or gloss of the surface of either painted product.

[0105] [Environmental test evaluation of painted products] The coated products prepared in Example 8 or Comparative Example 4 were subjected to an environmental test evaluation using a thermal shock apparatus TD-101-W manufactured by Espec Corp. The environmental test conditions were 80°C for 30 minutes and -30°C for 30 minutes, and 20 cycles were performed. When the appearance of the coated product was checked after the test, no particular problems were found in Example 8, but in Comparative Example 4, cracks had occurred in the resin portion. [Industrial Applicability]

[0106] The polycarbonate resin coated molded article of the present invention has excellent jet blackness and gloss, and is therefore suitable for a variety of applications, particularly applications requiring design, and is highly applicable in industry.

Claims

1. A polycarbonate resin coated molded article having a black coating layer on the surface of a molded article of a resin composition containing, relative to 100 parts by mass of polycarbonate resin (A), 8 to 60 parts by mass of at least one flow modifier (B) selected from the group consisting of an acrylonitrile-styrene copolymer (B1), a polycaprolactone polymer (B2), and a polycarbonate oligomer (B3), 10 to 85 parts by mass of a scaly glass filler (C) having an average thickness of 0.45 to 1 μm, and 10 to 60 parts by mass of a flat cross section glass fiber (D) having an aspect ratio of more than 1.5 and not more than 5, wherein the mass ratio (D) / (C) of the contents of the flat cross section glass fiber (D) to the contents of the scaly glass filler (C) is 0.1 to 2.5, and the mass ratio (C) / (B) of the contents of the scaly glass filler (C) to the contents of the flow modifier (B) is 0.8 to 7.

2. 2. The polycarbonate resin coated molded product according to claim 1, which is integrated with a metal plate.

3. 3. The polycarbonate resin coated molded product according to claim 1, wherein the thickness of the black coating layer is 5 to 50 μm.

4. The resin composition has a linear expansion coefficient of 2.1 × 10 in the MD direction and the TD direction measured according to ISO 11359-2. －５ / K ~ 2.8 x 10 －５ 3. The polycarbonate resin coated molded article according to claim 1, wherein the linear expansion coefficient ratio in MD to TD is 0.9 to 1.

1.

5. 3. The polycarbonate resin coated molded product according to claim 1, wherein the resin composition does not contain a phosphorus-based flame retardant, or if it contains one, the content thereof is 1 part by mass or less per 100 parts by mass of the polycarbonate resin (A).

6. 3. The polycarbonate resin coated molded product according to claim 1 or 2, wherein the resin composition does not contain a fibril-forming fluororesin, or if it contains one, the content of the fibril-forming fluororesin is 1 part by mass or less per 100 parts by mass of the polycarbonate resin (A).

7. 3. The polycarbonate resin coated molded product according to claim 1 or 2, which is a molded product selected from the group consisting of housing parts and lens barrels of cameras, telescopes, microscopes, projection exposure devices, and optical measuring devices; housing parts and mechanical parts of smartphone cameras, in-vehicle cameras, drive recorders, surveillance cameras, and small cameras mounted on drones; housings and mechanical parts of car collision prevention sensors, rear monitor sensors, vehicle speed sensors, temperature sensors, and security sensors; frame members and outer panel members of automobiles, motorcycles, bicycles, and wheelchairs; panel members and mechanical parts of home televisions, personal computer displays, in-vehicle monitors, smartphones, and head-mounted displays; and barcode reader and scanner housings and mechanical parts.

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