Polycarbonate resin composition for vapor-deposited molded article and vapor-deposited molded article

Abstract

To provide a polycarbonate resin composition capable of producing a vapor-deposited molded article that has few foreign substances on the surface and exhibits a superior appearance.SOLUTION: A polycarbonate resin composition for vapor-deposited molded articles, comprises a polycarbonate resin component containing recycled polycarbonate, wherein, on the surface of a molded article obtained from the polycarbonate resin composition by injection molding and vapor depositing, the number of defects having a maximum particle diameter of 30 μm or more, which are transparent foreign substances detectable by optical observation, is 12 or fewer per cm2.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition for vapor deposition molded products, which is suitable for use in molded products that are to be painted or metal vapor deposited in the fields of automobile interior and exterior parts, electrical and electronic equipment parts, housing materials, etc. [Background technology]

[0002] Polycarbonate resins have excellent heat resistance, mechanical properties, and electrical characteristics and are widely used industrially. Polymer alloys of aromatic polycarbonate resins with other thermoplastic resins are also widely used as materials for manufacturing parts in various industrial fields, such as vehicle parts, office automation equipment parts, electrical and electronic equipment parts, housing materials, and other industrial fields.

[0003] On the other hand, in recent years, there has been an increasing social demand for environmental friendliness, and there has been a trend toward stricter regulations under various legal systems. In Europe and the United States, there is a demand for the use of recycled resins in the exteriors and housings of vehicle parts and electronic devices, and there are also an increasing number of examples of using recycled materials in polycarbonate resin compositions (for example, Patent Document 1).

[0004] Material recycling, one method of recycling resins, involves crushing recovered used molded products, washing them with a cleaning solution, and separating the crushed thermoplastic plastic from the crushed mixture. However, these complex processes make recycled materials more susceptible to contamination with foreign matter than virgin materials. If a polycarbonate resin composition containing such foreign matter is used, the foreign matter will appear on the surface of the final molded product, causing unevenness and a poor appearance.

[0005] Foreign matter that appears on the surface of a molded product may form a crater-like shape by raising the resin around the foreign matter. If a surface treatment such as vapor deposition is applied to this crater, the foreign matter and the raised resin around it will become one and be detected as a foreign matter defect that is larger than its actual size.

[0006] As a method for reducing foreign matter, a method of filtering the melt-kneaded thermoplastic resin through a mesh and a method of removing magnetic metals using a magnet have been proposed (for example, Patent Document 2).

[0007] However, the inventors' investigation revealed that even after passing through a mesh, transparent foreign matter of 30 μm or more often occurs in the resin. Furthermore, it was found that this transparent foreign matter contains thermosetting resin components that are thought to be derived from recycled raw materials and cannot be collected by a magnet. Furthermore, while defects of several hundred μm or more can be detected by visual observation, small, transparent defects of several tens of μm are difficult to detect by visual observation. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2018-87295 [Patent Document 2] Japanese Patent Application Publication No. 2019-202499 Summary of the Invention [Problem to be solved by the invention]

[0009] An object of the present invention is to provide a polycarbonate resin composition that can give a vapor-deposited molded article having little foreign matter on the surface and excellent appearance. [Means for solving the problem]

[0010] According to the present inventors, the above-mentioned problem is solved by a polycarbonate resin composition containing a polycarbonate resin component containing recycled polycarbonate, wherein the number of defects having a maximum particle size of 30 μm or more, which are transparent foreign matters detectable by optical observation, on the surface of a molded article obtained by injection molding and vapor deposition from the polycarbonate resin composition is 12 / cm. 2 The present inventors have discovered that this can be achieved by a polycarbonate resin composition for vapor deposition molded products characterized by the following, and have completed the present invention.

[0011] That is, according to the present invention, the object of the invention is achieved as follows.

[0012] (1) A polycarbonate resin composition containing a polycarbonate resin component containing recycled polycarbonate, wherein the number of defects on the surface of a molded product obtained by injection molding and vapor deposition from the polycarbonate resin composition, which are transparent foreign matter detectable by optical observation and have a maximum particle size of 30 μm or more, is 12 / cm. 2 A polycarbonate resin composition for vapor deposition molding, characterized by: (2) The polycarbonate resin composition for vapor deposition moldings according to (1), wherein the polycarbonate resin component contains 30% by weight or more of recycled polycarbonate. (3) The polycarbonate resin composition for vapor-deposition molded products according to (1) or (2), wherein the polycarbonate resin component has a viscosity-average molecular weight of 10,000 to 25,000. (4) A vapor deposition molded article obtained by injection molding the polycarbonate resin composition according to any one of (1) to (3) above. (5) The molded article for deposition according to the above item (4), wherein the injection molding is carried out at a cylinder temperature of 250 to 350°C and a mold temperature of 60 to 120°C. [Effects of the Invention]

[0013] The polycarbonate resin composition of the present invention can give vapor-deposited molded articles with excellent appearance and with little foreign matter on the surface of the molded articles, and therefore has exceptional industrial effects. [Brief explanation of the drawings]

[0014] [Figure 1] 1 is a microscopic image of the surface of a test piece after vapor deposition in Example 1. [Figure 2] 1 is a microscopic image of the surface of a test piece after vapor deposition in Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present disclosure is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.

[0016] [Recycled polycarbonate] The recycled polycarbonate used in the present invention is preferably a recycled polycarbonate obtained by crushing recovered molded articles containing polycarbonate resin. The molded article may be a used product. Preferred examples of used products include soundproof walls, automobile windows, translucent roofing materials, various glazing materials such as automobile sunroofs, transparent components such as windshields and automobile headlamp lenses, containers such as water bottles, light guide plates, eyeglass lenses, and optical recording media. Crushed products obtained from non-conforming products, sprues, runners, etc., or pellets obtained by melting these may also be used.

[0017] In the present invention, unless otherwise specified, the term "defect" refers to a transparent foreign particle that can be detected by optical observation. A transparent foreign particle is a crater-shaped foreign particle that has a transparent core through which the substrate can be seen and that causes the surrounding resin to protrude in a circular ring shape.

[0018] [Polycarbonate resin component] In the present invention, a polycarbonate resin component containing recycled polycarbonate is used. The polycarbonate resin component preferably contains 30% by weight or more of recycled polycarbonate, more preferably 40% by weight or more, and even more preferably 50% by weight or more. Examples of polycarbonate resins other than recycled polycarbonate include new polycarbonate resins obtained by the following production methods.

[0019] The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor, and examples of the reaction method include interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

[0020] Representative examples of dihydric phenols used herein include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A or BPA), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)pentane, 4,4'-(p-phenylenediisopropylidene)diphenol, and the like. Examples of suitable dihydric phenols include phenol, 4,4'-(m-phenylenediisopropylidene)diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ester, bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene. Preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes, and among these, bisphenol A is particularly preferred and widely used in terms of impact resistance.

[0021] In the present invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, it is also possible to use special polycarbonate resins produced using other dihydric phenols as the polycarbonate resin component. For example, polycarbonate resins (homopolymers or copolymers) containing 4,4'-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF"), and 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter sometimes abbreviated as "BPEF") as part or all of the dihydric phenol components are suitable for applications requiring particularly strict resistance to dimensional change due to water absorption and dimensional stability. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, and especially 10 mol% or more, of the total dihydric phenol components constituting the polycarbonate resin. In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the polycarbonate resin component constituting the resin composition is a copolymer polycarbonate resin of the following (1) to (3).

[0022] (1) A copolymer polycarbonate resin in which, based on 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPM accounts for 20 to 80 mol% (more preferably 40 to 75 mol%, and even more preferably 45 to 65 mol%) and BCF and / or BPEF accounts for 20 to 80 mol% (more preferably 25 to 60 mol%, and even more preferably 35 to 55 mol%).

[0023] (2) A copolymer polycarbonate resin in which, out of 100 mol% of the dihydric phenol components constituting the polycarbonate resin, BPA accounts for 10 to 95 mol% (more preferably 50 to 90 mol%, even more preferably 60 to 85 mol%) and BCF and / or BPEF accounts for 5 to 90 mol% (more preferably 10 to 50 mol%, even more preferably 15 to 40 mol%).

[0024] (3) A copolymer polycarbonate resin in which, based on 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPM accounts for 20 to 80 mol% (more preferably 40 to 75 mol%, and even more preferably 45 to 65 mol%) and Bis-TMC accounts for 20 to 80 mol% (more preferably 25 to 60 mol%, and even more preferably 35 to 55 mol%).

[0025] These special polycarbonate resins may be used alone or in a suitable mixture of two or more. They may also be used in a mixture with a commonly used bisphenol A polycarbonate resin. The production methods and properties of these special polycarbonate resins are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580.

[0026] Among the various polycarbonate resins mentioned above, those having a water absorption rate and a glass transition temperature (Tg) within the following ranges by adjusting the copolymer composition and the like are particularly suitable in fields where dimensional stability is required, since the polymer itself has good hydrolysis resistance and exhibits significantly reduced warpage after molding: (i) a polycarbonate resin having a water absorption rate of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C, or (ii) a polycarbonate resin having a Tg of 160 to 250°C, preferably 170 to 230°C, and a water absorption rate of 0.10 to 0.30%, preferably 0.13 to 0.30%, and more preferably 0.14 to 0.27%.

[0027] Here, the water absorption rate of polycarbonate is a value measured by using a disk-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm and immersing it in water at 23°C for 24 hours in accordance with ISO 62-1980. Furthermore, Tg (glass transition temperature) is a value determined by differential scanning calorimetry (DSC) measurement in accordance with JIS K7121.

[0028] Carbonate precursors that can be used include carbonyl halides, carbonic acid diesters, and haloformates, and specific examples include phosgene, diphenyl carbonate, and dihaloformates of dihydric phenols.

[0029] When producing a polycarbonate resin by interfacial polymerization of the dihydric phenol and carbonate precursor, a catalyst, a terminal stopper, an antioxidant to prevent oxidation of the dihydric phenol, etc. may be used as needed. The polycarbonate resin of the present invention also includes branched polycarbonate resins copolymerized with a trifunctional or higher polyfunctional aromatic compound, polyester carbonate resins copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, copolymerized polycarbonate resins copolymerized with a bifunctional alcohol (including alicyclic), and polyester carbonate resins copolymerized with such bifunctional carboxylic acid and bifunctional alcohol. A mixture of two or more of the obtained polycarbonate resins may also be used.

[0030] The branched polycarbonate resin can impart anti-drip properties to the resin composition of the present invention. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1,1-bis(4- Examples of the 4-hydroxyphenyl ether include trisphenols such as {4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0031] The structural units derived from polyfunctional aromatic compounds in the branched polycarbonate are preferably 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and even more preferably 0.05 to 0.8 mol% out of the total 100 mol% of the structural units derived from dihydric phenols and the structural units derived from such polyfunctional aromatic compounds. In particular, in the case of the melt transesterification method, branched structural units may be generated as a side reaction, and the amount of such branched structural units is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol% out of the total 100 mol% of the structural units derived from dihydric phenols. The proportion of such branched structures is 1 It can be calculated by H-NMR measurement.

[0032] The aliphatic bifunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Preferred examples of the aliphatic bifunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosane diacid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The bifunctional alcohol is more preferably an alicyclic diol, such as cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0033] The reaction modes of the methods for producing the polycarbonate resin of the present invention, such as interfacial polymerization, melt transesterification, carbonate prepolymer solid-phase transesterification, and ring-opening polymerization of a cyclic carbonate compound, are well known in various literatures and patent publications.

[0034] The viscosity average molecular weight (M) of the polycarbonate resin component is not particularly limited, but is preferably 1.0×10 4 ~2.5×10 4 and more preferably 1.3 × 10 4 ~2.4×10 4 , and more preferably 1.5 × 10 4 ~2.3×10 4 is.

[0035] Viscosity average molecular weight is 1.0×10 4 On the other hand, a polycarbonate resin component with a viscosity average molecular weight of less than 2.5 × 10 may not provide good mechanical properties. 4 If the polycarbonate resin component exceeds this limit, the flowability during injection molding may be poor.

[0036] The polycarbonate resin component may be obtained by mixing components having a viscosity average molecular weight outside the above range. 4), the entropy elasticity of the resin is improved. As a result, good molding processability is exhibited in gas-assisted molding and foam molding, which are sometimes used when molding reinforced resin materials into structural members. Such improvement in molding processability is even better than that of the branched polycarbonate. In a more preferred embodiment, the polycarbonate resin component has a viscosity average molecular weight of 2.6×10 4 ~5×10 4 Polycarbonate resin (A-1 component) and viscosity average molecular weight 0.5 × 10 4 ~2.5×10 4 The viscosity average molecular weight of the polycarbonate resin (A-2 component) is 1.0 × 10 4 ~2.5×10 4 A polycarbonate resin (polycarbonate resin component) (hereinafter, sometimes referred to as a "polycarbonate resin containing a high molecular weight component") can also be used.

[0037] The high-molecular-weight component-containing polycarbonate resin can be obtained by mixing the A-1 and A-2 components in various ratios and adjusting the ratio to satisfy a predetermined molecular weight range. Preferably, the A-1 component is 2 to 40% by weight, more preferably 3 to 30% by weight, even more preferably 4 to 20% by weight, and particularly preferably 5 to 20% by weight, of 100% by weight of the polycarbonate resin component.

[0038] The viscosity average molecular weight in the present invention is determined by first calculating the specific viscosity (η SP ) was measured using an Ostwald viscometer from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The calculated specific viscosity (η SP ) and calculate the viscosity average molecular weight M using the following formula: η SP / c=[η]+0.45×[η] 2c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 M 0.83 c=0.7

[0039] After polycarbonate resin is produced by conventional methods, it is preferable to remove impurities and foreign matter, such as low-molecular-weight components and unreacted components, by filtering the solution or washing the granular raw material after granulation (desolventization) with a poor solvent such as acetone under heated conditions. Furthermore, during the extrusion process (pelletization) to obtain pelletized polycarbonate resin for injection molding, it is preferable to remove foreign matter by passing the molten resin through a sintered metal filter. To obtain a resin with a low level of foreign matter, particularly iron or iron-containing foreign matter, whose specific heat difference with the resin is 50 J / (kg·K) or more, it is particularly important to select raw materials with low levels of such foreign matter as polymerization raw materials and to use equipment that minimizes the generation of such foreign matter. Furthermore, after pelletization, it is also preferable to remove iron or iron-containing foreign matter using a magnetic separator. In any case, it is necessary to minimize the content of foreign matter, impurities, and solvents in the raw resin before injection molding.

[0040] [Polycarbonate resin composition] In the present invention, a polycarbonate resin composition is used in which the above-mentioned polycarbonate resin component is blended with various additives as described below. [Additives] The polycarbonate resin composition of the present invention may contain various stabilizers, mold release agents, coloring agents, etc. for preventing a decrease in molecular weight during molding and for stabilizing color tone.

[0041] (i) Phosphorus stabilizers, phenolic stabilizers, and other heat stabilizers The polycarbonate resin composition of the present invention preferably contains various heat stabilizers. Phosphorus-based stabilizers are suitable as such heat stabilizers. Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and their esters, as well as tertiary phosphines. These phosphorus-based stabilizers can be used alone or in combination of two or more.

[0042] Examples of the phosphite compound include trialkyl phosphites such as tridecyl phosphite, dialkyl monoaryl phosphites such as didecyl monophenyl phosphite, monoalkyl diaryl phosphites such as monobutyl diphenyl phosphite, triaryl phosphites such as triphenyl phosphite and tris(2,4-di-tert-butylphenyl)phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol, Examples include pentaerythritol phosphites such as bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and cyclic phosphites such as 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite and 2,2′-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite.

[0043] Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, and diisopropyl phosphate, and preferred are triphenyl phosphate and trimethyl phosphate.

[0044] Preferred examples of the phosphonite compound include tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenyl phosphonite, with tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenyl phosphonite being more preferred. Such phosphonite compounds can be used in combination with the above-mentioned phosphite compounds having an aryl group substituted with two or more alkyl groups, and are therefore preferred.

[0045] Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, etc. Examples of the tertiary phosphine include triphenylphosphine.

[0046] The content of such phosphorus-based stabilizer is preferably 0.001 to 3.0 parts by weight, more preferably 0.01 to 2.0 parts by weight, and even more preferably 0.05 to 1.0 part by weight, relative to 100 parts by weight of the polycarbonate resin component.

[0047] The hindered phenol compound may be any of various compounds that are usually incorporated into resins, such as α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, and 3,5-di-tert-butyl-4-hydroxybenzyl. Phosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methyl-benzyl-p-cresol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-butylidene-bis( 4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl-6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9 -Bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 4,4'-dithiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylene bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate nurate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetate, 3,9-bis[2-{3- Examples include {(3-tert-butyl-4-hydroxy-5-methylphenyl)acetyloxy}-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, 1,3,5-trimethyl-2,4,6-tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene, and tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)isocyanurate.

[0048] Among the above hindered phenol compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane are preferred in the present invention, with 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane being particularly preferred.

[0049] The above hindered phenol compounds can be used alone or in combination of two or more. The content of the hindered phenol compound is preferably 0.001 to 3.0 parts by weight, more preferably 0.01 to 2.0 parts by weight, and even more preferably 0.05 to 1.0 part by weight, per 100 parts by weight of the polycarbonate resin component.

[0050] The polycarbonate resin composition of the present invention can also contain heat stabilizers other than the phosphorus-based stabilizer and hindered phenol compound. Such other heat stabilizers are preferably used in combination with either one of these stabilizers or antioxidants, and particularly preferably in combination with both. Suitable examples of such other heat stabilizers include lactone-based stabilizers, such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (details of such stabilizers are described in JP-A-7-233160). This compound is commercially available under the trade name Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and this compound can be used. Furthermore, stabilizers containing this compound mixed with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the same company is a suitable example. Such premixed stabilizers can also be used in the present invention.

[0051] The content of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, and more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of the polycarbonate resin component.

[0052] Other examples of stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Such stabilizers are particularly effective when the resin composition is used for rotational molding.

[0053] The content of such sulfur-containing stabilizer is preferably 0.001 to 0.1 part by weight, more preferably 0.01 to 0.08 part by weight, per 100 parts by weight of the polycarbonate resin component.

[0054] (ii) Mold release agent To further improve releasability from a mold during melt molding, the polycarbonate resin composition of the present invention may be blended with a mold release agent within the scope of the present invention. Known mold release agents can be used. Examples of such mold release agents include saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymers, etc.; those modified with functional group-containing compounds, such as acid-modified waxes, can also be used), silicone compounds, fluorine compounds (fluorine oils, such as polyfluoroalkyl ethers), paraffin wax, and beeswax.

[0055] Among these, fatty acid esters are preferred as release agents. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such aliphatic alcohols may be monohydric alcohols or polyhydric alcohols having dihydric or higher hydric groups. The carbon number of the alcohol is in the range of 3 to 32, more preferably 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerols (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferred for the fatty acid esters of the present invention.

[0056] On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably has 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, icosanoic acid, and docosanoic acid, as well as unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferred. Among these, saturated aliphatic carboxylic acids are preferred. Stearic acid and palmitic acid are particularly preferred. The above-mentioned aliphatic carboxylic acids, such as stearic acid and palmitic acid, are usually produced from natural fats and oils, such as animal fats and oils typified by beef tallow and lard, and vegetable fats and oils typified by palm oil and sunflower oil, and therefore these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components with different numbers of carbon atoms. Therefore, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids, particularly stearic acid and palmitic acid, which are produced from such natural fats and oils and are in the form of a mixture containing other carboxylic acid components are preferably used.

[0057] The fatty acid ester may be either a partial ester or a full ester (full ester). However, partial esters usually have a high hydroxyl value, which can easily induce decomposition of the resin at high temperatures, so full esters are more preferred. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably in the range of 4 to 20, and even more preferably in the range of 4 to 12, from the viewpoint of thermal stability. The acid value can be substantially 0. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. The iodine value is preferably 10 or less. The iodine value can be substantially 0. These properties can be determined by the method specified in JIS K0070.

[0058] The amount of such a release agent to be added is preferably 0.01 to 5 parts by weight per 100 parts by weight of the polycarbonate resin component.

[0059] (iii) UV absorber The polycarbonate resin composition of the present invention may contain an ultraviolet absorber. Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridobenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0060] Benzotriazoles include, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, Examples include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as azole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, as well as copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer.

[0061] Examples of hydroxyphenyltriazines include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol.Further examples include compounds in which the phenyl group of the above-mentioned compounds is replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol.

[0062] Examples of cyclic iminoesters include 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one), and 2,2'-(2,6-naphthalene)bis(3,1-benzoxazin-4-one).

[0063] Examples of cyanoacrylates include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0064] Furthermore, the ultraviolet absorber may be a polymeric ultraviolet absorber obtained by copolymerizing such an ultraviolet absorbing monomer and / or a photostable monomer having a hindered amine structure with a monomer such as alkyl (meth)acrylate by adopting a structure of a radically polymerizable monomer compound. Suitable examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of a (meth)acrylic acid ester.

[0065] The content of the ultraviolet absorber is preferably 0.01 to 2.0 parts by weight, more preferably 0.02 to 1.5 parts by weight, and even more preferably 0.03 to 1.0 part by weight, relative to 100 parts by weight of the polycarbonate resin component.

[0066] (iv) Epoxy group-containing compounds The polycarbonate resin composition of the present invention can optionally contain an epoxy group-containing compound. The epoxy group-containing compound used is preferably an epoxy polymer containing a glycidyl group, more preferably an epoxy polymer containing glycidyl methacrylate in the copolymer, with polystyrene being preferred as the other component of the copolymer. Among these, polyglycidyl methacrylate-polystyrene copolymers are preferred. Examples of monomer components for the glycidyl group-containing polymer include allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, and epoxy succinic acid. Examples of polymers include terminal epoxy-modified polydimethylsiloxane and side chain epoxy-modified polydimethylsiloxane.

[0067] The content of the epoxy group-containing compound is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.8 parts by weight, and even more preferably 0.01 to 0.5 parts by weight, relative to 100 parts by weight of the polycarbonate resin component.

[0068] (v) Dyes and pigments The polycarbonate resin composition of the present invention can further contain various dyes and pigments to provide molded articles with a variety of designs. By blending a fluorescent brightening agent or other fluorescent dye that emits light, it is possible to impart even better design effects by taking advantage of the emitted color. It is also possible to provide a flame-retardant polycarbonate resin composition that is colored with a very small amount of dyes and pigments and has vivid color development.

[0069] Examples of fluorescent dyes (including fluorescent whitening agents) used in the present invention include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes are preferred because they have good heat resistance and are less susceptible to deterioration during molding and processing of polycarbonate resins.

[0070] Examples of dyes other than the bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. Suitable metallic pigments include those having a metal coating or a metal oxide coating on various plate-like fillers.

[0071] The content of such dyes and pigments is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 parts by weight, per 100 parts by weight of the polycarbonate resin component.

[0072] [Production of polycarbonate resin composition] The polycarbonate resin composition of the present invention is prepared by mixing the above components simultaneously or in any order using a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading roll, or extruder. Melt-kneading using a twin-screw extruder is preferred as the mixer. If necessary, any component is preferably fed into the other melt-mixed components through a second feed port using a side feeder or the like. The extruded resin as described above is either directly cut and pelletized, or formed into strands, which are then cut and pelletized using a pelletizer. If it is necessary to reduce the influence of external dust during pelletization, it is preferable to purify the atmosphere around the extruder. The resulting pellets can have common shapes such as cylinders, prisms, and spheres, but cylinders are more preferred. The diameter of the cylinders is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.5 mm. The length of the cylinders is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 4 mm.

[0073] [Regarding molded articles produced by injection molding from the polycarbonate resin composition of the present invention] The polycarbonate resin composition of the present invention can be injection molded into various products using pellets obtained by the above-described method. Injection molding can be performed using not only conventional molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including supercritical fluid injection), insert molding, in-mold coating molding, insulated mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding, depending on the purpose. The advantages of these molding methods are widely known. Molding can be performed using either a cold runner or hot runner system. Considering the objectives of the present invention, it is preferable to maintain the molding process in an environment as clean as possible. It is also important to thoroughly dry the material to be molded to remove moisture and to avoid retention that could lead to decomposition of the molten resin. Furthermore, injection molding is preferably performed under conditions of a cylinder temperature of 250 to 350°C and a mold temperature of 60 to 120°C.

[0074] [About vapor deposition molded products] In the present invention, it is preferable to deposit a deposition material onto a molded article obtained by injection molding the polycarbonate resin composition of the present invention. As the deposition method, a conventionally known method can be used, for example, electrothermal heating, sputtering, ion plating, ion beam, etc., using a continuous or batch type vacuum deposition machine.

[0075] In the present invention, the number of defects with a maximum particle size of 30 μm or more, which are transparent foreign matters detectable by optical observation, on the surface of a molded article obtained by injection molding and vapor deposition from a polycarbonate resin composition is 12 / cm. 2 Less than 11 pieces / cm 2 The following is preferred: [Example]

[0076] The embodiments for carrying out the present invention are a summary of the preferred ranges of each of the above-mentioned requirements, and representative examples are described in the following examples. Of course, the present invention is not limited to these embodiments. Evaluations were carried out by the following methods.

[0077] [Evaluation of Resin Composition] (i) Number of defects The square plates (length 150 mm x width 150 mm x thickness 2 mm) obtained by the method described below were measured for the size and number of defects using the following procedure.

[0078] Optical observation was performed in the thickness direction using a microscope (Keyence VHX-8000) with reflected light (coaxial unidirectional illumination). Defects were marked on the images obtained by the observation, and the number of defects with a maximum diameter of 30 μm or more was counted at 100x magnification. In the examples and comparative examples described here, the core was transparent, and crater-like defects were detected, with the surrounding base resin raised in an annular shape, so these were counted. During measurement, the boundary between the defect and its periphery was determined by the difference in contrast between the raised base resin around the core and the surrounding area, and its size was defined as the maximum distance between two points on the boundary line. The observation area of ​​the molded product was 1 cm² per area, and five areas were selected from any part of the molded product for observation.

[0079] (ii) Appearance of molded product The appearance of the square plates (length 150 mm x width 150 mm x thickness 2 mm) obtained by the method described below was visually evaluated according to the following criteria. ◯: The number of transparent foreign matter particles according to (i) is 12 or less, and there is almost no surface roughness. ×: The number of transparent foreign matter particles (i) is more than 12, and the surface is very rough.

[0080] [Examples 1 and 2, Comparative Example 1] A mixture of the components listed in Table 1 was fed through the first feed port of an extruder. This mixture was obtained by blending in a V-type blender. The extrusion was performed using a 30 mm diameter vented twin-screw extruder (TEX30α-38.5BW-3V, manufactured by The Japan Steel Works, Ltd.) at a screw rotation speed of 200 rpm, a discharge rate of 20 kg / h, and a vent vacuum of 3 kPa to obtain pellets. The extrusion temperature was 280°C from the first feed port to the die. A portion of the obtained pellets was dried in a hot air circulation dryer at 100°C for 6 hours and then molded into test specimens (square plates) for evaluation using an injection molding machine (cylinder temperature 280°C, mold temperature 80°C). Next, the obtained test specimens were vacuum-depressurized to 2.0 Pa using a vapor deposition device, and platinum was vapor-deposited at a deposition rate of 50 nm / sec. The number of defects and appearance evaluation were performed on the surface before and after vapor deposition.

[0081] The following raw materials were used: (Component A) A-1: Aromatic polycarbonate resin (Teijin Ltd.: CM-1000, viscosity average molecular weight 15,500) A-2: Aromatic polycarbonate resin (Teijin Ltd.: L-1225WX, viscosity average molecular weight 19,700) A-3: Aromatic polycarbonate resin (Teijin Ltd.: L-1250WP, viscosity average molecular weight 23,900) A-4: Recycled polycarbonate resin (recycled polycarbonate resin pellets recycled from polycarbonate resin sheets, viscosity average molecular weight 20,500) A-5: Recycled polycarbonate resin (recycled polycarbonate resin pellets recycled from polycarbonate resin discs, viscosity average molecular weight 15,200)

[0082] (Other ingredients) (heat stabilizer) B-1: Triphenylphosphine (Johoku Chemical Industry Co., Ltd.: JC-263) B-2: Tris(2,4-di-tert-butylphenyl)phosphite (manufactured by BASF Japan Ltd.: Irgafos168) (mold release agent) B-3: Pentaerythritol tetrastearate (NOF Corporation: Unistar H-476-S) (Epoxy group-containing compound) B-4: Styrene and glycidyl methacrylate copolymer (NOF Corporation: Marproof G-0250SP) (coloring agent) B-5: Carbon black (manufactured by Resino Color Industries Co., Ltd.: SBF-T-5669G)

[0083] [Table 1] [Industrial Applicability]

[0084] The present invention relates to a polycarbonate resin composition for vapor deposition molded products, which is suitable for use in molded products that are to be painted or metal vapor deposited in the fields of automobile interior and exterior parts, electrical and electronic equipment parts, housing materials, etc.

Claims

1. A polycarbonate resin composition containing a polycarbonate resin component containing recycled polycarbonate, wherein the number of defects having a maximum particle size of 30 μm or more, which are transparent foreign matters detectable by optical observation, on the surface of a molded article obtained by injection molding and vapor deposition from the polycarbonate resin composition is 12 / cm. ２ A polycarbonate resin composition for vapor deposition molding, characterized by:

2. 2. The polycarbonate resin composition for vapor-deposition molded products according to claim 1, wherein the polycarbonate resin component contains 30% by weight or more of recycled polycarbonate.

3. 2. The polycarbonate resin composition for vapor-deposition molded products according to claim 1, wherein the polycarbonate resin component has a viscosity average molecular weight of 10,000 to 25,000.

4. A vapor deposition molded article obtained by injection molding the polycarbonate resin composition according to any one of claims 1 to 3.

5. 5. The molded article for vapor deposition according to claim 4, wherein the injection molding is carried out at a cylinder temperature of 250 to 350°C and a mold temperature of 60 to 120°C.

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