Aromatic polycarbonate resin composition and molded article thereof

Abstract

The present invention provides: an aromatic polycarbonate resin composition that is excellent in terms of thermal stability and moisture-heat resistance and gives molded articles having wavelength-selective absorption characteristics, which are excellent in terms of thermal stability and light stability; and a molded article of the aromatic polycarbonate resin composition.　This aromatic polycarbonate resin composition comprises 100 parts by weight of (A) an aromatic polycarbonate resin (A component), 0.03-1.2 parts by weight of (B) a colorant (B component) having a maximal absorption at less than 650 nm, 0.001-0.3 parts by weight of (C) a colorant (C component) having a maximal absorption at 650 nm or greater but less than 870 nm, 0.001-0.3 parts by weight of (D) a colorant (D component) having a maximal absorption at 870 nm or greater but less than 1,000 nm, and 0.003-0.5 parts by weight of (E) a phosphorus-compound thermal stabilizer and / or a phenolic thermal stabilizer (E component), and is characterized in that a 3-mm-thick molded article thereof has an average thickness-direction light transmittance at 400-870 nm of 1.5% or less.

Description

[Technical Field]

[0001] The present invention relates to an aromatic polycarbonate resin composition which has excellent thermal stability and moist heat resistance, and which provides molded articles having wavelength-selective absorption properties, and which further has excellent thermal and light stability of the absorption properties. [Background technology]

[0002] Autonomous driving technology has rapidly developed in recent years. Infrared sensing systems play an important role in autonomous driving technology. Examples of infrared sensing systems include driver monitoring systems that monitor the driver and LiDAR that detects other vehicles and buildings. Near-infrared light of approximately 700 nm and above is generally used for sensing. However, when performing infrared sensing, visible light to near-infrared light becomes noise, so a cover material is required that transmits the wavelength range used for sensing and blocks transmission of wavelengths below that range. Glass and resin are used as cover materials. Transparent resins such as acrylic resin and polycarbonate resin are commonly used, but there is a great demand for polycarbonate resin, which has good transparency and excellent impact resistance and heat resistance. Wavelength-selectively controlled polycarbonate resins have been investigated in the past. These involve the combined use of multiple colorants with different absorption wavelength bands to cut light from the visible light range to a portion of the near-infrared range (see Patent Documents 1 to 6). In particular, in recent years, as shown in Patent Documents 5 and 6, technology has been established that cuts light up to relatively long wavelengths of approximately 1000 to 1100 nm. The background to this is that as autonomous driving levels become more advanced (e.g., level 4 and above), further improvements in sensing accuracy are required, making it necessary to cut sunlight noise down to even longer wavelengths. However, these documents do not disclose the stability of absorption characteristics. In reality, the cover materials for infrared sensors used in autonomous driving technology are molded to thin thicknesses of approximately 1 to 3 mm. Therefore, polycarbonate resins with a viscosity-average molecular weight of 24,000 or less and relatively high fluidity are preferred, and molding temperatures are also high, at 300 to 340°C. Therefore, the thermal stability of wavelength characteristics during high-temperature molding is extremely important. Furthermore, resins are constantly exposed to light inside automobiles, so it is important that wavelength characteristics remain stable even after prolonged exposure to light. In other words, in order to realize a safe autonomous driving society, infrared sensor cover materials must have thermal and light stability in their absorption characteristics. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 5040827 [Patent Document 2] Patent No. 6354888 [Patent Document 3] WO2019 / 022169 publication [Patent Document 4] Patent No. 6658942 [Patent Document 5] Patent Publication No. 2021-188011 [Patent Document 6] Patent Publication No. 2021-147470 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide an aromatic polycarbonate resin composition which has excellent thermal stability and moist heat resistance, and when a molded article made from the composition has wavelength-selective absorption properties, the composition also has excellent thermal stability and light stability of the absorption properties, and a molded article made from the composition. [Means for solving the problem]

[0005] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by an aromatic polycarbonate resin composition containing a specific colorant and a heat stabilizer. That is, the present inventors have found that the above-mentioned problems can be solved by the following aromatic polycarbonate resin composition and molded article thereof. 1. A resin composition containing 100 parts by weight of (A) aromatic polycarbonate resin (component A), (B) 0.03 to 1.2 parts by weight of a colorant (component B) having an absorption maximum at less than 650 nm, (C) 0.001 to 0.3 parts by weight of a colorant (component C) having an absorption maximum at 650 nm or more but less than 870 nm, (D) 0.001 to 0.3 parts by weight of a colorant (component D) having an absorption maximum at 870 nm or more but less than 1000 nm, and (E) 0.003 to 0.5 parts by weight of a phosphorus-based heat stabilizer and / or a phenol-based heat stabilizer (component E), wherein the resin composition has an average light transmittance in the thickness direction of a molded article molded to a thickness of 3 mm at 400 nm to 870 nm of 1.5% or less. 2. The resin composition according to item 1, wherein the average light transmittance in the thickness direction of a molded article having a thickness of 3 mm is 1.5% or less at wavelengths from 2.870 nm to which the absorption of component D is maximum. 3. A resin composition according to item 1 or 2 above, wherein component C and component D are at least one colorant selected from the group consisting of anthraquinone-based colorants, phthalocyanine-based colorants, perylene-based colorants, and heterocyclic colorants. 4. The resin composition according to any one of items 1 to 3 above, which comprises 0.01 to 1 part by weight of (F) a benzotriazole-based ultraviolet absorber (component F) per 100 parts by weight of component A. 5. The resin composition according to any one of items 1 to 4 above, wherein component A has a viscosity average molecular weight of 24,000 or less. 6. A molded article obtained by molding the resin composition according to any one of items 1 to 5 above. 7. The molded product described in the preceding paragraph 6, which is a cover material for covering an infrared sensor. 8. The molded article described in the preceding paragraph 7, which is a cover material for an infrared sensor used in LiDAR for detecting vehicles and buildings. [Effects of the Invention]

[0006] The resin composition of the present invention has excellent thermal stability and moist heat resistance, and molded articles made therefrom have wavelength-selective absorption characteristics and also have excellent thermal and light stability of the absorption characteristics. There are multiple standards for infrared light sources used in infrared sensors in autonomous driving systems, and the wavelength characteristics requirements vary depending on the vehicle manufacturer. Therefore, the resin composition of the present invention can meet the requirements of different vehicle manufacturers. Furthermore, molded articles made from the resin composition of the present invention have excellent thermal and light stability of the absorption characteristics, and are therefore stable under all molding conditions and also under conditions of long-term exposure to light. Therefore, the resin composition of the present invention is particularly useful as a cover material for covering infrared sensors, particularly as a cover material for covering infrared sensors used in driver monitoring systems that monitor drivers and LiDAR that detects other vehicles and buildings, and can contribute to the safe autonomous driving systems of the future. DETAILED DESCRIPTION OF THE INVENTION

[0007] (Component A: aromatic polycarbonate resin) The aromatic polycarbonate resin used as component A in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

[0008] 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), 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-phenylene) Examples of suitable dihydric phenols include 4,4'-(m-phenylenediisopropylidene)diphenol, 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, and 9,9-bis(4-hydroxy-3-methylphenyl)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.

[0009] In the present invention, in addition to bisphenol A type polycarbonate resins, which are general-purpose polycarbonates, it is also possible to use special polycarbonate resins produced using other dihydric phenols as the A component.

[0010] 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, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF") as part or all of the dihydric phenol component 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 particularly 10 mol% or more, of the total dihydric phenol components constituting the polycarbonate resin.

[0011] In particular, when high rigidity and better hydrolysis resistance are required, it is particularly suitable that the component A constituting the resin composition is a copolymer polycarbonate resin of the following (1) to (3). (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 accounts for 20 to 80 mol% (more preferably 25 to 60 mol%, and even more preferably 35 to 55 mol%). (2) A copolymer polycarbonate resin in which, based on 100 mol% of the dihydric phenol components constituting the polycarbonate resin, BPA accounts for 10 to 95 mol% (more preferably 50 to 90 mol%, and even more preferably 60 to 85 mol%) and BCF accounts for 5 to 90 mol% (more preferably 10 to 50 mol%, and even more preferably 15 to 40 mol%). (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%).

[0012] These special polycarbonate resins may be used alone or in a suitable mixture of two or more types, or may be used in a mixture with a commonly used bisphenol A polycarbonate resin.

[0013] The production methods and properties of these special polycarbonate resins are described in detail in, for example, Japanese Patent Application Laid-Open Nos. 6-172508, 8-27370, 2001-55435 and 2002-117580.

[0014] Among the various polycarbonate resins mentioned above, those in which the copolymer composition and the like are adjusted to bring the water absorption rate and Tg (glass transition temperature) into the ranges (i) or (ii) below have good hydrolysis resistance of the polymer itself and are remarkably excellent in low warpage after molding, and are therefore particularly suitable in fields where dimensional stability is required. (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. (ii) A polycarbonate resin having a Tg of 160 to 250°C, preferably 170 to 230°C, and a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

[0015] Here, the water absorption rate of polycarbonate resin 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, and then measuring the moisture content. Also, Tg (glass transition temperature) is a value determined by differential scanning calorimetry (DSC) measurement in accordance with JIS K7121.

[0016] 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.

[0017] 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.

[0018] The branched polycarbonate resin can impart anti-drip properties to the resin composition of the present invention. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate resin 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.

[0019] The structural units derived from a polyfunctional aromatic compound in the branched polycarbonate resin preferably account for 0.01 to 1 mol %, more preferably 0.05 to 0.9 mol %, and even more preferably 0.05 to 0.8 mol %, of the total 100 mol % of the structural units derived from a dihydric phenol and the structural units derived from such a polyfunctional aromatic compound.

[0020] 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 %, based on the total of 100 mol % including the structural units derived from the dihydric phenol. 1 It can be calculated by H-NMR measurement.

[0021] 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.

[0022] The reaction modes of the methods for producing the aromatic 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.

[0023] The melt volume rate (300°C, 1.2 kg load) of the aromatic polycarbonate resin in the present invention is not particularly limited, but is preferably 1 to 60 cm 3 / 10 min, more preferably 3 to 30 cm 3 / 10 min, more preferably 5 to 20 cm 3 / 10min. Melt volume rate is 1cm 3 Resin compositions obtained from aromatic polycarbonate resins with a melt volume rate of less than 60 cm / 10 min may be less versatile due to poor fluidity during injection molding. 3 Aromatic polycarbonate resins with a melt volume rate above 10 min / 10 min may not be able to achieve good mechanical properties. Melt volume rate is also known as "MVR" and is measured in accordance with ISO 1133.

[0024] The viscosity average molecular weight (M) of the aromatic polycarbonate resin in the present invention is preferably 24,000 or less, more preferably 22,500 or less, and even more preferably 20,000 or less. If the viscosity average molecular weight exceeds 24,000, the flowability is poor, and therefore, in order to obtain a thin-walled molded product with a thickness of 1 to 3 mm to be used as a sensor cover material, the molding conditions must be high temperature, which may make the resin or coloring agent prone to thermal decomposition. Furthermore, the lower limit of the viscosity average molecular weight is not particularly limited, but from the viewpoint of impact resistance, it is preferable that it be 14,000 or more. The viscosity average molecular weight (M) referred to in the present invention is first calculated by the specific viscosity (η) calculated by the following formula: 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:

[0025] η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 M 0.83 c=0.7 The aromatic polycarbonate resin of the present invention may be a polycarbonate-polydiorganosiloxane copolymer resin, preferably a copolymer resin prepared by copolymerizing a dihydric phenol represented by the following general formula (1) with a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3):

[0026] [ka]

[0027] [In the above general formula (1), R 1 and R 2 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are multiple of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2):

[0028] [ka]

[0029] [In the above general formula (2), R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R 19 and R 20 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are multiple groups, they may be the same or different; g is an integer of 1 to 10, and h is an integer of 4 to 7.

[0030] [ka]

[0031] [In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. Examples of the dihydric phenol (I) represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2- Bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)propane 4,4'-dihydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'- Dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,Examples include 4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

[0032] Among these, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane is the most suitable due to its excellent strength and durability. These may be used alone or in combination of two or more.

[0033] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), for example, the compounds shown below are preferably used.

[0034] [ka]

[0035] Hydroxyaryl-terminated polydiorganosiloxanes (II) can be easily produced by hydrosilylation of a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol, at the end of a polysiloxane chain having a predetermined degree of polymerization. Among these, (2-allylphenol)-terminated polydiorganosiloxanes and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxanes are preferred, with (2-allylphenol)-terminated polydimethylsiloxanes and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxanes being particularly preferred. The molecular weight distribution (Mw / Mn) of the hydroxyaryl-terminated polydiorganosiloxanes (II) is preferably 3 or less. To achieve even better low outgassing properties during high-temperature molding and low-temperature impact resistance, the molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and even more preferably 2 or less. If the upper limit of this preferred range is exceeded, the amount of outgassing during high-temperature molding may be large, and low-temperature impact resistance may be poor.

[0036] Furthermore, in order to achieve high impact resistance, the diorganosiloxane degree of polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300. The diorganosiloxane degree of polymerization (p+q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. Below the lower limit of this preferred range, the impact resistance that is a characteristic of polycarbonate-polydiorganosiloxane copolymer resins is not effectively exhibited, while above the upper limit of this preferred range, poor appearance appears.

[0037] The polydiorganosiloxane content of the polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.1 to 50% by weight. The polydiorganosiloxane content is more preferably 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. At or above the lower limit of this preferred range, excellent impact resistance and flame retardancy are achieved, while at or below the upper limit of this preferred range, a stable appearance that is less susceptible to the effects of molding conditions is easily achieved. The polydiorganosiloxane polymerization degree and polydiorganosiloxane content are 1 It can be calculated by H-NMR measurement.

[0038] In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.

[0039] Furthermore, other comonomers than the dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in an amount of up to 10% by weight based on the total weight of the copolymer, provided that this does not interfere with the present invention.

[0040] In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting a dihydric phenol (I) with a carbonate-forming compound in a mixed solution of a water-insoluble organic solvent and an aqueous alkaline solution.

[0041] In producing an oligomer of the dihydric phenol (I), the entire amount of the dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at once, or a part of the oligomer may be added as a post-added monomer as a reaction raw material to the interfacial polycondensation reaction in the subsequent stage. The post-added monomer is added to rapidly proceed with the polycondensation reaction in the subsequent stage, and there is no need to add it if it is not necessary.

[0042] The method for this oligomer formation reaction is not particularly limited, but it is usually preferable to carry out the reaction in a solvent in the presence of an acid binder.

[0043] The proportion of the carbonate ester-forming compound used may be adjusted appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. When a gaseous carbonate ester-forming compound such as phosgene is used, it is preferable to blow it into the reaction system.

[0044] Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Similarly, the proportion of the acid binder used may be determined appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid binder relative to the number of moles of the dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0045] As the solvent, various solvents inert to reactions, such as those used in the production of known polycarbonate resins, may be used alone or in combination. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0046] The reaction pressure for oligomer formation is not particularly limited and may be atmospheric, elevated, or reduced pressure, but it is usually advantageous to carry out the reaction under atmospheric pressure. The reaction temperature is selected from the range of -20 to 50°C, and since heat is often generated during polymerization, water or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified in general, but is usually carried out for 0.2 to 10 hours. The pH range for the oligomer formation reaction is similar to that of known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

[0047] In the present invention, after obtaining a mixed solution containing an oligomer of a dihydric phenol (I) having terminal chloroformate groups in this manner, the mixed solution is stirred and a hydroxyaryl-terminated polydiorganosiloxane (II) represented by general formula (3), which has been highly purified to a molecular weight distribution (Mw / Mn) of 3 or less, is added to the dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer resin.

[0048] When carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate, taking into account the stoichiometric ratio (equivalents) of the reaction. Examples of acid binders that can be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) used, or a portion of the dihydric phenol (I) as described above, is added to this reaction stage as a post-added monomer, it is preferable to use 2 equivalents or more of alkali relative to the total moles of the post-added dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

[0049] The polycondensation by interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixture.

[0050] In such polymerization reactions, a terminal terminator or a molecular weight modifier is usually used. Examples of terminal terminators include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of the total dihydric phenol compounds used, and it is of course possible to use two or more compounds in combination.

[0051] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.

[0052] The reaction time for such a polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

[0053] A branching agent can be used in combination with the above-mentioned dihydric phenol compound to produce a branched polycarbonate-polydiorganosiloxane copolymer resin. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)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-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, trisphenols such as 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 which 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. The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9 mol %, even more preferably 0.01 to 0.8 mol %, and particularly preferably 0.05 to 0.4 mol %, based on the total amount of the branched polycarbonate-polydiorganosiloxane copolymer resin. 1 It can be calculated by H-NMR measurement.

[0054] The reaction pressure can be reduced, normal, or increased, but is usually preferably normal pressure or the inherent pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and in many cases, water or ice cooling is desirable because heat is generated during polymerization. The reaction time cannot be generally determined because it varies depending on other conditions such as the reaction temperature, but is usually 0.5 to 10 hours.

[0055] In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is subjected to appropriate physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduced viscosity [η SP It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin of formula [ / c].

[0056] The resulting reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods to recover a polycarbonate-polydiorganosiloxane copolymer resin of the desired purity (degree of purification).

[0057] The average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 40 nm. This average size is more preferably 1 to 30 nm, and even more preferably 5 to 25 nm. Below the lower limit of this preferred range, impact resistance and flame retardancy may not be fully exhibited, while above the upper limit of this preferred range, impact resistance may not be stably exhibited. This provides a resin composition with excellent impact resistance and appearance. The average domain size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded articles of the present invention was evaluated using small-angle X-ray scattering (SAXS). Small-angle X-ray scattering measures the diffuse scattering and diffraction that occur in the small-angle region of scattering angles (2θ) less than 10°. In this method, if a substance contains regions with different electron densities of approximately 1 to 100 nm in size, the diffuse scattering of X-rays is measured based on the electron density difference. The particle size of the object being measured is determined based on the scattering angle and scattering intensity. In the case of polycarbonate-polydiorganosiloxane copolymer resins, which form an aggregate structure in which polydiorganosiloxane domains are dispersed within a polycarbonate polymer matrix, the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains causes diffuse scattering of X-rays. The scattering intensity I at each scattering angle (2θ) within a range of less than 10° is measured to obtain a small-angle X-ray scattering profile. Assuming that the polydiorganosiloxane domains are spherical and that there is variation in particle size distribution, a simulation is performed using commercially available analysis software based on a hypothetical particle size and a hypothetical particle size distribution model to determine the average size of the polydiorganosiloxane domains. Small-angle X-ray scattering allows for accurate, simple, and reproducible measurement of the average size of polydiorganosiloxane domains dispersed in a polycarbonate polymer matrix, which cannot be accurately measured by observation using a transmission electron microscope. The term "average domain size" used in connection with this invention refers to the measurement obtained by measuring a 1.0 mm thick section of a three-tiered plate prepared by the method described in the Examples using the small-angle X-ray scattering method. Furthermore, analysis is performed using an isolated particle model that does not take into account interparticle interactions (interparticle interference). (Component B: Coloring agent with an absorption maximum below 650 nm) The colorant used as component B in the present invention is a colorant having an absorption maximum at less than 650 nm. The lower limit of the absorption maximum is not particularly specified, but is preferably 400 nm or greater. The colorant can be selected from dyes (organic or inorganic), pigments (organic or inorganic), and the like, and is not particularly limited as long as the aromatic polycarbonate resin composition of the present invention can be obtained. Dyes are preferably used as colorants because they do not cause diffused reflection of light on the particle surfaces. Examples of dye-based colorants include anthraquinone-based colorants, perinone-based colorants, perylene-based colorants, methine-based colorants, azo-based colorants, quinoline-based colorants, phthalocyanine-based colorants, squarylium-based colorants, and heterocyclic-based colorants. The content of Component B is 0.03 to 1.2 parts by weight, preferably 0.05 to 1.0 part by weight, and more preferably 0.1 to 0.5 parts by weight, per 100 parts by weight of Component A. If the content of Component B is less than 0.03 part by weight, sufficient cutoff characteristics in the range of 400 nm to 870 nm cannot be obtained. On the other hand, if the content exceeds 1.2 parts by weight, the thermal stability of the resin composition deteriorates. (Component C: a coloring agent with an absorption maximum between 650 nm and 870 nm) The colorant used as component C in the present invention is a colorant having an absorption maximum at 650 nm or more and less than 870 nm. The colorant can be selected from dyes (organic or inorganic), pigments (organic or inorganic), etc., and is not particularly limited as long as the aromatic polycarbonate resin composition of the present invention can be obtained. Dyes are preferred as the colorant because they do not cause diffused reflection of light on the particle surface. Examples of dye-based colorants include anthraquinone-based colorants, perinone-based colorants, perylene-based colorants, methine-based colorants, azo-based colorants, quinoline-based colorants, phthalocyanine-based colorants, squarylium-based colorants, and heterocyclic-based colorants. Among these, anthraquinone-based colorants, phthalocyanine-based colorants, perylene-based colorants, and heterocyclic-based colorants, which have high heat resistance, are more preferred. The content of Component C is 0.001 to 0.3 parts by weight, preferably 0.003 to 0.2 parts by weight, and more preferably 0.005 to 0.1 parts by weight, per 100 parts by weight of Component A. If the content of Component C is less than 0.001 part by weight, sufficient cutoff characteristics in the range of 400 nm to 870 nm cannot be obtained. On the other hand, if the content exceeds 0.3 part by weight, the thermal stability of the resin composition deteriorates. (Component D: a coloring agent with an absorption maximum between 870 nm and 1000 nm) The colorant used as component D in the present invention is a colorant having an absorption maximum at 870 nm or more and less than 1000 nm. The colorant can be selected from dyes (organic or inorganic), pigments (organic or inorganic), etc., and is not particularly limited as long as the aromatic polycarbonate resin composition of the present invention can be obtained. As the colorant, dyes are preferably used because they do not cause diffused reflection of light on the particle surface. Examples of dye-based colorants include anthraquinone-based colorants, perinone-based colorants, perylene-based colorants, methine-based colorants, azo-based colorants, quinoline-based colorants, phthalocyanine-based colorants, squarylium-based colorants, and heterocyclic-based colorants. Among these, anthraquinone-based colorants, phthalocyanine-based colorants, perylene-based colorants, and heterocyclic-based colorants, which have high heat resistance, are more preferred. The content of component D is 0.001 to 0.3 parts by weight, preferably 0.003 to 0.2 parts by weight, and more preferably 0.005 to 0.1 parts by weight, per 100 parts by weight of component A. If the content of component D is less than 0.001 part by weight, sufficient cutoff characteristics cannot be obtained from 870 nm to the wavelength where component D has maximum absorption. On the other hand, if the content exceeds 0.3 part by weight, the thermal stability of the resin composition deteriorates. (Component E: Heat stabilizer) The aromatic polycarbonate resin composition of the present invention contains a phosphorus-based heat stabilizer and / or a phenol-based heat stabilizer. The phosphorus-based heat stabilizer improves thermal stability during production or molding processing, and improves mechanical properties, color, and molding stability. Examples of phosphorus-based heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and their esters, as well as tertiary phosphines. Specific examples of the phosphite compound include triphenyl phosphite, tris(nonylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, tris(diethylphenyl)phosphite, tris(di-isopropylphenyl)phosphite, and tris(di-n-butylphenyl)phosphite. bis(2,6-di-tert-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, etc. Furthermore, as other phosphite compounds, those which react with dihydric phenols to have a cyclic structure can also be used.For example, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, and the like can be mentioned. Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate, and preferred are triphenyl phosphate and trimethyl phosphate.

[0058] Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl ... Examples of suitable phosphonite compounds include (2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite. Preferred are tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, with tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite being more preferred. These phosphonite compounds can be used in combination with phosphite compounds having an aryl group substituted with two or more alkyl groups, which is preferred. Examples of suitable phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Examples of tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.The phosphorus-based heat stabilizer can be used alone or in combination of two or more. Among the phosphorus-based heat stabilizers, it is preferable to use an alkyl phosphate compound, such as trimethyl phosphate. It is also a preferred embodiment to use such an alkyl phosphate compound in combination with a phosphite compound and / or a phosphonite compound.

[0059] The phenolic heat stabilizer is not particularly limited as long as it has an antioxidant function, and examples thereof include n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, tetrakis{methylene-3-(3',5'-di-t-butyl-4-hydroxyphenyl)propionate}methane, distearyl(4-hydroxy-3-methyl-5-t-butylbenzyl)malonate, triethyleneglycol-bis{3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate}, 1,6-hexanediol-bis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, pentaerythrityl-tetrakis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, 2,2-thiodiethyl Benzenebis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, 2,2-thiobis(4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 2,4-bis{(octylthio) methyl}-o-cresol, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,5,7,8-tetramethyl-2(4',8',12'-trimethyltridecyl)chroman-6-ol, 3,3',3",5,5',5"-hexa-t-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, and the like.

[0060] Among these, n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, pentaerythrityl-tetrakis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, 3,3',3",5,5',5"-hexa-t-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, 2,2-thiodiethylenebis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, and the like are preferred.

[0061] The content of component E is 0.003 to 0.5 parts by weight, preferably 0.005 to 0.3 parts by weight, and more preferably 0.01 to 0.2 parts by weight, per 100 parts by weight of component A. If the content of component E is less than 0.003 parts by weight, the thermal stability of the resin composition and the thermal stability of the absorption characteristics will also deteriorate. On the other hand, if the content exceeds 0.5 parts by weight, the moist heat resistance of the resin composition will deteriorate. (Component F: Benzotriazole-based UV absorber) The aromatic polycarbonate resin composition of the present invention preferably contains a benzotriazole-based ultraviolet absorber. Examples of the benzotriazole-based ultraviolet absorber include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, and 2,2'-methylenebiphenyl. [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-octyl Examples include 2-hydroxyphenyl-2H-benzotriazole skeleton-containing polymers such as 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole, 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, and copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and vinyl monomers copolymerizable with said monomers, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and vinyl monomers copolymerizable with said monomers. Furthermore, the ultraviolet absorber may have a structure of a radically polymerizable monomer compound, and may be a polymeric ultraviolet absorber obtained by copolymerizing such an ultraviolet absorbing monomer and / or a photostable monomer with a monomer such as alkyl (meth)acrylate.Suitable examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton in the ester substituent of a (meth)acrylic acid ester. Among them, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, such as Tinuvin 234 (BASF Japan Ltd.), and 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, such as Tinuvin 326 (BASF Japan Ltd.), are more preferred.

[0062] The content of component F is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.8 parts by weight, and even more preferably 0.1 to 0.5 parts by weight, relative to 100 parts by weight of component A. If the content of component F is less than 0.01 part by weight, the light stability of the absorption characteristics may deteriorate, while if it exceeds 1 part by weight, the thermal stability of the resin composition may decrease. (Other additives) In order to improve the thermal stability and designability of the aromatic polycarbonate resin composition of the present invention, additives used to improve these properties can be advantageously used. These additives will be specifically described below. (I) Heat stabilizers other than component E The aromatic polycarbonate resin composition of the present invention can also contain heat stabilizers other than the phosphorus-based heat stabilizer and phenol-based heat stabilizer. Suitable examples of such 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 Japanese Patent Application Laid-Open No. 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 in combination with various phosphite compounds and hindered phenol compounds are commercially available. A suitable example is Irganox HP-2921 manufactured by the same company. The content of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, per 100 parts by weight of Component A. Other examples of stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. The content of such sulfur-containing stabilizers is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of Component A. An epoxy compound can be blended into the polycarbonate resin composition of the present invention as needed. Such epoxy compounds are blended for the purpose of inhibiting mold corrosion, and essentially any compound having an epoxy functional group can be used. Specific examples of preferred epoxy compounds include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, copolymer of methyl methacrylate and glycidyl methacrylate, copolymer of styrene and glycidyl methacrylate, etc. The content of such epoxy compounds is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, and even more preferably 0.005 to 0.1 parts by weight, per 100 parts by weight of Component A. (II) Mold release agent The aromatic polycarbonate resin composition of the present invention may contain a mold release agent in order to further improve releasability from a mold during melt molding, within the scope of the present invention.

[0063] Examples of such release agents include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefin waxes, olefin waxes containing a carboxy group and / or a carboxylic acid anhydride group, silicone oil, organopolysiloxane, etc. Preferred higher fatty acid esters are partial or complete esters of monohydric or polyhydric alcohols having 1 to 20 carbon atoms with saturated fatty acids having 10 to 30 carbon atoms. Examples of such partial or complete esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearate monosorbitate, stearyl stearate, behenic acid monoglyceride, behenyl behenate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, and 2-ethylhexyl stearate. Among these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferred. As the higher fatty acid, saturated fatty acids having 10 to 30 carbon atoms are preferred. Such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid.

[0064] These release agents may be used alone or in combination of two or more. The content of such release agents is preferably 0.01 to 5 parts by weight per 100 parts by weight of component A. <Method of manufacturing resin composition> Any method can be used to produce the aromatic polycarbonate resin composition of the present invention. For example, the components and optionally other components can be premixed, followed by melt-kneading and pelletizing. Examples of premixing methods include a Nauta mixer, a V-blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. Premixing can also be performed using an extrusion granulator or briquetting machine. After premixing, the mixture is melt-kneaded in a melt mixer, typically a vented twin-screw extruder, and pelletized using a pelletizer or other device. Other examples of melt mixers include a Banbury mixer, a kneading roll, and a thermostatically controlled stirring vessel. A vented twin-screw extruder is preferred. Alternatively, the components and optionally other components can be fed independently to a melt mixer, typically a twin-screw extruder, without premixing. <About molded products> The aromatic polycarbonate resin composition of the present invention obtained as described above can be injection-molded into various products. Furthermore, it is also possible to directly form sheets, films, profile extrusions, and injection-molded articles from the melt-kneaded resin in an extruder without first passing through the pelletizing process. In such injection molding, molded articles can be obtained 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, adiabatic 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 various molding methods are already widely known. Molding can be performed using either a cold runner system or a hot runner system. The resin composition of the present invention can also be extrusion-molded into various profile extrusions and sheets. Molded articles made from the aromatic polycarbonate resin composition of the present invention must have an average light transmittance in the thickness direction of a 3 mm-thick molded article at 400 to 870 nm of 1.5% or less. The average light transmittance is more preferably 1.0% or less, and even more preferably 0.5% or less. If the average light transmittance exceeds 1.5%, the amount of sunlight that becomes noise increases, adversely affecting sensing. While there is no particular lower limit for the average light transmittance, it is preferably 0%.

[0065] Furthermore, a molded article made from the aromatic polycarbonate resin composition of the present invention preferably has an average light transmittance in the thickness direction of a 3 mm-thick molded article at wavelengths from 870 nm to the wavelength at which the absorption of component D is maximum of 1.5% or less, more preferably 1.0% or less, and even more preferably 0.5% or less. If the average light transmittance exceeds 1.5%, the amount of sunlight that becomes noise increases, which may adversely affect sensing. There is no particular lower limit to the average light transmittance, but 0% is preferred. [Example]

[0066] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" are parts by weight. Evaluations were carried out by the following methods. [Evaluation of Resin Composition] 1. Average light transmittance at wavelengths from 400 nm to 870 nm and from 870 nm to the maximum absorption wavelength of component D The spectral light transmittance of the continuously molded product produced by the method described below was measured in the range of 300 nm to 2500 nm using an ultraviolet-visible-near-infrared spectrophotometer (V-770 manufactured by JASCO Corporation). From the obtained spectral spectrum, the average light transmittance from 400 nm to 870 nm and the average light transmittance from 870 nm to the absorption maximum wavelength of component D were calculated. 2. Thermal stability of absorption characteristics The spectral light transmittance of the continuous molded product was measured using the same method as in "1. Average light transmittance at wavelengths from 400 nm to 870 nm and from 870 nm to the absorption maximum wavelength of component D." The obtained spectrum was scanned from a wavelength of 400 nm toward longer wavelengths, and the wavelength at which transmittance first reached 70% or more (transmission wavelength λt) was read. The transmission wavelength λtr was also read using the same method for the retention molded product. λtr-λt of 0 to 5 was marked with a ◎, 6 to 10 with a 〇, 11 to 20 with a △, and 21 or more with an ×. 3.Photostability of absorption properties: The spectral light transmittance of the light-exposed sample was measured using the same method as in "1. Average light transmittance at wavelengths from 400 nm to 870 nm and from 870 nm to the absorption maximum wavelength of component D." The obtained spectrum was scanned from a wavelength of 400 nm toward longer wavelengths, and the wavelength at which transmittance first reached 70% or more (transmission wavelength λtx) was read. |λtx - λt| was marked as ◎ when it was between 0 and 5, as ○ when it was between 6 and 10, as △ when it was between 11 and 20, and as × when it was 21 or more. 4. Thermal stability of resin composition (viscosity average molecular weight): The viscosity average molecular weight (M0) of the continuous molded product and the viscosity average molecular weight (M1) of the retention molded product were measured by the following method. When M0-M1<1,000 was satisfied, it was marked as ◯, and when it was not, it was marked as ×.

[0067] The viscosity average molecular weight (M) is calculated by first calculating the specific viscosity (η SP ) was measured using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of the molded product obtained by the method described below 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 ) was calculated using the following formula:

[0068] η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 M0.83 c=0.7 5. Moisture and heat resistance of resin composition (viscosity average molecular weight): The viscosity average molecular weight (M0) of the continuous molded product and the viscosity average molecular weight (M2) of the moist heat treated product were measured in the same manner as in "5. Thermal stability of resin composition." Cases where M0 - M2 < 1,000 were satisfied were marked with an O, and cases where this was not satisfied were marked with an X. [Examples 1 to 27, Comparative Examples 1 to 8] [Production of resin pellets] Based on the components and amounts shown in Tables 1 to 3, various components were mixed using a tumbler and melt-kneaded using a twin-screw extruder (TEX30α, manufactured by The Japan Steel Works, Ltd.) at a cylinder temperature of 280°C to obtain various pellets. The components used are as follows: [Production of molded products by injection molding] The pellets obtained by the above method were dried in a hot air circulation dryer at 120°C for 5 hours, and then molded into 3mm thick plate-shaped test pieces using an injection molding machine (ROBOSHOT α-S100iA, manufactured by FANUC Corporation) under conditions of a cylinder temperature of 340°C and a mold temperature of 80°C. Molding was performed continuously, with injection stopped for 10 minutes while resin was still in the cylinder, and then molding was performed again. Products molded continuously without stopping injection midway were designated continuous molded products, and products molded after stopping injection for 10 minutes while resin was still in the cylinder were designated retention molded products. [Light exposure treatment of molded products] The continuous molded product obtained by the above method was subjected to a xenon weather meter (Suga Testing Instruments Co., Ltd. NX75Z) at a black panel temperature of 63°C, a chamber temperature of 50°C, a relative humidity of 50%, and an irradiation intensity of 0.35 W / m 2 The molded product was subjected to light exposure treatment for 1000 hours under the condition of (@340 nm) and was designated as the light-exposed product. [Moist heat treatment of molded products] The continuous molded product obtained by the above method was subjected to a moist heat treatment for 1000 hours under conditions of a temperature of 80°C and a humidity of 85% using a thermo-hygrostat (Espec Corporation PR-3J). The resulting molded product was designated as a moist heat-treated product. (Component A) A-1: Teijin Ltd. Panlite L-1225WX (viscosity average molecular weight: 19,700) A-2: Teijin Ltd. Panlite L-1225WP (viscosity average molecular weight: 22,400) A-3: Polycarbonate resin produced by the following method A reactor equipped with a thermometer, stirrer, and reflux condenser was charged with 3,844 parts of 48% aqueous sodium hydroxide solution and 22,380 parts of ion-exchanged water, to which 1,992 parts of 2,2-bis(4-hydroxy-3-methylphenyl)propane (Bis-C, Honshu Chemical Co., Ltd.), 1,773 parts of 2,2-bis(4-hydroxyphenyl)propane (Bis-A, Nippon Steel Chemical Co., Ltd.), and 7.53 parts of hydrosulfite (Wako Pure Chemical Industries, Ltd.) were dissolved. 13,210 parts of methylene chloride was added, and 2,000 parts of phosgene was blown in over approximately 60 minutes at 15 to 25°C with stirring. After completion of the phosgene blowing, 640 parts of 48% aqueous sodium hydroxide solution and 93.2 parts of p-tert-butylphenol were added, stirring was resumed, and after emulsification, 3.24 parts of triethylamine was added. The mixture was further stirred at 28 to 33°C for 1 hour to complete the reaction. After the reaction was complete, the product was diluted with methylene chloride and washed with water, then acidified with hydrochloric acid and washed with water. This process was repeated until the conductivity of the aqueous phase was nearly the same as that of ion-exchanged water, yielding a methylene chloride solution of polycarbonate resin. This solution was then passed through a 0.3 μm filter and added dropwise to warm water in a kneader with an isolation chamber and a foreign matter outlet in the bearing section. The polycarbonate resin was flaked while the methylene chloride was distilled off. The liquid-impregnated flakes were then crushed and dried to obtain a powder. The viscosity-average molecular weight was 20,000. (B component) B-1: NUBIAN BLACK PC-5857 (Orient Chemical Industries, Ltd., maximum absorption wavelength 599 nm) (C component) C-1: Anthraquinone colorant SDO-11 (Arimoto Chemical Industry Co., Ltd., maximum absorption wavelength 761 nm) C-2: Perylene colorant Lumogen IR-765 (BASF Japan Ltd., maximum absorption wavelength 769 nm) C-3: Heterocyclic colorant SDO-C33 (Arimoto Chemical Industry Co., Ltd., maximum absorption wavelength 847 nm) (D component) D-1: Phthalocyanine colorant FDN-005 (Yamada Chemical Co., Ltd., maximum absorption wavelength 911 nm) D-2: Phthalocyanine colorant FDN-007 (Yamada Chemical Co., Ltd., maximum absorption wavelength 956 nm) D-3: Phthalocyanine colorant FDN-008 (Yamada Chemical Co., Ltd., maximum absorption wavelength 992 nm) (E component) E-1: Phosphorus-based heat stabilizer ADK STAB 2112 (ADEKA Corporation) E-2: Phenolic heat stabilizer AO-50 (ADEKA Corporation) (F component) F-1: Benzotriazole-based UV absorber Tinuvin 234 (BASF Japan Ltd.) F-2: Benzotriazole-based UV absorber Tinuvin 326 (BASF Japan Ltd.) F-3: Benzotriazole-based UV absorber Seesorb 709 (Shipro Chemical Co., Ltd.) (Other ingredients) G-1: Unistar H476S (NOF Corporation) G-2: Rikestar EW-400 (Riken Vitamin Co., Ltd.) H-1: Marproof G-0250SP (NOF Corporation)

[0069] [Table 1]

[0070] [Table 2]

[0071] [Table 3]

[0072] The examples listed in Tables 1 to 3 all have excellent thermal stability and moist heat resistance of the resin compositions, and have wavelength-selective absorption properties, making them compatible with the various infrared light sources used in infrared sensors for autonomous driving systems. Furthermore, the results showed excellent thermal and light stability of the absorption properties. When the contents of components B and C were less than the lower limits, the average light transmittance from 400 nm to 870 nm exceeded 1.5%. When the content of component D was less than the lower limit, the average light transmittance from 870 nm to the absorption maximum wavelength of component D exceeded 1.5%. On the other hand, when the content exceeded the upper limit, the thermal stability of the resin composition deteriorated. When the content of component E was less than the lower limit, the thermal stability of the resin composition and absorption characteristics was poor, and when it exceeded the upper limit, the moist heat resistance of the resin composition was poor.

Claims

1. 1. A resin composition comprising 100 parts by weight of (A) an aromatic polycarbonate resin (Component A), 0.03 to 1.2 parts by weight of (B) one coloring agent (Component B) having an absorption maximum at less than 650 nm, 0.001 to 0.3 parts by weight of (C) one coloring agent (Component C) having an absorption maximum at 650 nm or more but less than 870 nm, 0.001 to 0.3 parts by weight of (D) one coloring agent (Component D) having an absorption maximum at 870 nm or more but less than 1000 nm, 0.003 to 0.5 parts by weight of (E) a phosphorus-based heat stabilizer and / or a phenol-based heat stabilizer (Component E), and 0.01 to 0.2 parts by weight of (F) a benzotriazole-based ultraviolet absorber (Component F), wherein the resin composition has an average light transmittance of 1.5% or less in the thickness direction of a molded product at 400 nm to 870 nm when molded to a thickness of 3 mm under conditions of a cylinder temperature of 340°C and a mold temperature of 80°C.

2. The resin composition according to claim 1, wherein the average light transmittance in the thickness direction of a molded article having a thickness of 3 mm is 1.5% or less at wavelengths from 870 nm to the wavelength at which the absorption of component D is maximum.

3. 3. The resin composition according to claim 1, wherein the components C and D are at least one colorant selected from the group consisting of anthraquinone-based colorants, phthalocyanine-based colorants, perylene-based colorants, and heterocyclic colorants.

4. 3. The resin composition according to claim 1, wherein the viscosity average molecular weight of component A is 24,000 or less.

5. A molded article obtained by molding the resin composition according to claim 1 or 2.

6. 6. The molded article according to claim 5, which is a cover material for covering an infrared sensor.

7. The molded article according to claim 6, which is a cover material for covering an infrared sensor used in LiDAR for detecting vehicles and buildings.

Images