Aromatic polycarbonate resin composition and molded article thereof

Abstract

The present invention provides an aromatic polycarbonate resin composition and a molded article thereof, which have excellent thermal stability and wet heat resistance, and a molded article made from the same has wavelength-selective absorption characteristics, and further has excellent thermal stability and light stability of the absorption characteristics. The present invention relates to a resin composition and a method for manufacturing the same. The present invention relates to an aromatic polycarbonate resin composition containing, per 100 parts by weight of (A) an aromatic polycarbonate resin (component A), 0.03-1.2 parts by weight of (B) a colorant having an absorption maximum at less than 650 nm (component B), 0.001-0.3 parts by weight of (C) a colorant having an absorption maximum at 650 nm or more and less than 870 nm (component C), 0.001-0.3 parts by weight of (D) a colorant having an absorption maximum at 870 nm or more and less than 1000 nm (component D), and 0.003-0.003 parts by weight of (E) a phosphorus-based heat stabilizer and / or a phenol-based heat stabilizer (component E). The average value of the light transmittance in the thickness direction of a molded article molded to a thickness of 3 mm at a wavelength of 400-870 nm is 1.5% or less.

Description

Technical Field

[0001] The present invention relates to an aromatic polycarbonate resin composition having excellent thermal stability and moisture-heat resistance, and a molded article made therefrom has wavelength-selective absorption characteristics, and further has excellent thermal stability and light stability of the absorption characteristics. Background Art

[0002] In recent years, autonomous driving technology has achieved rapid development. Sensing systems using infrared rays play an important role in autonomous driving technology. As sensing systems using infrared rays, for example, driver monitoring device systems that monitor drivers and LiDARs that detect other vehicles and buildings conform to the above-mentioned sensing systems, and near-infrared rays after about 700nm are generally used in sensing. Moreover, when performing sensing using infrared rays, since visible light to near-infrared light becomes noise, a cover material is required to transmit the wavelength region used for sensing and block the transmission of the wavelength region below it. As the cover material, glass or resin is used. Among the resins, acrylic resins, polycarbonate resins, etc., which are transparent materials, are generally used, but there is a greater demand for polycarbonate resins that have good transparency and excellent impact resistance and heat resistance.

[0003] In the past, research on wavelength selective control of polycarbonate resins has also been conducted. They are technologies that block the visible light region to a part of the near-infrared region by using multiple colorants with different absorption bands (see patent documents 1 to 6). In particular, in recent years, as shown in patent documents 5 and 6, technologies that block to the longer wavelength side of about 1000 to 1100 nm have also been established. As a background, it can be cited that as the level of autonomous driving increases (level 4 or above), the sensing accuracy is required to be further improved, so it is necessary to block the sunlight noise to the longer wavelength side.

[0004] However, the stability of the absorption characteristics is not disclosed in these documents. In fact, the cover material of the infrared sensor used for autonomous driving technology is molded with a thin wall thickness of about 1 to 3 mm, so as the viscosity average molecular weight of the polycarbonate resin, a relatively high flow material of less than 24,000 is preferred, and the molding temperature also reaches a high temperature of 300 to 340°C. Therefore, the thermal stability of the wavelength characteristics of high-temperature molding is very important. Moreover, in automobiles, the resin is in an environment where it is constantly exposed to light, so it is important that its wavelength characteristics continue to be stable even if it is irradiated with light for a long time. That is, in order to realize a safe autonomous driving society, the cover material of the infrared sensor requires thermal stability and light stability of the absorption characteristics.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Patent No. 5040827

[0008] Patent Document 2: Patent Publication No. 6354888

[0009] Patent Document 3: WO2019 / 022169

[0010] Patent Document 4: Patent No. 6658942

[0011] Patent Document 5: Japanese Patent Application Publication No. 2021-188011

[0012] Patent Document 6: Japanese Patent Application Publication No. 2021-147470 Summary of the invention

[0013] An object of the present invention is to provide an aromatic polycarbonate resin composition and a molded article thereof, which are excellent in thermal stability and moisture-heat resistance and the molded article produced therefrom has wavelength-selective absorption characteristics and further has excellent thermal stability and light stability of the absorption characteristics.

[0014] The present inventors have conducted intensive studies and 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 its molded article.

[0015] 1. A resin composition comprising: (B) 0.03 to 1.2 parts by weight of a colorant having an absorption maximum at less than 650 nm (component B), (C) 0.001 to 0.3 parts by weight of a colorant having an absorption maximum at 650 nm or more and less than 870 nm (component C), (D) 0.001 to 0.3 parts by weight of a colorant having an absorption maximum at 870 nm or more and less than 1000 nm (component D), and (E) 0.003 to 0.5 parts by weight of a phosphorus-based heat stabilizer and / or a phenolic heat stabilizer (component E), based on 100 parts by weight of (A) an aromatic polycarbonate resin (component A), wherein the average value of light transmittance in the thickness direction of a molded article having a thickness of 3 mm at a wavelength of 400 nm to 870 nm is 1.5% or less.

[0016] 2. The resin composition according to item 1 above, wherein the average value of light transmittance in the thickness direction of a molded article having a thickness of 3 mm at a wavelength of 870 nm to where the absorption of the D component reaches a maximum value is 1.5% or less.

[0017] 3. The resin composition according to the above item 1 or 2, wherein the components C and D are at least one colorant selected from anthraquinone colorants, phthalocyanine colorants, perylene colorants and heterocyclic colorants.

[0018] 4. The resin composition according to any one of the above 1 to 3, characterized in that the resin composition contains 0.01 to 1 part by weight of a benzotriazole-based ultraviolet absorber (component F) based on 100 parts by weight of component A.

[0019] 5. The resin composition according to any one of the above 1 to 4, wherein the viscosity average molecular weight of component A is 24,000 or less.

[0020] 6. A molded article obtained by molding the resin composition according to any one of 1 to 5 above.

[0021] 7. The molded article according to item 6 above, which is a cover material covering an infrared sensor.

[0022] 8. The molded article according to the above item 7, which is a cover material for covering an infrared sensor used in LiDAR for detecting vehicles and buildings.

[0023] The resin composition of the present invention has excellent thermal stability and moisture and heat resistance, and the molded product made therefrom has wavelength-selective absorption characteristics, and the thermal stability and light stability of the absorption characteristics are excellent. The infrared light source of the infrared sensor for the automatic driving system has multiple specifications and the requirements for wavelength characteristics vary according to the vehicle manufacturer, so the resin composition of the present invention can meet the requirements of different vehicle manufacturers. Moreover, the thermal stability and light stability of the absorption characteristics of the molded product made of the resin composition of the present invention are excellent, so it is stable for all molding conditions, and in addition, it is also stable for the conditions of long-term light exposure. Therefore, the resin composition of the present invention is particularly useful as a cover material for covering infrared sensors, wherein the cover material of the infrared sensor used as a driver monitoring device system for covering the driver monitoring the driver, and the LiDAR for detecting other vehicles and buildings is useful, and can contribute to future safe automatic driving systems. DETAILED DESCRIPTION

[0024] (Component A: aromatic polycarbonate resin)

[0025] In the present invention, the aromatic polycarbonate resin used as the A component is the aromatic polycarbonate resin that dihydric phenol and carbonate precursor reaction obtain.As an example of reaction method, can enumerate the solid phase transesterification method of interfacial polymerization, melt transesterification method, carbonate prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc.

[0026] Representative examples of the dihydric phenols used herein include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (also 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)-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)- ... )pentane, 4,4'-(p-phenylene diisopropylidene)diphenol, 4,4'-(m-phenylene diisopropylidene)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 them, bisphenol A is particularly preferred from the viewpoint of impact resistance and is commonly used.

[0027] In the present invention, in addition to bisphenol A type polycarbonate resin which is a general-purpose polycarbonate, a special polycarbonate resin produced using other dihydric phenols can be used as the A component.

[0028] For example, polycarbonate resins (homopolymers or copolymers) using 4,4'-(m-phenylene diisopropylidene) diphenol (hereinafter, sometimes referred to as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter, sometimes referred to as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter, sometimes referred to as "BCF") as part or all of the dihydric phenol components are suitable for applications where the requirements for dimensional change or morphological stability due to water absorption are particularly strict. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more of the total dihydric phenol components constituting the polycarbonate resin, and particularly preferably 10 mol% or more.

[0029] In particular, when high rigidity and better hydrolysis resistance are required, the component A constituting the resin composition is preferably a copolymerized polycarbonate resin of the following (1) to (3).

[0030] (1) A copolymer polycarbonate resin, wherein, based on 100 mol % of a dihydric phenol component constituting the polycarbonate resin, BPM is 20 to 80 mol % (more preferably 40 to 75 mol %, and further preferably 45 to 65 mol %), and BCF is 20 to 80 mol % (more preferably 25 to 60 mol %, and further preferably 35 to 55 mol %).

[0031] (2) A copolymer polycarbonate resin, wherein, in 100 mol % of the dihydric phenol component constituting the polycarbonate resin, BPA accounts for 10 to 95 mol % (more preferably 50 to 90 mol %, and further preferably 60 to 85 mol %), and BCF accounts for 5 to 90 mol % (more preferably 10 to 50 mol %, and further preferably 15 to 40 mol %).

[0032] (3) A copolymer polycarbonate resin, wherein, in 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 %).

[0033] These special polycarbonate resins may be used alone or in combination of two or more thereof, or may be mixed with a general-purpose bisphenol A type polycarbonate resin.

[0034] 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.

[0035] It should be noted that among the various polycarbonate resins mentioned above, the polycarbonate resin whose copolymer composition is adjusted so that the water absorption rate and Tg (glass transition temperature) are within the range of (i) or (ii) below is particularly suitable in fields requiring morphological stability because the polymer itself has good resistance to hydrolysis and is also particularly excellent in low warpage after molding.

[0036] (i) A polycarbonate resin having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C.

[0037] (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%.

[0038] Here, the water absorption of the polycarbonate resin is a value obtained by measuring the water content of a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm after immersion in water at 23° C. for 24 hours in accordance with ISO 62-1980. In addition, Tg (glass transition temperature) is a value obtained by differential scanning calorimetry (DSC) in accordance with JIS K 7121.

[0039] As the carbonate precursor, a hydroxyhalide, a carbonic acid diester, a halogenated format, or the like can be used. Specific examples thereof include phosgene, diphenyl carbonate, and a dihalogenated format of a dihydric phenol.

[0040] When utilizing above-mentioned dihydric phenol and carbonate precursor to manufacture polycarbonate resin by interfacial polymerization, can use catalyst, end-capping agent, antioxidant that is used to prevent dihydric phenol from being oxidized etc. as required.In addition, polycarbonate resin of the present invention comprises: the branched polycarbonate resin that makes the copolymerization of trifunctional or more polyfunctional aromatic compound, the polyester carbonate resin that makes the copolymerization of aromatic or aliphatic (comprising alicyclic) difunctional carboxylic acid, the copolymerization polycarbonate resin that makes difunctional alcohol (comprising alicyclic) copolymerize, and the polyester carbonate resin that makes the above-mentioned difunctional carboxylic acid and difunctional alcohol copolymerize together.In addition, also can be the mixture that 2 or more of the polycarbonate resin that obtain are mixed.

[0041] 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 the branched polycarbonate resin include pyrogallol, pentahydroxybiphenyl or 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-methyl The present invention can be used in combination with any of the foregoing inventions and / or the invention can be used to prepare trisphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetrakis(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene or 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.

[0042] The structural unit derived from the polyfunctional aromatic compound of the branched polycarbonate resin is preferably 0.01 to 1 mol %, more preferably 0.05 to 0.9 mol %, and even more preferably 0.05 to 0.8 mol % in the total 100 mol % of the structural units derived from the diphenol and the structural units derived from the above-mentioned polyfunctional aromatic compound.

[0043] In addition, in particular, in the case of the melt transesterification method, a branched structural unit may be generated as a side reaction. The amount of the branched structural unit is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and further preferably 0.01 to 0.8 mol%, based on 100 mol% of the total of the structural unit derived from the dihydric phenol. 1 It was calculated by H-NMR measurement.

[0044] The aliphatic difunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. As the aliphatic difunctional carboxylic acid, for example, straight-chain saturated aliphatic dicarboxylic acids such as sebacic acid (decane dioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, eicosanedioic acid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid can be preferably cited. As the difunctional alcohol, alicyclic diols are more preferably exemplified, for example, cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol can be exemplified.

[0045] Reaction forms such as the interfacial polymerization method, the melt transesterification method, the solid phase transesterification method of carbonate prepolymers, and the ring-opening polymerization method of cyclic carbonate compounds as the production method of the aromatic polycarbonate resin of the present invention are well known in various documents and patent publications.

[0046] The melt volume rate (300°C, 1.2 kg load) of the aromatic polycarbonate resin of the present invention is not particularly limited, but is preferably 1 to 60 cm 3 / 10min, more preferably 3 to 30cm 3 / 10min, more preferably 5 to 20cm 3 / 10min. The melt volume rate is less than 1cm 3 / 10min. The resin composition obtained by using an aromatic polycarbonate resin having a melt volume rate of more than 60cm / 10min may have poor versatility due to poor fluidity during injection molding. 3 In the case of an aromatic polycarbonate resin having a melt volume rate of 0.1 mol / lmin, good mechanical properties may not be obtained. The melt volume rate is also referred to as "MVR" and can be measured in accordance with ISO1133.

[0047] The viscosity average molecular weight (M) of the aromatic polycarbonate resin of the present invention is preferably 24,000 or less, more preferably 22,500 or less, and further preferably 20,000 or less. If the viscosity average molecular weight exceeds 24,000, due to poor fluidity, it is necessary to set the molding conditions to high temperature in order to obtain a thin-walled molded product with a thickness of 1 to 3 mm used as a sensor cover material, and sometimes the resin or colorant becomes easily thermally decomposed. In addition, although the lower limit of the viscosity average molecular weight is not particularly limited, it is preferably 14,000 or more from the viewpoint of impact resistance. It should be noted that the viscosity average molecular weight (M) referred to in the present invention is calculated as follows. First, using an Ostwald viscometer, the specific viscosity (η) calculated according to the following formula is calculated from a solution formed by dissolving 0.7 g of a polycarbonate resin in 100 ml of dichloromethane at 20°C. SP ),

[0048] Specific viscosity (η SP )=(t-t0) / t0

[0049] [t0 is the falling seconds of dichloromethane, t is the falling seconds of the sample solution]

[0050] The specific viscosity (η SP ), and the viscosity average molecular weight M was calculated according to the following formula.

[0051] η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity)

[0052] [η] = 1.23 × 10 －4 M 0.83

[0053] c=0.7

[0054] As the aromatic polycarbonate resin of the present invention, a polycarbonate-polydiorganosiloxane copolymer resin may also be used. The polycarbonate-polydiorganosiloxane copolymer resin is preferably a copolymer resin prepared by copolymerizing a dihydric phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3).

[0055] [Chemical formula 1]

[0056]

[0057] [In the above general formula (1), R 1 and R 2Each independently represents a group selected from 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 cycloalkyloxy 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 carboxyl group; when there are a plurality of each, they may be the same or different; e and f are each an integer of 1 to 4; and W is a single bond or at least one group selected from the groups represented by the following general formula (2).]

[0058] [Chemical formula 2]

[0059]

[0060] [In the above general formula (2), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 Each independently represents a group selected from 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, and R 19 and R 20 Each independently represents a group selected from 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 cycloalkyloxy 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 carboxyl group. When there are a plurality of such 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.]

[0061] [Chemical formula 3]

[0062]

[0063] [In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 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, R 9 and R 10Each is 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 from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.]

[0064] 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(4-hydroxyphenyl)-3-isopropylphenyl)propane, 2,2-bis(4-hydroxyphenyl)-1-phenylethane. 2-bis(3-tert-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)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'-dimethyl diphenyl ether, 4,4'-sulfonyl diphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyl diphenol, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyl diphenol, 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, 1,4-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, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, etc.

[0065] Among them, 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 them, 2,2-bis(4-hydroxyphenyl)propane is most preferred because of its excellent strength and good durability. These may be used alone or in combination of two or more.

[0066] As the hydroxyaryl-terminated polydiorganosiloxane represented by the general formula (3), for example, the following compounds can be preferably used.

[0067] [Chemical formula 4]

[0068]

[0069] Hydroxyaryl-terminated polydiorganosiloxane (II) can be easily produced by subjecting phenols having olefinic unsaturated carbon-carbon bonds, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol, to a hydrosilylation reaction at the end of a polysiloxane chain having a predetermined degree of polymerization. Among them, (2-allylphenol)-terminated polydiorganosiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane are preferred, and (2-allylphenol)-terminated polydimethylsiloxane and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxane are particularly preferred. Hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw / Mn) of 3 or less. In order to achieve further excellent low outgassing properties and low-temperature impact properties during high-temperature molding, the molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and more preferably 2 or less. If the upper limit of the above preferred range is exceeded, the amount of outgassing generated during high temperature molding may increase, and the low temperature impact resistance may be poor.

[0070] In order to achieve high impact resistance, the diorganosiloxane polymerization degree (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is preferably 10 to 300. The diorganosiloxane polymerization degree (p+q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. If the degree of polymerization is less than the lower limit of the preferred range, the impact resistance that is a characteristic of the polycarbonate-polydiorganosiloxane copolymer resin cannot be effectively achieved, and if the degree of polymerization exceeds the upper limit of the preferred range, the appearance is poor.

[0071] The content of polydiorganosiloxane is preferably 0.1 to 50% by weight of the total weight of the polycarbonate-polydiorganosiloxane copolymer resin. The content of the above-mentioned polydiorganosiloxane component is more preferably 0.5 to 30% by weight, and further preferably 1 to 20% by weight. If it is above the lower limit of the above-mentioned preferred range, the impact resistance and flame retardancy are excellent. If it is below the upper limit of the above-mentioned preferred range, it is easy to obtain a stable appearance that is not easily affected by molding conditions. The above-mentioned degree of polymerization of polydiorganosiloxane and content of polydiorganosiloxane can be 1 It was calculated by H-NMR measurement.

[0072] In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.

[0073] Furthermore, other comonomers other than the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in an amount of 10% by weight or less based on the total weight of the copolymer within the range not impairing the present invention.

[0074] 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) and a carbonate-forming compound in a mixed solution of a water-immiscible organic solvent and an alkaline aqueous solution.

[0075] When generating the oligomer of dihydric phenol (I), the total amount of dihydric phenol (I) used in the method of the present invention can be made into oligomer at one time, or a part of it can be added as a post-added monomer as a reaction raw material in the interfacial polycondensation reaction of the latter stage. The post-added monomer refers to a monomer added in order to make the polycondensation reaction of the latter stage proceed quickly, and it is not necessary to add it when it is not necessary.

[0076] The method of the oligomer formation reaction is not particularly limited, but is usually preferably a method in which the reaction is carried out in a solvent in the presence of an acid binder.

[0077] The ratio of the carbonate-forming compound to be used can be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. In addition, when a gaseous carbonate-forming compound such as phosgene is used, a method of blowing it into the reaction system can be preferably adopted.

[0078] As the above-mentioned acid binding agent, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide can be used; alkali metal carbonates such as sodium carbonate and potassium carbonate; organic bases such as pyridine or their mixtures, etc. The use ratio of the acid binding agent can also be appropriately determined by considering the stoichiometric ratio (equivalent) of the reaction in the same manner as above. Specifically, it is preferred to use an acid binding agent in an amount of 2 equivalents or slightly excessive relative to the mole number (usually 1 mole is equivalent to 2 equivalents) of the dihydric phenol (I) used for the formation of the oligomer.

[0079] As the above-mentioned solvent, a solvent inert to various reactions such as a solvent used in the manufacture of a known polycarbonate resin can be used alone, or it can be used as a mixed solvent. As representative examples, for example, hydrocarbon solvents such as xylene, methylene chloride, and chlorobenzene can be cited as halogenated hydrocarbon solvents, etc. It is particularly preferred to use halogenated hydrocarbon solvents such as methylene chloride.

[0080] The reaction pressure for oligomer formation is not particularly limited, and normal pressure, pressurization, and reduced pressure are all possible. It is advantageous to conduct the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50°C. In most cases, water cooling or ice cooling is expected because heat is generated with polymerization. Although the reaction time is affected by other conditions and cannot be generally specified, it is usually carried out for 0.2 to 10 hours. The pH range of the oligomer formation reaction is the same as the known interfacial reaction conditions, and the pH is often adjusted to 10 or more.

[0081] The present invention obtains a polycarbonate-polydiorganosiloxane copolymer resin in this way. After obtaining a mixed solution of oligomers of a dihydric phenol (I) having a terminal chloroformate group, a hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (3) with a molecular weight distribution (Mw / Mn) highly purified to less than 3 is added to the dihydric phenol (I) while stirring the mixed solution, and the hydroxyaryl-terminated polydiorganosiloxane (II) is subjected to interfacial condensation polymerization with the oligomer, thereby obtaining a polycarbonate-polydiorganosiloxane copolymer resin.

[0082] When the interfacial polycondensation reaction is carried out, an acid-binding agent can be appropriately added in consideration of the stoichiometric ratio (equivalent) of the reaction. As the acid-binding agent, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal hydrochlorides such as sodium carbonate and potassium carbonate; organic bases such as pyridine or mixtures thereof, etc. can be used. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) used or a part of the dihydric phenol (I) as described above is added as a post-added monomer at this reaction stage, it is preferred to use a base that is 2 equivalents or more than the total molar number of the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) of the post-added part (usually 1 mole is equivalent to 2 equivalents).

[0083] The polycondensation utilizing the interfacial polycondensation reaction between the oligomer of the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixed solution.

[0084] In the above-mentioned polymerization reaction, an end-capping agent or a molecular weight regulator is usually used. As the end-capping agent, a compound having a monovalent phenolic hydroxyl group can be cited, and in addition to common phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., examples thereof include long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl esters, alkyl ether phenols, etc. The amount used is 100 to 0.5 moles, preferably 50 to 2 moles, relative to 100 moles of all dihydric phenol compounds used, and of course, two or more compounds can be used in combination.

[0085] In order to promote the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.

[0086] The reaction time of the above polymerization reaction is preferably 30 minutes or longer, and more preferably 50 minutes or longer. A small amount of an antioxidant such as sodium sulfite or sodium dithionite may be added as needed.

[0087] A branching agent can be used together with the above-mentioned dihydric phenolic compound to prepare a branched polycarbonate-polydiorganosiloxane copolymer resin. Examples of the trifunctional or higher polyfunctional aromatic compound used for the above-mentioned branched polycarbonate-polydiorganosiloxane copolymer resin include pyrogallol, pentahydroxybiphenyl or 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) The present invention also includes triphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetrakis(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene or 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 ratio of the multifunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, further preferably 0.01 to 0.8 mol%, and particularly preferably 0.05 to 0.4 mol% of the total amount of the branched polycarbonate-polydiorganosiloxane copolymer resin. 1 Calculated by H-NMR measurement.

[0088] Regarding the reaction pressure, reduced pressure, normal pressure, and increased pressure are all possible, and it can usually be appropriately carried out under normal pressure or the self-pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C. In most cases, since heat is generated with polymerization, water cooling or ice cooling is preferred. The reaction time varies depending on other conditions such as the reaction temperature, so it cannot be generally specified, but it is usually carried out for 0.5 to 10 hours.

[0089] The obtained polycarbonate-polydiorganosiloxane copolymer resin may be subjected to appropriate physical treatment (mixing, separation, etc.) and / or chemical treatment (polymerization reaction, crosslinking treatment, partial decomposition treatment, etc.) as appropriate to obtain a desired reduced viscosity [η SP / c] polycarbonate-polydiorganosiloxane copolymer resin is obtained.

[0090] The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (degree of purification) by subjecting the obtained reaction product (crude product) to various post-treatments such as known separation and purification methods.

[0091] The average size of the polydiorganosiloxane domain in the polycarbonate-polydiorganosiloxane copolymer resin molded product is preferably in the range of 1 to 40 nm. The above average size is more preferably 1 to 30 nm, and further preferably 5 to 25 nm. If it is less than the lower limit of the above preferred range, the impact resistance and flame retardancy cannot be fully exerted, and if it exceeds the upper limit of the above preferred range, the impact resistance may not be stably exerted. Thus, a resin composition with excellent impact resistance and appearance can be provided.

[0092] The average domain size of the polydiorganosiloxane domains of the polycarbonate-polydiorganosiloxane copolymer resin molded article of the present invention is evaluated by small angle X-ray scattering (SAXS). Small angle X-ray scattering is a method of measuring diffuse scattering and diffraction generated in a small angle region within a scattering angle (2θ) of less than 10°. In the small angle X-ray scattering method, if there are regions with different electron densities of about 1 to 100 nm in a substance, the diffuse scattering of X-rays can be measured based on the electron density difference. The particle size of the measured object is calculated based on the scattering angle and the scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin in which the polydiorganosiloxane domains are dispersed in the matrix of the polycarbonate polymer to form a cohesive structure, diffuse scattering of X-rays is generated due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity I at each scattering angle (2θ) in the range of scattering angle (2θ) less than 10° is measured, and the small-angle X-ray scattering distribution is measured. It is assumed that the polydiorganosiloxane phase domain is a spherical phase domain and there is a deviation in the particle size distribution. The commercially available analysis software is used to simulate the assumed particle size and the assumed particle size distribution model to obtain the average size of the polydiorganosiloxane phase domain. The small-angle X-ray scattering method can be used to measure the average size of the polydiorganosiloxane phase domain dispersed in the matrix of the polycarbonate polymer, which cannot be correctly measured by observation using a transmission electron microscope, with high precision, simplicity and good reproducibility. The average phase domain size means the number average of the sizes of each phase domain. The term "average phase domain size" used in connection with the present invention represents the measured value obtained by measuring the 1.0 mm thickness portion of the three-stage mold plate made by the method described in the embodiment according to the above-mentioned small-angle X-ray scattering method. In addition, the analysis is performed using an independent particle model that does not consider the interaction between particles (inter-particle interference). (Component B: a colorant having an absorption maximum in a region less than 650 nm)

[0093] In the present invention, the colorant used as component B is a colorant having an absorption maximum in a region less than 650nm. It should be noted that the lower limit of the absorption maximum is not particularly specified, but is preferably above 400nm. The colorant can be selected from dyes (organic, inorganic), pigments (organic, inorganic), etc., and there is no particular restriction as long as the aromatic polycarbonate resin composition targeted by the present invention can be obtained. As a colorant, since the dye does not have diffuse reflection of light on the particle surface, a dye is preferably used. As a dye-based colorant, for example, anthraquinone-based colorants, purple ring ketone-based colorants, perylene-based colorants, methine-based colorants, azo-based colorants, quinoline-based colorants, phthalocyanine-based colorants, square acid-based colorants, heterocyclic colorants, etc. can be cited.

[0094] The content of component B is 0.03 to 1.2 parts by weight, preferably 0.05 to 1.0 parts by weight, and more preferably 0.1 to 0.5 parts by weight relative to 100 parts by weight of component A. When the content of component B is less than 0.03 parts by weight, sufficient blocking properties of 400 nm to 870 nm cannot be obtained. On the other hand, if it exceeds 1.2 parts by weight, the thermal stability of the resin composition deteriorates.

[0095] (Component C: a colorant having an absorption maximum in a range of 650 nm or more and less than 870 nm)

[0096] In the present invention, the colorant used as component C is a colorant with an absorption maximum in a region above 650nm and less than 870nm. The colorant can be selected from dyes (organic, inorganic), pigments (organic, inorganic), etc., and there is no particular restriction as long as the aromatic polycarbonate resin composition as the target of the present invention can be obtained. As a colorant, because the dye does not have diffuse reflection of light on the surface of the particles, it is preferred to use a dye. As a dye-based colorant, for example, anthraquinone-based colorants, purple ring ketone-based colorants, perylene-based colorants, methine-based colorants, azo-based colorants, quinoline-based colorants, phthalocyanine-based colorants, square acid-based colorants, heterocyclic colorants, etc. can be cited. Among them, more preferably anthraquinone-based colorants, phthalocyanine-based colorants, perylene-based colorants and heterocyclic colorants with high heat resistance.

[0097] 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 relative to 100 parts by weight of component A. When the content of component C is less than 0.001 parts by weight, sufficient blocking properties at 400 nm to 870 nm cannot be obtained. On the other hand, if it exceeds 0.3 parts by weight, the thermal stability of the resin composition deteriorates.

[0098] (Component D: a colorant having an absorption maximum in a region of 870 nm or more and less than 1000 nm)

[0099] In the present invention, the colorant used as component D is a colorant with an absorption maximum in a region of more than 870nm and less than 1000nm. The colorant can be selected from dyes (organic, inorganic), pigments (organic, inorganic), etc., and there is no particular restriction as long as the aromatic polycarbonate resin composition as the target of the present invention can be obtained. As a colorant, since the dye does not have diffuse reflection of light on the surface of the particles, a dye is preferably used. As a dye-based colorant, for example, anthraquinone-based colorants, purple ring ketone-based colorants, perylene-based colorants, methine-based colorants, azo-based colorants, quinoline-based colorants, phthalocyanine-based colorants, square acid-based colorants, heterocyclic colorants, etc. can be cited. Among them, anthraquinone-based colorants, phthalocyanine-based colorants, perylene-based colorants and heterocyclic colorants with high heat resistance are more preferably used.

[0100] 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 relative to 100 parts by weight of component A. When the content of component D is less than 0.001 parts by weight, sufficient blocking properties cannot be obtained at wavelengths where the absorption of component D is a maximum value from 870 nm to 100 parts by weight. On the other hand, if it exceeds 0.3 parts by weight, the thermal stability of the resin composition deteriorates.

[0101] (Component E: heat stabilizer)

[0102] 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 the thermal stability during manufacturing or molding, and improves the mechanical properties, color and molding stability. Examples of the phosphorus-based heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters and tertiary phosphines. Specifically, as the phosphite compound, for example, triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tri(octadecyl) 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(diisopropylphenyl) phosphite, tris(di-octylphenyl) phosphite, The phosphite esters include tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-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. As other phosphite compounds, phosphite compounds having a cyclic structure by reacting with dihydric phenols 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'-ethylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, etc. can be mentioned. Examples of the phosphate ester compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenylmono-o-biphenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc., and triphenyl phosphate and trimethyl phosphate are preferred.

[0103] Examples of the phosphite compound include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphite, bis(2,4-di-tert-butylphenyl)-4 The phosphite compound is preferably phenyl-2-phenyl-phosphite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phosphite, bis(2,6-di-n-butylphenyl)-3-phenyl-phosphite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phosphite, bis(2,6-di-tert-butylphenyl)-3-phenyl-phosphite, etc., preferably tetrakis(di-tert-butylphenyl)-biphenylene diphosphite and bis(di-tert-butylphenyl)-phenyl-phosphite, and more preferably tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphite and bis(2,4-di-tert-butylphenyl)-phenyl-phosphite. The above phosphite compound is preferably used in combination with the above phosphite compound having an aryl group substituted with two or more alkyl groups. As the phosphonate compound, dimethyl phenylphosphonate, diethyl phenylphosphonate and dipropyl phenylphosphonate can be cited. As the tertiary phosphine, triethyl phosphine, tripropyl phosphine, tributyl phosphine, trioctyl phosphine, tripentyl phosphine, dimethylphenyl phosphine, dibutylphenyl phosphine, diphenylmethyl phosphine, diphenyloctyl phosphine, triphenyl phosphine, tri-p-tolyl phosphine, trinaphthyl phosphine and diphenylbenzyl phosphine can be exemplified. A particularly preferred tertiary phosphine is triphenyl phosphine. The above-mentioned phosphorus-based heat stabilizer can be used not only as one, but also as a mixture of two or more. Among the above-mentioned phosphorus-based heat stabilizers, it is preferred to use an alkyl phosphate compound represented by trimethyl phosphate. In addition, the above-mentioned alkyl phosphate compound and a phosphite compound and / or a phosphite compound are also preferably used in combination.

[0104] 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-tert-butylphenyl) propionate, tetrakis{methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl) propionate}methane, distearyl(4-hydroxy-3-methyl-5-tert-butylbenzyl) malonate, triethylene glycol-bis{3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis{3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, pentaerythritol-tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, 2,2-thiodiethylenebis{ 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, 2,2-thiobis(4-methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 2,4-bis{(octylthio)methyl}-o-cresol, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,5,7,8-tetramethyl-2(4',8',12'-trimethyltridecyl)chroman-6-ol, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, etc.

[0105] Among these, preferred are n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, pentaerythritol-tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, and 2,2-thiodiethylenebis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}.

[0106] 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 relative to 100 parts by weight of component A. When the content of component E is less than 0.003 parts by weight, the thermal stability of the resin composition deteriorates, and the thermal stability of the absorption characteristics also deteriorates. On the other hand, if it exceeds 0.5 parts by weight, the moisture and heat resistance of the resin composition deteriorates. (Component F: benzotriazole-based ultraviolet absorber)

[0107] The aromatic polycarbonate resin composition of the present invention preferably contains a benzotriazole-based ultraviolet absorber. Examples of the benzotriazole 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, 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, and 2-(2-hydroxy-5-tert-octylphenyl)-5-chlorobenzotriazole. Benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)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-methacryloyloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer, copolymers of 2-(2'-hydroxy-5-acryloyloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer, and the like having a 2-hydroxyphenyl-2H-benzotriazole skeleton. Furthermore, the above-mentioned ultraviolet absorber can be a polymer type ultraviolet absorber obtained by copolymerizing the above-mentioned ultraviolet absorbing monomer and / or light stabilizing monomer with monomers such as (meth) alkyl acrylate by adopting the structure of a monomer compound capable of free radical polymerization. As the above-mentioned ultraviolet absorbing monomer, a compound containing a benzotriazole skeleton in the ester substituent of (meth) acrylate can be preferably exemplified. Among them, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole represented by Tinuvin 234 (BASF JAPAN Co., Ltd.) and 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole represented by Tinuvin 326 (BASF JAPAN Co., Ltd.) are more preferred.

[0108] The content of component F is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.8 part by weight, and further preferably 0.1 to 0.5 part by weight relative to 100 parts by weight of component A. When the content of component F is less than 0.01 parts by weight, the light stability of the absorption characteristics may deteriorate, while when it exceeds 1 part by weight, the thermal stability of the resin composition may decrease.

[0109] (Other additives)

[0110] In order to improve the thermal stability of the aromatic polycarbonate resin composition of the present invention in a designed manner, additives for improving these properties can be advantageously used. These additives are specifically described below.

[0111] (I) Heat stabilizer other than component E

[0112] Other heat stabilizers other than the phosphorus-based heat stabilizer and the phenol-based heat stabilizer may also be added to the aromatic polycarbonate resin composition of the present invention. As the other heat stabilizers, for example, a lactone-based stabilizer represented by a reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene can be preferably exemplified. The details of the stabilizer are described in Japanese Patent Publication No. 7-233160. The compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and the compound can be used. In addition, stabilizers in which the compound is mixed with various phosphite compounds and hindered phenol compounds are also commercially available. For example, Irganox HP-2921 manufactured by the above company can be preferably exemplified. 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, relative to 100 parts by weight of component A. In addition, as other stabilizers, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-dodecylthiopropionate) and glycerol-3-stearylthiopropionate and other sulfur-containing stabilizers can be exemplified. The content of the above-mentioned sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, and more preferably 0.01 to 0.08 parts by weight relative to 100 parts by weight of component A. An epoxy compound can be added to the polycarbonate resin composition of the present invention as needed. The above-mentioned epoxy compound is a compound added for the purpose of inhibiting metal mold corrosion, and basically all epoxy compounds 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, copolymers of methyl methacrylate and glycidyl methacrylate, copolymers of styrene and glycidyl methacrylate, etc. The content of the epoxy compound 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 relative to 100 parts by weight of component A.

[0113] (II) Release agent

[0114] In order to further improve the releasability from a metal mold during melt molding, the aromatic polycarbonate resin composition of the present invention may contain a release agent within a range not impairing the object of the present invention.

[0115] Examples of the release agent include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefin wax, olefin wax containing carboxyl and / or carboxylic anhydride groups, silicone oil, organopolysiloxane, etc. As the higher fatty acid ester, partial or full esters of monohydric or polyhydric alcohols having 1 to 20 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms are preferred. As partial esters or full esters of the above-mentioned monohydric or polyhydric alcohols and saturated fatty acids, for example, monoglyceryl stearate, diglyceryl stearate, triglyceryl stearate, monosorbitol stearate, stearyl stearate, monoglyceryl behenate, behenyl behenate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenolate, sorbitan monostearate, 2-ethylhexyl stearate, etc. Among them, monoglyceryl stearate, triglyceryl stearate, pentaerythritol tetrastearate, behenyl behenate are preferably used. As higher fatty acids, saturated fatty acids having 10 to 30 carbon atoms are preferred. Examples of the fatty acid include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid.

[0116] These release agents may be used alone or in combination of two or more. The content of the release agent is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the A component.

[0117] <Method for producing resin composition>

[0118] Any method can be used to manufacture the aromatic polycarbonate resin composition of the present invention. For example, a method in which each component is premixed with any other component and then melt-kneaded and granulated can be cited. As means of premixing, a Nauta mixer, a V-type mixer, a Henschel mixer, a mechanochemical device, an extrusion mixer, etc. can be cited. In the premixing, granulation can be performed using an extrusion granulator, a molding machine, etc. as appropriate. After premixing, melt-kneading is performed using a melt-kneading machine represented by a vented twin-shaft extruder, and granulation is performed using equipment such as a granulator. As a melt-kneading machine, in addition to this, a Banbury mixer, a mixing roll, a constant heat stirring container, etc. can also be cited, but a vented twin-shaft extruder is preferably used. In addition, a method in which each component is not premixed with any other component, but each is independently supplied to a melt-kneading machine represented by a twin-shaft extruder.

[0119] <About molded products>

[0120] The aromatic polycarbonate resin composition of the present invention obtained as described above can usually be used to manufacture various products by injection molding the particles manufactured as described above. Furthermore, the resin obtained by melt mixing can be directly made into sheets, films, special-shaped extrusion molded products and injection molded products by using an extruder without using particles. In the above-mentioned injection molding, not only the usual molding method can be used, but also the injection molding methods such as injection compression molding, injection pressure molding, gas-assisted injection molding, foam molding (including molding using injection of supercritical fluid), insert molding, in-mold coating molding, insulation metal mold molding, rapid heating and cooling metal mold molding, two-color molding, sandwich molding and ultra-high-speed injection molding can be used to obtain molded products according to appropriate purposes. The advantages of these various molding methods are well known. In addition, the molding can select any one of the cold runner method and the hot runner method. In addition, the resin composition of the present invention can be molded into various special-shaped extrusion molded products and sheets by extrusion molding.

[0121] Regarding the molded article made of the aromatic polycarbonate resin composition of the present invention, the average value of the light transmittance in the thickness direction of the molded article with a thickness of 3 mm in the region of 400 to 870 nm needs to be 1.5% or less. The average value of the light transmittance is more preferably 1.0% or less, and further preferably 0.5% or less. If the average value of the light transmittance exceeds 1.5%, the amount of sunlight that becomes noise increases, which has a negative impact on sensing. It should be noted that the lower limit of the average value of the light transmittance is not particularly limited, but is preferably 0%.

[0122] In addition, the average value of the light transmittance in the thickness direction of the molded article made of the aromatic polycarbonate resin composition of the present invention is preferably 1.5% or less, more preferably 1.0% or less, and further preferably 0.5% or less at a wavelength of 870nm to the maximum absorption value of the D component and a thickness of 3mm. If the average value of the light transmittance exceeds 1.5%, the amount of sunlight that becomes noise increases, which sometimes has a negative impact on sensing. It should be noted that the lower limit of the average value of the light transmittance is not particularly limited, but is preferably 0%.

[0123] Example

[0124] Hereinafter, the present invention will be further specifically described according to the examples, but the present invention is not limited to these examples. It should be noted that, unless otherwise specified, "parts" are parts by weight. It should be noted that the evaluation was carried out according to the following method.

[0125] [Evaluation of resin composition]

[0126] 1. Average value of light transmittance from 400nm to 870nm and from 870nm to the absorption maximum wavelength of component D

[0127] The spectral light transmittance of the continuous molded product produced by the following method was measured in the range of 300nm to 2500nm using an ultraviolet-visible-near-infrared spectrophotometer (V-770 manufactured by JASCO Corporation). Based on the obtained spectral spectrum, the average value of the light transmittance from 400nm to 870nm and the average value of the light transmittance from 870nm to the absorption maximum wavelength of the D component were calculated.

[0128] 2. Thermal stability of absorption properties

[0129] The spectral light transmittance of the continuous molded product is measured in the same way as the "average value of the light transmittance at the absorption maximum wavelength of the component D from 1.400nm to 870nm and from 870nm". The obtained spectral spectrum is scanned from a wavelength of 400nm to the long wavelength side, and the wavelength (transmission wavelength λt) at which the transmittance first reaches 70% or more is read. The same method is used for the retained molded product to read the transmission wavelength λtr. The case where λtr-λt is 0 to 5 is set as ◎, the case where it is 6 to 10 is set as 0, the case where it is 11 to 20 is set as △, and the case where it is 21 or more is set as ×.

[0130] 3. Photostability of absorption characteristics:

[0131] The spectral light transmittance of the light-exposed product is measured in the same manner as the "average value of the light transmittance at the absorption maximum wavelength of the component D from 1.400nm to 870nm and from 870nm". The obtained spectral spectrum is scanned from a wavelength of 400nm to the long wavelength side, and the wavelength (transmission wavelength λtx) at which the transmittance first reaches 70% or more is read. The case where |λtx-λt| is 0 to 5 is set as ◎, the case where it is 6 to 10 is set as 0, the case where it is 11 to 20 is set as △, and the case where it is 21 or more is set as ×.

[0132] 4. Thermal stability of resin composition (viscosity average molecular weight):

[0133] The viscosity average molecular weight (M0) of the continuous molded product and the viscosity average molecular weight (M1) of the retained molded product were measured by the following method: The case where M0-M1<1000 was satisfied was marked as ○, and the case where it was not satisfied was marked as ×.

[0134] The viscosity average molecular weight (M) is calculated as follows: First, using an Ostwald viscometer, 0.7 g of the molded product obtained by the following method is dissolved in 100 ml of dichloromethane at 20° C. to obtain a specific viscosity (η) calculated according to the following formula: SP ),

[0135] Specific viscosity (η SP )=(t-t0) / t0

[0136] [t0 is the falling seconds of dichloromethane, t is the falling seconds of the sample solution]

[0137] The specific viscosity (η SP ), and calculate it according to the following formula.

[0138] η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity)

[0139] [η] = 1.23 × 10 －4 M 0.83

[0140] c=0.7

[0141] 5. Moisture and heat resistance of resin composition (viscosity average molecular weight):

[0142] The viscosity average molecular weight (M0) of the continuous molded product and the viscosity average molecular weight (M2) of the wet heat treated product were measured by the same method as in "5. Thermal stability of resin composition". The case where M0-M2<1000 was satisfied was marked as ○, and the case where it was not satisfied was marked as ×.

[0143] [Examples 1 to 27, Comparative Examples 1 to 8]

[0144] [Production of resin pellets]

[0145] Various ingredients were mixed using a drum mixer according to the ingredients and contents shown in Tables 1 to 3, and melt-kneaded using a twin-screw extruder (TEX30α, The Nippon Steel Works, Ltd.) at a cylinder temperature of 280° C. to obtain various pellets. The ingredients used were as follows.

[0146] [Production of molded products by injection molding]

[0147] The pellets obtained by the above method were dried for 5 hours at 120°C using a hot air circulation dryer, and then molded into a plate-shaped test piece with a thickness of 3 mm using an injection molding machine (ROBOSHOTα-S100iA manufactured by FANUC Corporation) at a cylinder temperature of 340°C and a metal mold temperature of 80°C. Regarding molding, continuous molding was implemented, and the injection molding was stopped for 10 minutes while the resin was in the cylinder and then molded again. The product that was continuously molded without stopping the injection molding midway was regarded as a continuously molded product, and the product that was molded after the injection molding was stopped for 10 minutes while the resin was in the cylinder was regarded as a retained molded product.

[0148] [Light exposure treatment of molded products]

[0149] A xenon lamp weathering test chamber (NX75Z, manufactured by SUGA Testing Instruments Co., Ltd.) was used with a black panel temperature of 63°C, a tank temperature of 50°C, a relative humidity of 50%, and an irradiation intensity of 0.35 W / m 2 The continuous molded product obtained by the above method was subjected to light exposure treatment for 1000 hours under the condition of 100 nm (@340 nm), and the molded product thus obtained was referred to as a light-exposed product.

[0150] [Wet heat treatment of molded products]

[0151] The continuous molded product obtained by the above method was subjected to a wet heat treatment for 1000 hours under the conditions of a temperature of 80° C. and a humidity of 85% using a thermohygrostat (ESPEC Corporation PR-3J). The molded product thus obtained was used as a wet heat treated product.

[0152] (A ingredient)

[0153] A-1: PANLITE L-1225WX manufactured by Teijin Limited (viscosity average molecular weight: 19700)

[0154] A-2: PANLITE L-1225WP manufactured by Teijin Limited (viscosity average molecular weight: 22400)

[0155] A-3: Polycarbonate resin produced by the following method

[0156] 3844 parts of 48% sodium hydroxide aqueous solution and 22380 parts of ion exchange water were placed in a reactor equipped with a thermometer, a stirrer and a circulation cooler, 1992 parts of 2,2-bis(4-hydroxy-3-methylphenyl)propane (Bis-C, manufactured by Honshu Chemical), 1773 parts of 2,2-bis(4-hydroxyphenyl)propane (Bis-A, manufactured by Nippon Steel Chemical), and 7.53 parts of sodium dithionite (manufactured by Wako Pure Chemical Industries) were dissolved therein, and then 13210 parts of dichloromethane were added, and 2000 parts of phosgene were blown into the mixture at 15 to 25° C. for about 60 minutes while stirring. After the blowing of phosgene was completed, 640 parts of 48% sodium hydroxide aqueous solution and 93.2 parts of p-tert-butylphenol were added, stirring was resumed, and 3.24 parts of triethylamine was added after emulsification, and the mixture was further stirred at 28 to 33° C. for 1 hour to terminate the reaction. After the reaction is completed, the product is diluted with dichloromethane and washed with water, and then washed with hydrochloric acid. The water washing is repeated until the conductivity of the aqueous phase becomes approximately the same as that of ion exchange water, thereby obtaining a dichloromethane solution of a polycarbonate resin. Next, the solution is passed through a filter with a mesh of 0.3 μm and then dripped into warm water in a kneader with an isolation chamber having a foreign matter removal port in the bearing portion, and the polycarbonate resin is flaked while distilling off the dichloromethane. Then, the liquid-containing flakes are crushed and dried to obtain powders. The viscosity average molecular weight is 20,000.

[0157] (Component B)

[0158] B-1: NUBIAN BLACK PC-5857 (Orient Chemical Industry Co., Ltd., absorption maximum wavelength 599nm)

[0159] (Component C)

[0160] C-1: Anthraquinone colorant SDO-11 (Arimoto Chemical Industry Co., Ltd., absorption maximum wavelength 761nm)

[0161] C-2: Perylene colorant Lumogen IR-765 (BASF JAPAN Co., Ltd., absorption maximum wavelength 769nm)

[0162] C-3: Heterocyclic colorant SDO-C33 (Arimoto Chemical Industry Co., Ltd., absorption maximum wavelength 847nm)

[0163] (Component D)

[0164] D-1: Phthalocyanine colorant FDN-005 (Yamada Chemical Industry Co., Ltd., absorption maximum wavelength 911nm)

[0165] D-2: Phthalocyanine colorant FDN-007 (Yamada Chemical Industry Co., Ltd., absorption maximum wavelength 956nm)

[0166] D-3: Phthalocyanine colorant FDN-008 (Yamada Chemical Industry Co., Ltd., absorption maximum wavelength 992nm)

[0167] (Ingredient E)

[0168] E-1: Phosphorus-based heat stabilizer ADEKA STAB 2112 (ADEKA Corporation)

[0169] E-2: Phenolic heat stabilizer AO-50 (ADEKA Corporation)

[0170] (F component)

[0171] F-1: Benzotriazole UV absorber Tinuvin 234 (BASF JAPAN Co., Ltd.)

[0172] F-2: Benzotriazole UV absorber Tinuvin 326 (BASF JAPAN Co., Ltd.)

[0173] F-3: Benzotriazole UV absorber SEESORB 709 (SHIPRO KASEI Co., Ltd.)

[0174] (Other ingredients)

[0175] G-1: UNISTAR-H476S (NOF Corporation)

[0176] G-2: RIKESTAR-EW-400 (Riken Vitamin Co., Ltd.) H-1: Marproof G-0250SP (NOF Co., Ltd.)

[0177]

[0178]

[0179]

[0180] The resin compositions of the examples described in Tables 1 to 3 have excellent thermal stability and moisture and heat resistance and have wavelength-selective absorption characteristics, so they can be used for various infrared light sources used in infrared sensors of autonomous driving systems. In addition, the thermal stability and light stability of the absorption characteristics are excellent.

[0181] When the content of component B and component C is less than the lower limit, the result is that the average value of the light transmittance at 400nm to 870nm exceeds 1.5%. When the content of component D is less than the lower limit, the result is that the average value of the light transmittance at the absorption maximum wavelength of component D from 870nm exceeds 1.5%. On the other hand, when the content exceeds the upper limit, the thermal stability of the resin composition deteriorates. When the content of component E is less than the lower limit, the result is that the thermal stability of the resin composition and the absorption characteristics is poor, and when it exceeds the upper limit, the result is that the resistance to moisture and heat of the resin composition is poor.

Claims

1. A resin composition, characterized in that The invention comprises 0.03 to 1.2 parts by weight of (B) a colorant having an absorption maximum at less than 650 nm, that is, component B; 0.001 to 0.3 parts by weight of (C) a colorant having an absorption maximum at not less than 650 nm and not more than 870 nm, that is, component C; 0.001 to 0.3 parts by weight of (D) a colorant having an absorption maximum at not less than 870 nm and not more than 1000 nm, that is, component D; and 0.003 to 0.5 parts by weight of (E) a phosphorus-based heat stabilizer and / or a phenol-based heat stabilizer, that is, component E, relative to 100 parts by weight of (A) an aromatic polycarbonate resin, that is, component A. The average value of the light transmittance in the thickness direction of a molded article having a thickness of 3 mm at a wavelength of 400 to 870 nm is 1.5% or less.

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

3. The resin composition according to claim 1 or 2, characterized in that The component C and the component D are at least one colorant selected from the group consisting of anthraquinone-based colorants, phthalocyanine-based colorants, perylene-based colorants, and heterocyclic-based colorants.

4. The resin composition according to claim 1 or 2, characterized in that The (F) benzotriazole ultraviolet absorber, that is, component F, is contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of component A.

5. The resin composition according to claim 1 or 2, characterized in that The viscosity average molecular weight of component A is 24,000 or less. 6 . A molded article obtained by molding the resin composition according to claim 1 or 2.

7. The molded article according to claim 6, characterized in that It is a cover material that covers the infrared sensor.

8. The molded article according to claim 7, characterized in that This is a cover material that covers the infrared sensor used in LiDAR for detecting vehicles and buildings.

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