WO2023145197A1

WO2023145197A1 - Aromatic polycarbonate resin composition and molded article thereof

Info

Publication number: WO2023145197A1
Application number: PCT/JP2022/042176
Authority: WO
Inventors: 晋輔磯江
Original assignee: 帝人株式会社
Priority date: 2022-01-28
Filing date: 2022-11-14
Publication date: 2023-08-03

Abstract

The present invention provides an aromatic polycarbonate resin composition that has exceptional heat stability and moist heat resistance and that yields a molded article having wavelength-selective absorption characteristics and furthermore having exceptional heat stability and light stability in terms of absorption characteristics.　The present invention is a resin composition containing, per 100 parts by weight of (A) an aromatic polycarbonate resin (component A), 0.055-1.3 parts by weight of (B) a colorant (component B) that includes (B1) a colorant (component B1) having an absorption maximum of less than 650 nm and (B2) a colorant (component B2) having an absorption maximum of 650-880 nm, and 0.003-0.5 parts by weight of (C) a phosphorus-based heat stabilizer and/or a phenol-based heat stabilizer (component C), wherein the resin composition is characterized in that the average value of thickness-direction light transmittance of a molded article molded to a thickness of 3 mm at 400-700 nm is 1.5% or less.

Description

Aromatic polycarbonate resin composition and molded article thereof

The present invention relates to an aromatic polycarbonate resin composition which is excellent in heat stability and resistance to moist heat, has wavelength-selective absorption characteristics in molded articles formed from it, and has excellent heat stability and light stability of absorption characteristics. .

Autonomous driving technology has made rapid progress in recent years. Infrared sensing systems play an important role in autonomous driving technology. Sensing systems using infrared rays include, for example, driver monitoring systems that monitor drivers and LiDARs that detect other vehicles and buildings, and near infrared rays in the vicinity of 800 to 1000 nm are generally used for sensing. . However, when infrared sensing is performed, visible light to near-infrared light becomes noise, so a cover material that transmits the wavelength range used for sensing and cuts the transmission of the wavelength range below that is required. As the cover material, glass or resin is used, and acrylic resin, polycarbonate resin, etc., which are transparent materials, are generally used as the resin, but polycarbonate resin has good transparency and is excellent in impact resistance and heat resistance. there is a great need for
Studies on wavelength-selective control polycarbonate resins have been made in the past. These are techniques for cutting the visible light region to a part of the near-infrared region by using a plurality of colorants with different absorption wavelength bands (see Patent Documents 1 to 4). However, the stability of the absorption properties is not disclosed in those documents. In addition, since the cover material of the infrared sensor used in automatic driving technology is molded with a thin thickness of about 1 to 3 mm, polycarbonate resin with a relatively high flow viscosity average molecular weight of 24,000 or less is preferred. The molding temperature is also as high as 300-340°C. Therefore, thermal stability of wavelength characteristics in high-temperature molding is very important. Furthermore, in an automobile, the resin is in an environment where it is constantly exposed to light, and it is important that the wavelength characteristics continue to be stable even when exposed to light for a long period of time. In other words, in order to realize a safe autonomous driving society, infrared sensor cover materials must have thermal and light absorption properties.

Japanese Patent No. 5040827 Japanese Patent No. 6354888 WO2019/022169 Japanese Patent No. 6658942

An object of the present invention is to provide an aromatic polycarbonate resin composition which is excellent in thermal stability and resistance to moisture and heat, has wavelength-selective absorption properties in molded articles formed from it, and is excellent in thermal stability and light stability of absorption properties. It is to provide a product and its molded product.

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by an aromatic polycarbonate resin composition containing a specific coloring agent and a heat stabilizer. That is, the present inventors have found that the above objects can be achieved by the following aromatic polycarbonate resin composition and molded article thereof.
1. (A) Per 100 parts by weight of the aromatic polycarbonate resin (component A), (B) (B1) a coloring agent having an absorption maximum at less than 650 nm (component B1) and (B2) a coloring agent having an absorption maximum at 650 to 880 nm 0.055 to 1.3 parts by weight of a colorant (B component) containing (B2 component) and 0.003 to 0.5 parts by weight of (C) a phosphorus heat stabilizer and/or a phenolic heat stabilizer (C component) wherein the average value of the light transmittance in the thickness direction of a molded article having a thickness of 3 mm at 400 to 700 nm is 1.5% or less. .
2. 2. The resin composition according to item 1, wherein the ratio (weight ratio) of B1 component and B2 component (B1 component/B2 component) is 2/1 to 40/1.
3. The above item 1 or 2, wherein the maximum value of light transmittance in the thickness direction of a molded product molded to a thickness of 3 mm at a wavelength from 400 nm to the maximum absorption of the B2 component is 5.0% or less. The resin composition according to .
4. 3. Any one of the preceding items 1 to 3, wherein the B2 component is at least one colorant selected from the group consisting of anthraquinone colorants, phthalocyanine colorants, perylene colorants and heterocyclic colorants. The described resin composition.
5. 5. The resin composition according to any one of the preceding items 1 to 4, characterized by containing 0.01 to 1 part by weight of (D) a benzotriazole-based ultraviolet absorber (component D) with respect to 100 parts by weight of component A.
6. 6. The resin composition as described in any one of 1 to 5 above, wherein the viscosity average molecular weight of component A is 24,000 or less.
7. A molded article obtained by molding the resin composition according to any one of 1 to 6 above.
8. 8. The molded product according to the preceding item 7, which is a cover material for covering the infrared sensor.
9. 9. The molded article according to item 8, which is a cover material for covering an infrared sensor used in a driver monitoring system that monitors a driver and LiDAR for detecting other vehicles and buildings.

The resin composition of the present invention has excellent thermal stability and resistance to moist heat, and molded articles made from it have wavelength-selective absorption properties. The infrared light source used for the infrared sensor of the automatic driving system has multiple standards such as 805 nm, 850 nm, 905 nm, and 940 nm, and the requirements for wavelength characteristics differ depending on the vehicle manufacturer. can meet the demand for Furthermore, since the molded article made of the resin composition of the present invention is excellent in the thermal stability and light stability of the absorption characteristics, it is stable under all molding conditions and even under conditions where it is exposed to light for a long period of time. Stable. Accordingly, the resin composition of the present invention is particularly useful as a cover material for covering infrared sensors, especially covering infrared sensors used in driver monitoring systems for monitoring drivers and LiDAR for detecting other vehicles and buildings. It is useful as a material and can contribute to future safe autonomous driving systems.

(A component: aromatic polycarbonate resin)
The aromatic polycarbonate resin used as component A in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of reaction methods include an interfacial polymerization method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

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-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. be done. Preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes, of which bisphenol A is particularly preferred from the standpoint of impact resistance and is widely used.

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

For example, as part or all of the dihydric phenol component, 4,4′-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis(4-hydroxy phenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. Suitable for applications with particularly stringent demands on change and morphological stability. These dihydric phenols other than BPA are preferably used in an amount of 5 mol % or more, particularly 10 mol % or more, of the total dihydric phenol components constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that component A constituting the resin composition is the following copolymerized polycarbonate (1) to (3). be.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, still more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF is 20 to 80 mol % (more preferably 25 to 60 mol %, still more preferably 35 to 55 mol %).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, still more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF is 5 to 90 mol % (more preferably 10 to 50 mol %, still more preferably 15 to 40 mol %).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, still more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis - A copolymerized polycarbonate in which the TMC is 20-80 mol% (more preferably 25-60 mol%, still more preferably 35-55 mol%).

These special polycarbonates may be used singly or in combination of two or more. Moreover, these can also be used by mixing with a widely used bisphenol A type polycarbonate.

The manufacturing method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435 and JP-A-2002-117580. ing.

Among the various polycarbonates described above, those having a water absorption rate and Tg (glass transition temperature) within the range of (i) or (ii) below by adjusting the copolymer composition etc. are resistant to water of the polymer itself. Since it has good degradability and is remarkably excellent in low warpage after molding, it is particularly suitable in fields where shape stability is required.
(i) Polycarbonate having a water absorption of 0.05-0.15%, preferably 0.06-0.13%, and a Tg of 120-180°C.
(ii) Tg is 160 to 250° C., preferably 170 to 230° C., and water absorption is 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to Polycarbonate at 0.27%.

Here, the water absorption rate of polycarbonate is a value obtained by measuring the water content after immersing a disk-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm in water at 23 ° C. for 24 hours in accordance with ISO62-1980. be. Further, Tg (glass transition temperature) is a value determined by differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.

Carbonate precursors include carbonyl halides, diesters of carbonic acid, haloformates, and the like, and specific examples include phosgene, diphenyl carbonate, and dihaloformates of dihydric phenols.

In producing a polycarbonate resin by interfacial polymerization of the dihydric phenol and the carbonate precursor, if necessary, a catalyst, a terminal terminator, an antioxidant for preventing oxidation of the dihydric phenol, and the like are added. may be used. The polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, and a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. , copolymerized polycarbonate resins copolymerized with difunctional alcohols (including alicyclic), and polyester carbonate resins copolymerized with such difunctional carboxylic acids and difunctional alcohols. Moreover, the mixture which mixed 2 or more types of obtained polycarbonate resin may be sufficient.

The branched polycarbonate resin can impart anti-drip performance and the like to the resin composition of the present invention. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucine, phloroglucide, 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-methylphenol, 4-{4-[ trisphenols such as 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(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 others, 1,1,1-tris(4-hydroxy Phenyl)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.

Structural units derived from a polyfunctional aromatic compound in the branched polycarbonate are preferably 0.01 to 1 mol %, more preferably 0.05 to 0.9 mol %, still more preferably 0.05 to 0.8 mol %.

In addition, particularly in the case of the melt transesterification method, branched structural units may occur as a side reaction. It is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9 mol %, still more preferably 0.01 to 0.8 mol %. The ratio of such branched structures can be calculated by ¹ H-NMR measurement.

The aliphatic bifunctional carboxylic acid is preferably α,ω-dicarboxylic acid. Examples of aliphatic bifunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid, and cyclohexanedicarboxylic acid. Alicyclic dicarboxylic acids such as are preferably exemplified. Alicyclic diols are more suitable as bifunctional alcohols, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

Reaction formats such as the interfacial polymerization method, the melt transesterification method, the carbonate prepolymer solid-phase transesterification method, and the ring-opening polymerization method of a cyclic carbonate compound, which are the methods for producing the aromatic polycarbonate resin of the present invention, can be found in various literatures and patents. This method is well known in publications and the like.

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, and even more preferably. is 5 to 20 cm ³ /10 min. A resin composition obtained from an aromatic polycarbonate resin having a melt volume rate of less than 1 cm ³ /10 min may be inferior in versatility due to poor fluidity during injection molding. On the other hand, aromatic polycarbonate resins with a melt volume rate exceeding 60 cm ³ /10 min may not provide good mechanical properties. The melt volume rate is also called "MVR" and is measured according to ISO1133.

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, still more preferably 20,000 or less. If the viscosity-average molecular weight exceeds 24,000, the fluidity is poor. Therefore, in order to obtain a thin-walled molded product with a thickness of 1 to 3 mm, which is used as a sensor cover material, it is necessary to set the molding conditions to high temperatures. It may be prone to thermal decomposition. 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. The viscosity-average molecular weight (M) referred to in the present invention is obtained by first measuring the specific viscosity (η _SP ) calculated by the following formula at 20° C. with an Ostwald viscometer using a solution of 0.7 g of a polycarbonate resin dissolved in 100 ml of methylene chloride. and
Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
The viscosity-average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.

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
A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the aromatic polycarbonate resin (component A) of the present invention. A polycarbonate-polydiorganosiloxane copolymer resin is a copolymer 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). It is preferably a polymeric resin.

[In the above general formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, cycloalkyl group having 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, aryloxy group having 6 to 14 carbon atoms, carbon atom represents a group selected from the group consisting of 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; e and f are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula (2). ]

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

[In the 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 group having 6 to 12 carbon atoms. or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and 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. ]
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-isopropyl phenyl)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)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, 1,4-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 and the like.

Among others, 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, 1,4-bis{ 2-(4-Hydroxyphenyl)propyl}benzene is preferred, especially 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4′- Sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are preferred. Among them, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is most preferable. Moreover, these may be used alone or in combination of two or more.

As the hydroxyaryl-terminated polydiorganosiloxane represented by the general formula (3), for example, the following compounds are preferably used.

Hydroxyaryl-terminated polydiorganosiloxane (II) is selected from phenols having olefinically unsaturated carbon-carbon bonds, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol. It is easily produced by subjecting the end of a polysiloxane chain having a degree of polymerization to a hydrosilylation reaction. Among them, (2-allylphenol)-terminated polydiorganosiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane are preferred, and (2-allylphenol)-terminated polydimethylsiloxane, (2-methoxy-4 -allylphenol) terminated polydimethylsiloxane is preferred. The hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw/Mn) of 3 or less. The molecular weight distribution (Mw/Mn) is more preferably 2.5 or less, still more preferably 2 or less, in order to achieve even better low-outgassing properties and low-temperature impact resistance during high-temperature molding. If the upper limit of the preferred range is exceeded, a large amount of outgas is generated during high-temperature molding, and the low-temperature impact resistance may be poor.

In addition, the diorganosiloxane polymerization degree (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300 in order to achieve high impact resistance. Such a diorganosiloxane polymerization degree (p+q) is preferably 10-200, more preferably 12-150, still more preferably 14-100. Below the lower limit of the preferred range, impact resistance characteristic of the polycarbonate-polydiorganosiloxane copolymer is not effectively exhibited, and above the upper limit of the preferred range, poor appearance appears.

The polydiorganosiloxane content in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.1 to 50% by weight. The content of such polydiorganosiloxane component is more preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight. Above the lower limit of the preferred range, the impact resistance and flame retardancy are excellent, and below the upper limit of the preferred range, a stable appearance that is less susceptible to molding conditions is likely to be obtained. Such polydiorganosiloxane polymerization degree and polydiorganosiloxane content can be calculated by ¹ H-NMR measurement.

In the present invention, only one type of hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more types may be used.

In addition, other comonomers than the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) are added in an amount of 10% by weight or less based on the total weight of the copolymer, as long as they do not interfere with the present invention. They can also be used in combination.

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-insoluble organic solvent and an alkaline aqueous solution. do.

In producing the oligomer of dihydric phenol (I), the whole amount of dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at one time, or part of it may be used as a post-addition monomer to form an interface in the latter stage. It may be added as a reaction raw material to the polycondensation reaction. The post-addition monomer is added in order to facilitate the subsequent polycondensation reaction, and it is not necessary to add it unless necessary.

Although the method of this oligomer-forming reaction is not particularly limited, a method of performing in a solvent in the presence of an acid binder is usually preferred.

The ratio of the carbonate-forming compound to be used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalents) of the reaction. When a gaseous carbonate-forming compound such as phosgene is used, a method of blowing it into the reaction system can be preferably employed.

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. The ratio of the acid binder to be used may also be appropriately determined in consideration of the stoichiometric ratio (equivalents) of the reaction in the same manner as described above. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of the acid binder with respect to the number of moles of the dihydric phenol (I) used to form the oligomer (usually 1 mol corresponds to 2 equivalents). .

As the solvent, a solvent inert to various reactions, such as those used in the production of known polycarbonates, may be used singly or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene, and the like. In particular, halogenated hydrocarbon solvents such as methylene chloride are preferably used.

The reaction pressure for oligomer production is not particularly limited, and may be normal pressure, increased pressure, or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of −20 to 50° C. In many cases, heat is generated with polymerization, so water cooling or ice cooling is desirable. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours. The pH range of the oligomer-forming reaction is the same as the well-known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

In the present invention, after obtaining a mixed solution containing an oligomer of dihydric phenol (I) having a terminal chloroformate group, the mixed solution is stirred until the molecular weight distribution (Mw/Mn) is 3 or less. A highly purified hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (3) is added to the dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are interfacially polycondensed. A polycarbonate-polydiorganosiloxane copolymer is thus obtained.

When performing the interfacial polycondensation reaction, an acid binder may be added as appropriate in consideration of the stoichiometric ratio (equivalents) of the reaction. 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. Specifically, if a portion of the hydroxyaryl-terminated polydiorganosiloxane (II) used or, as noted above, the dihydric phenol (I) is added to this reaction step as a post-add monomer, two of the post-add monomers It is preferable to use 2 equivalents or more of the alkali with respect to the total number of moles of the phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mol corresponds to 2 equivalents).

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 mixed solution.

A terminal terminator or molecular weight modifier is usually used in such a polymerization reaction. Examples of terminal terminating agents include compounds having a monovalent phenolic hydroxyl group, such as usual phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, long-chain alkylphenols and aliphatic carboxylic acids. Examples include 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 all dihydric phenol compounds used, and it is of course possible to use two or more kinds of compounds together. be.

A catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added to promote the polycondensation reaction.

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

A branching agent can be used in combination with the above dihydric phenolic compound to form a branched polycarbonate-polydiorganosiloxane. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucine, phloroglucide, 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-methylphenol, trisphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxy phenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among others, 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 polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9, based on the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. mol %, more preferably 0.01 to 0.8 mol %, particularly preferably 0.05 to 0.4 mol %. The amount of such branched structures can be calculated by ¹ H-NMR measurement.

The reaction pressure can be any of reduced pressure, normal pressure, and increased pressure, but usually normal pressure or the self-pressure of the reaction system can be suitably used. The reaction temperature is selected from the range of −20 to 50° C. In many cases, heat is generated with polymerization, so water cooling or ice cooling is desirable. The reaction time varies depending on other conditions such as the reaction temperature and cannot be generally defined, but is usually 0.5 to 10 hours.

In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and/or chemical treatment (polymer reaction, cross-linking treatment, partial decomposition treatment, etc.) to achieve the desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin with a viscosity of [η _SP /c].

The obtained reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods, and recovered as a polycarbonate-polydiorganosiloxane copolymer resin of desired purity (purity).　

The average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molding is preferably in the range of 1 to 40 nm. Such average size is more preferably 1 to 30 nm, more preferably 5 to 25 nm. Below the lower limit of the preferred range, sufficient impact resistance and flame retardancy may not be exhibited, and above the upper limit of the preferred range, impact resistance may not be exhibited stably. This provides a resin composition with excellent impact resistance and appearance.

The average domain size of polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded article of the present invention was evaluated by small angle X-ray scattering (SAXS). The small-angle X-ray scattering method is a method of measuring diffuse scattering/diffraction occurring in a small-angle region within a scattering angle (2θ)<10°. In this small-angle X-ray scattering method, if there are regions with different electron densities on the order of 1 to 100 nm in a substance, diffuse scattering of X-rays is measured from the difference in electron densities. Based on this scattering angle and scattering intensity, the particle diameter of the object to be measured is obtained. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregate structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, diffuse scattering of X-rays occurs due to the electron density difference between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity I at each scattering angle (2θ) in the range of less than 10° scattering angle (2θ) is measured to measure the small-angle X-ray scattering profile, and the polydiorganosiloxane domain is a spherical domain and the particle size distribution varies. Assuming the existence of , the average size of the polydiorganosiloxane domains is obtained by performing a simulation using commercially available analysis software from the hypothetical particle size and hypothetical particle size distribution model. According to the small-angle X-ray scattering method, the average size of the polydiorganosiloxane domains dispersed in the polycarbonate polymer matrix, which cannot be accurately measured by observation with a transmission electron microscope, can be measured accurately, easily, and with good reproducibility. can. Average domain size means the number average of individual domain sizes. The term "average domain size" used in connection with the present invention is a measured value obtained by measuring a 1.0 mm thick portion of a three-tiered plate produced by the method described in Examples by such a small-angle X-ray scattering method. show. In addition, the analysis is performed using an isolated particle model that does not consider the interaction between particles (interference between particles).
(B component: colorant)
The coloring agent used as the B component in the present invention is a coloring agent containing a coloring agent having an absorption maximum at less than 650 nm (B1 component) and a coloring agent having an absorption maximum at 650 to 880 nm (B2 component). The ratio (weight ratio) of B1 component and B2 component in B component (B1 component/B2 component) is preferably 2/1 to 40/1, more preferably 2.5/1 to 30/1. It is preferably 3/1 to 25/1, and more preferably 3/1 to 25/1. If the ratio is less than 2/1, sufficient cut characteristics may not be obtained at 700 nm or less, and if it exceeds 40/1, absorption characteristics at 650 to 880 nm may be insufficient. The amount of sunlight that enters the sensor as noise increases, which may adversely affect sensing accuracy.

The coloring agent can be selected from dyes (organic, inorganic), pigments (organic, inorganic), etc., and is not particularly limited as long as the aromatic polycarbonate resin composition aimed at by the present invention can be obtained. . As the colorant, it is preferable to use a dye because the dye does not cause diffuse reflection of light on the surface of the particles. Dye-based coloring agents include, for example, anthraquinone-based coloring agents, perinone-based coloring agents, perylene-based coloring agents, methine-based coloring agents, azo-based coloring agents, quinoline-based coloring agents, phthalocyanine-based coloring agents, squarylium-based coloring agents, and complex coloring agents. Cyclic coloring agents and the like. Among them, anthraquinone-based coloring agents, phthalocyanine-based coloring agents, perylene-based coloring agents, and heterocyclic coloring agents having high heat resistance are more preferable.

The content of component B is 0.055 to 1.3 parts by weight, preferably 0.08 to 1.0 parts by weight, and 0.1 to 0.5 parts by weight with respect to 100 parts by weight of component A. Part is more preferred. If the content of component B is less than 0.055 parts by weight, sufficient cutting properties in the range of 400 to 700 nm cannot be obtained. On the other hand, when it exceeds 1.3 parts by weight, the thermal stability of the resin composition deteriorates.
(C component: heat stabilizer)
The aromatic polycarbonate resin composition of the present invention contains a phosphorus heat stabilizer and/or a phenol heat stabilizer. Phosphorus-based heat stabilizers improve heat stability during production or molding, and improve mechanical properties, color, and molding stability. Examples of phosphorus-based heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters, and tertiary phosphines. Specific examples of phosphite compounds include triphenylphosphite, tris(nonylphenyl)phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenyl Phosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, tris( diethylphenyl)phosphite, tris(di-iso-propylphenyl)phosphite, tris(di-n-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2, 6-di-tert-butylphenyl)phosphite, distearylpentaerythritol 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, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl)penta Erythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like. Furthermore, as other phosphite compounds, those having a cyclic structure which react 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′-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite. Phosphate compounds 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, Diisopropyl phosphate and the like can be mentioned, and triphenyl phosphate and trimethyl phosphate are preferred.

Phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenedi Phosphonite, Tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, Tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite , tetrakis(2,6-di-tert-butylphenyl)-4,3′-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(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, bis(2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite and the like, preferably tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, tetrakis(2, 4-di-tert-butylphenyl)-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group substituted with two or more alkyl groups, and is therefore preferable. Phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, and the like. Tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, and tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine. The phosphorus-based heat stabilizers may be used singly or in combination of two or more. Among the above phosphorus-based heat stabilizers, it is preferable to blend an alkyl phosphate compound represented by trimethyl phosphate. In addition, the combination use of such an alkyl phosphate compound with a phosphite compound and/or a phosphonite compound is also a preferred embodiment.

The phenolic heat stabilizer is not particularly limited as long as it has an antioxidant function. , tetrakis{methylene-3-(3′,5′-di-t-butyl-4-hydroxyphenyl)propionate}methane, distearyl(4-hydroxy-3-methyl-5-t-butylbenzyl)malonate, tri Ethylene glycol-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-thiodiethylenebis{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, etc. is mentioned.

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.

The content of component C is 0.003 to 0.5 parts by weight, preferably 0.005 to 0.3 parts by weight, and 0.01 to 0.2 parts by weight with respect to 100 parts by weight of component A. Part is more preferred. When the content of the C component is less than 0.003 parts by weight, the thermal stability of the resin composition deteriorates, and the thermal stability of the absorption properties also deteriorates. On the other hand, when it exceeds 0.5 parts by weight, the moist heat resistance of the resin composition deteriorates.
(Component D: Benzotriazole UV absorber)
The aromatic polycarbonate resin composition of the present invention preferably contains a benzotriazole ultraviolet absorber. Examples of benzotriazole-based UV absorbers 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, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octyl oxyphenyl)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 2-(2′-hydroxy-5-methacryloxyethylphenyl)-2H-benzo a copolymer of triazole and a vinyl-based monomer copolymerizable with the monomer, or 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and a vinyl-based monomer copolymerizable with the monomer; and polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton such as copolymers of. Further, the above ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbing monomer and/or photostable monomer and a monomer such as alkyl (meth)acrylate It may be a polymer-type ultraviolet absorber obtained by copolymerizing with a body. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton in the ester substituent of (meth)acrylic acid ester. Among them, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole represented by Tinuvin 234 (BASF Japan Ltd.), Tinuvin 326 (BASF Japan) Ltd.) is more preferable.

The content of component D is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.8 part by weight, more preferably 0.1 to 0.1 part by weight, per 100 parts by weight of component A. More preferably 5 parts by weight. If the content of component D is less than 0.01 parts by weight, the light stability of absorption characteristics may deteriorate, while if it exceeds 1 weight, the thermal stability of the resin composition may deteriorate. .
(Other additives)
Additives used for these improvements are advantageously used in the aromatic polycarbonate resin composition of the present invention in order to improve its thermal stability and design properties. These additives will be specifically described below.
(I) Heat stabilizer other than component C The aromatic polycarbonate resin composition of the present invention may contain other heat stabilizers than the phosphorus-based heat stabilizer and the phenol-based heat stabilizer. Such other heat stabilizers are preferably lactone-based stabilizers represented by reaction products of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. be done. Details of such stabilizers are described in JP-A-7-233160. Such a compound is available commercially as Irganox HP-136 (trademark, CIBA SPECIALTY CHEMICALS). Further, stabilizers obtained by mixing said compound with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is a suitable example. The content of the lactone 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 stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. exemplified. The content of the sulfur-containing stabilizer 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. The polycarbonate resin composition of the present invention may optionally contain an epoxy compound. Such epoxy compounds are blended for the purpose of suppressing mold corrosion, and basically all those having epoxy functional groups can be applied. Specific examples of preferred epoxy compounds include 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexylcarboxylate, 2,2-bis(hydroxymethyl)-1-butanol of 1,2-epoxy-4- (2-oxiranyl) cyclohexane adducts, copolymers of methyl methacrylate and glycidyl methacrylate, copolymers of styrene and glycidyl methacrylate, and the like. The content of such an epoxy compound is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, and still more preferably 0.005 to 0.005 parts by weight with respect to 100 parts by weight of component A. 0.1 parts by weight.
(II) Release agent The aromatic polycarbonate resin composition of the present invention contains a release agent within a range that does not impair the object of the present invention in order to further improve the releasability from the mold during melt molding. is also possible.

Examples of such release agents include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefinic waxes, olefinic waxes containing carboxy groups and/or carboxylic acid anhydride groups, silicone oils, organopolysiloxane and the like. Preferred higher fatty acid esters are 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. Partial or full esters of monohydric or polyhydric alcohols with saturated fatty acids include, for example, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, stearyl stearate, behenic acid monoglyceride, and behenic acid. Behenyl, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphene -to, sorbitan monostearate, 2-ethylhexyl stearate and the like. Among them, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used. As higher fatty acids, saturated fatty acids having 10 to 30 carbon atoms are preferred. Such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.

One of these release agents may be used alone, or two or more thereof may be used in combination. The content of the release agent is preferably 0.01 to 5 parts by weight per 100 parts by weight of component A.
<Method for producing resin composition>
Any method is employed to produce the polycarbonate resin composition of the present invention. For example, a method of premixing each component and optionally other components, followed by melt-kneading and pelletizing can be mentioned. Means for premixing include a Nauta mixer, a V-type blender, a Henschel mixer, a mechanochemical device, an extrusion mixer, and the like. In the pre-mixing, granulation can be performed by an extrusion granulator, a briquetting machine, or the like. After pre-mixing, the mixture is melt-kneaded by a melt-kneader typified by a vented twin-screw extruder, and pelletized by a device such as a pelletizer. Other examples of the melt-kneader include a Banbury mixer, a kneading roll, a constant temperature stirring vessel and the like, but a vented twin-screw extruder is preferred. Alternatively, each component and, optionally, other components may be supplied independently to a melt-kneader typified by a twin-screw extruder without being premixed.
<About molded products>
The polycarbonate resin composition of the present invention obtained as described above can be used to produce various products by injection molding the pellets produced as described above. Further, it is also possible to directly form a sheet, film, profile extrusion molded product, and injection molded product from the resin melt-kneaded in an extruder without going through pellets. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluid), insert molding, Molded articles can be obtained using injection molding methods such as in-mold coating molding, adiabatic molding, rapid heat and cool molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The advantages of these various molding methods are already widely known. For molding, either cold runner method or hot runner method can be selected. Moreover, the resin composition of the present invention can also be molded into various shaped extruded products and sheets by extrusion molding.

A molded article made of the resin composition of the present invention must have an average light transmittance of 1.5% or less in the thickness direction of a molded article having a thickness of 3 mm at a wavelength of 400 to 700 nm. The average light transmittance is more preferably 1.0% or less, more preferably 0.5% or less. If the average value of the light transmittance exceeds 1.5%, the amount of sunlight that causes noise increases, adversely affecting sensing. Although the lower limit of the average light transmittance is not particularly limited, it is preferably 0% or more.

In addition, the molded article made of the resin composition of the present invention has a maximum light transmittance of 5.0 in the thickness direction of a molded article molded to a thickness of 3 mm at a wavelength from 400 nm to the wavelength at which the absorption of the B2 component is maximum. % or less, more preferably 3.0% or less, even more preferably 2.0% or less. If the maximum light transmittance exceeds 5.0%, light near the maximum transmittance becomes noise, which may adversely affect sensing. Although the lower limit of the maximum value of the light transmittance is not particularly limited, it is preferably 0% or more.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. "Parts" are parts by weight unless otherwise specified. In addition, evaluation was implemented by the following method.
[Evaluation of Resin Composition]
1. Average value of light transmittance at 400 to 700 nm For a continuous molded product produced by the following method, using an ultraviolet visible near infrared spectrophotometer (V-770 manufactured by JASCO Corporation), in the range of 300 to 2500 nm Spectral light transmittance was measured. The average light transmittance of 400 to 700 nm was calculated from the obtained spectrum.
2. Maximum value of light transmittance at absorption maximum wavelength of component B2 from 400 nm Spectral light transmittance was measured in the same manner as "Average value of light transmittance at 1.400 to 700 nm". From the obtained spectrum, the maximum value of light transmittance was read from 400 nm to the maximum absorption wavelength of the B2 component.
3. Thermal Stability of Absorption Characteristics The spectral light transmittance of the continuous molded product was measured in the same manner as the "average value of light transmittance at 1.400 to 700 nm". The spectral spectrum obtained was scanned from a wavelength of 1100 nm toward the lower wavelength side, and the wavelength (transmission wavelength λt) at which the transmittance reached 80% or less for the first time was read. The transmitted wavelength λtr was read in the same manner for the staying molded product. When λtr-λt is 0 to 5, it is evaluated as ⊚, when it is 6 to 10, it is evaluated as ◯, when it is 11 to 20, it is evaluated as Δ, and when it is 21 or more, it is evaluated as ×.
4. Photostability of Absorption Characteristics The transmission wavelength λtx of the light-exposed product was read in the same manner as the “average value of light transmittance in the range of 1.400 to 700 nm”. When |λtx−λt| is 0 to 5, the case is ⊚;
5. Thermal stability of resin composition (viscosity average molecular weight)
The viscosity average molecular weight (M ₀ ) of the continuously molded product and the viscosity average molecular weight (M ₁ ) of the staying molded product were measured by the following methods. A case where M ₀ −M ₁ <1,000 was satisfied was evaluated as ◯, and a case where M 0 −M 1 <1,000 was not satisfied was evaluated as X.

The viscosity-average molecular weight (M) is obtained by first calculating the specific viscosity (η _SP ) calculated by the following formula at 20° C. by dissolving 0.7 g of the molded product obtained by the following method in 100 ml of methylene chloride, and then calculating the Ostwald viscosity. using a meter,
Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
was calculated from the obtained specific viscosity (η _SP ) by the following formula.

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
6. Wet heat resistance of resin composition (viscosity average molecular weight)
The viscosity-average molecular weight (M ₀ ) of the continuously molded product and the viscosity-average molecular weight (M ₂ ) of the wet-heat-treated product were measured in the same manner as in “5. Thermal stability of resin composition”. A case where M ₀ −M ₂ <1,000 was satisfied was indicated by ◯, and a case where it was not satisfied was indicated by ×.
[Examples 1 to 41, Comparative Examples 1 to 4]
[Production of resin pellets]
Based on the components and contents shown in Tables 1 to 4, various ingredients are mixed using a tumbler and melt-kneaded at a cylinder temperature of 280 ° C. using a twin-screw extruder (Japan Steel Works, Ltd. TEX30α). Various pellets were obtained. The components used are as follows.
[Preparation of molded product by injection molding]
After drying the pellets obtained by the above method in a hot air circulation dryer at 120 ° C. for 5 hours, an injection molding machine (FANUC Co., Ltd. ROBOSHOT α-S100iA) was used, and the cylinder temperature was 340 ° C. The mold A plate-shaped specimen with a thickness of 3 mm was formed at a temperature of 80°C. Molding was carried out continuously, and injection was stopped for 10 minutes while resin was present in the cylinder, and then molding was carried out again. A continuously molded product was obtained by molding continuously without stopping the injection, and a staying molded product was obtained by molding after stopping the injection for 10 minutes while the resin was present in the cylinder.
[Light exposure treatment of molded product]
Using a xenon weather meter (Suga Test Instruments Co., Ltd. NX75Z), the continuously molded product obtained by the above method was measured at a black panel temperature of 63°C, a chamber temperature of 50°C, a relative humidity of 50%, and an irradiation intensity of 0.5°C. A molded article subjected to light exposure treatment for 1000 hours under the condition of 35 W/m ² (@ 340 nm) was used as a light exposure treated article.
[Wet heat treatment of molded product]
The continuous molded product obtained by the above method is subjected to wet heat treatment for 1000 hours at a temperature of 80 ° C. and a humidity of 85% using a constant temperature and humidity chamber (Espec Co., Ltd. PR-3J). The product was treated as a wet heat treated product.
(A component)
A-1: Panlite L-1225WX manufactured by Teijin Limited (viscosity average molecular weight: 19,700)
A-2: Panlite L-1225WP manufactured by Teijin Limited (viscosity average molecular weight: 22,400)
A-3: Polycarbonate resin produced by the following method A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 3844 parts of a 48% sodium hydroxide aqueous solution and 22,380 parts of ion-exchanged water. , 2-bis (4-hydroxy-3-methylphenyl) propane (Bis-C, manufactured by Honshu Chemical) 1,992 parts, 2,2-bis (4-hydroxyphenyl) propane (Bis-A, Nippon Steel Chemical After dissolving 1,773 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries, Ltd.) and 7.53 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries, Ltd.), 13,210 parts of methylene chloride was added, and 2,000 parts of phosgene was added to about 2,000 parts of phosgene at 15 to 25°C while stirring. It was blown for 60 minutes. After the completion of blowing of phosgene, 640 parts of a 48% aqueous sodium hydroxide solution and 93.2 parts of p-tert-butylphenol are added, stirring is resumed, 3.24 parts of triethylamine is added after emulsification, and the mixture is further stirred at 28 to 33°C for 1 hour. to terminate the reaction. After the completion of the reaction, the product was diluted with methylene chloride and washed with water, then acidified with hydrochloric acid and washed with water. The washing with water was repeated until the conductivity of the aqueous phase became approximately the same as that of ion-exchanged water. Obtained. Next, this solution is passed through a filter with a mesh size of 0.3 μm, and is added dropwise to hot water in a kneader with an isolated chamber having a foreign matter outlet at the bearing portion to flake the polycarbonate resin while distilling off the methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder. The viscosity average molecular weight was 20,000.
(B1 component)
B1-1: NUBIAN BLACK PC-5857 (Orient Chemical Industry Co., Ltd., absorption maximum wavelength 599 nm)
(B2 component)
B2-1: Phthalocyanine colorant FDR-004 (Yamada Chemical Industry Co., Ltd., maximum absorption wavelength 720 nm)
B2-2: Anthraquinone colorant SDO-7 (Arimoto Chemical Industry Co., Ltd., absorption maximum wavelength 676 nm)
B2-3: Anthraquinone colorant SDO-11 (Arimoto Chemical Industry Co., Ltd., absorption maximum wavelength 761 nm)
B2-4: heterocyclic coloring agent SDO-C33 (Arimoto Chemical Industry Co., Ltd., absorption maximum wavelength 847 nm)
B2-5: Perylene colorant Lumogen IR-765 (BASF Japan Co., Ltd., maximum absorption wavelength 769 nm)
(C component)
C-1: Phosphorus-based heat stabilizer ADEKA STAB 2112 (ADEKA Corporation)
C-2: Phenolic heat stabilizer AO-50 (ADEKA Corporation)
(D component)
D-1: Benzotriazole-based UV absorber Tinuvin 234 (BASF Japan Ltd.)
D-2: Benzotriazole-based UV absorber Tinuvin 326 (BASF Japan Ltd.)
D-3: Benzotriazole-based UV absorber Seesorb 709 (Shipro Kasei Co., Ltd.)
(Other ingredients)
E-1: Unistar H476S (NOF Corporation)
E-2: Likester EW-400 (Riken Vitamin Co., Ltd.)
G-1: Phthalocyanine colorant FDN-004 (Yamada Chemical Industry Co., Ltd., maximum absorption wavelength 887 nm)

The examples listed in Tables 1 to 4 are all excellent in thermal stability and resistance to moisture and heat, and have wavelength-selective absorption characteristics, so they can be used with various infrared light sources used in infrared sensors for automatic driving systems. . Furthermore, the result was excellent in the thermal stability and light stability of the absorption characteristics.

Regarding the B component, if the content is less than the lower limit, the average value of the light transmittance at 400 nm to 700 nm exceeds 1.5%, and the maximum light transmittance at the wavelength of 400 nm to the maximum absorption of the B2 component is 5. The result exceeded 0%. When the content exceeded the upper limit, the thermal stability of the resin composition deteriorated. Regarding the C component, when the content was less than the lower limit, the result was poor thermal stability of absorption characteristics, and when the content exceeded the upper limit, the result was poor heat and humidity resistance of the resin composition.

Claims

(A) Per 100 parts by weight of the aromatic polycarbonate resin (component A), (B) (B1) a coloring agent having an absorption maximum at less than 650 nm (component B1) and (B2) a coloring agent having an absorption maximum at 650 to 880 nm 0.055 to 1.3 parts by weight of a colorant (B component) containing (B2 component) and 0.003 to 0.5 parts by weight of (C) a phosphorus heat stabilizer and/or a phenolic heat stabilizer (C component) wherein the average value of the light transmittance in the thickness direction of a molded article having a thickness of 3 mm at 400 to 700 nm is 1.5% or less. .
The resin composition according to claim 1, wherein the ratio (weight ratio) of the B1 component and the B2 component (B1 component/B2 component) is 2/1 to 40/1.
2. The maximum value of the light transmittance in the thickness direction of a molded article having a thickness of 3 mm is 5.0% or less at a wavelength from 400 nm to which the absorption of the B2 component is maximum. The resin composition according to .
4. The B2 component is at least one colorant selected from the group consisting of anthraquinone colorants, phthalocyanine colorants, perylene colorants and heterocyclic colorants. The resin composition according to .
The resin composition according to any one of claims 1 to 4, characterized by containing 0.01 to 1 part by weight of (D) a benzotriazole-based ultraviolet absorber (component D) with respect to 100 parts by weight of component A. .
The resin composition according to any one of claims 1 to 5, wherein the viscosity average molecular weight of component A is 24,000 or less.
A molded product obtained by molding the resin composition according to any one of claims 1 to 6.
The molded article according to claim 7, which is a cover material for covering the infrared sensor.
9. The molded article of claim 8, which is a cover material for covering infrared sensors used in driver monitoring systems to monitor drivers and LiDAR to detect other vehicles and buildings.