JP7587405B2 - Wavelength-selectively transparent polycarbonate resin composition - Google Patents

Description

The present invention relates to a wavelength-selectively transparent polycarbonate resin composition, and more specifically, to a polycarbonate resin composition that has wavelength-selective transparency and does not transmit visible light but transmits infrared light.

One of the known remote sensing techniques using light is LIDAR (Light Detection and Ranging, Laser Imaging Detection and Ranging), which measures the scattered light from a pulsed laser and analyzes the distance to and characteristics of a distant target. This technique is similar to radar, but replaces radar's radio waves with light. The distance to the target is calculated from the time it takes for the light to be reflected after it is emitted. LIDAR uses electromagnetic waves with much shorter wavelengths than radar, typically ultraviolet, visible, or near-infrared.

Autonomous driving technology for automobiles has been developing rapidly in recent years. To support level 3, which is conditional autonomous driving, and levels 4 to 5, which do not assume the driver is at the wheel, a function for safe autonomous driving on highways and general roads is required. For this reason, in addition to cameras and millimeter-wave radar, lidar is attracting attention as a way to ensure sensing redundancy. To support autonomous driving, it is necessary to further improve the accuracy of lidar, and there is a demand to develop wavelength selection filters with superior performance.

Patent Document 1 discloses that an epoxy resin cured body containing an azoanthraquinone-based mixture has an average transmittance of 0% in the wavelength range of 380 nm and an optical transmittance of 80% or more at a wavelength of 900 nm, and is therefore suitable for use when the laser light wavelength used in Lidar is in the range of 850 to 950 nm (see Patent Document 1, Examples 1 to 2, [0050], [Figure 1]). Furthermore, Patent Document 1 discloses that an epoxy resin cured body containing an azoanthraquinone-based mixture has an average transmittance of 0% in the wavelength range of 380 nm and an optical transmittance of 80% or more at a wavelength of 1550 nm, and is therefore suitable for use when the laser light wavelength used in Lidar is in the range of 1500 to 1600 nm (see Patent Document 1, Examples 1 to 3, [0050], [Figure 1]).

JP 2017-167484 A

Patent Document 1 discloses a cured epoxy resin, but the cured epoxy resin is not necessarily suitable for providing in large quantities at low cost. Considering future developments in Lidar, it is necessary to provide a composition and molded products thereof that can be mass-produced at low cost.

The present inventors focused on molded articles of polycarbonate, which has excellent transparency and mechanical strength, but noticed that because polycarbonate has a high molding temperature, the transmittance may decrease and/or increase during molding of a polycarbonate resin composition at high temperatures, that is, the transmittance (optical properties) may change. Changes in optical properties may cause malfunctions. Therefore, the object of the present invention is to provide a polycarbonate resin composition and molded articles thereof that have wavelength selective transmittance and do not substantially change in optical properties even when molded at high temperatures.

As a result of intensive research, the present inventors have found that a polycarbonate resin composition containing a colorant (e.g., an anthraquinone-based dye) with a maximum absorption wavelength of less than 1200 nm and a phosphoric acid or phosphoric acid ester-based compound provides a polycarbonate resin composition and a molded article thereof that exhibit wavelength selective transparency without substantial change in optical properties even when molded at high temperatures. Furthermore, they have found that such a resin composition and molded article can be suitably used for Lidar applications, and have thus completed the present invention.

The wavelength-selective transmitting polycarbonate resin molded article according to the present invention comprises an aromatic polycarbonate resin (A), a colorant (B) containing a dye having a maximum absorption wavelength of less than 1200 nm, and phosphoric acid (C 2 ), the polymer component being made of the aromatic polycarbonate resin (A), the colorant (B) being 0.001 to 2.0 parts by mass and the phosphoric acid (C2) being 0.0001 to 0.004 parts by mass relative to 100 parts by mass of the aromatic polycarbonate resin (A), or the polymer component being made of the aromatic polycarbonate resin (A), the colorant (B) containing a dye having a maximum absorption wavelength of less than 1200 nm, and a phosphoric acid ester compound or phosphoric acid (C), the polymer component being made of the aromatic polycarbonate resin (A), the colorant (B) containing an anthraquinone dye, and the phosphoric acid ester compound or phosphoric acid (C) being at least one selected from the group consisting of phosphoric acid ester compounds or phosphoric acid represented by the following general formula (I):
Formula (I):
O=P(OH) _n (OR) _3-n
[In general formula (I), R is an alkyl group or an aryl group, and n is an integer of 2.]
The composition contains 0.29 to 2.0 parts by mass of a colorant (B) relative to 100 parts by mass of an aromatic polycarbonate resin (A), and, with respect to the phosphate ester compound or phosphoric acid (C), contains 0.005 to 0.3 part by mass of a phosphate ester compound (C1) or 0.0001 to 0.004 part by mass of phosphoric acid (C2) .

The wavelength-selectively transparent polycarbonate resin molded article according to the present invention contains the wavelength-selectively transparent aromatic polycarbonate resin composition described above.

The method for producing a wavelength-selectively transparent polycarbonate resin molded article according to the present invention includes molding the above-mentioned resin composition.

The polycarbonate resin composition of the embodiment of the present invention can be molded using a conventional device to produce a molded article, and the optical properties do not change substantially during the molding process. Therefore, the polycarbonate resin composition of the embodiment of the present invention can provide a molded article that has appropriate wavelength selectivity and does not substantially change in optical properties. The molded article can be suitably used for Lidar applications.

The wavelength-selectively transparent polycarbonate resin composition according to an embodiment of the present invention includes an aromatic polycarbonate resin (A), a colorant (B) containing a dye having a maximum absorption wavelength of less than 1200 nm, and a phosphate ester compound or phosphoric acid (C), and contains 0.001 to 2.0 parts by mass of the colorant (B) relative to 100 parts by mass of the aromatic polycarbonate resin (A), and the phosphoric acid or phosphate ester compound (C) contains 0.005 to 0.3 parts by mass of the phosphate ester compound (C1) or 0.0001 to 0.004 parts by mass of the phosphoric acid (C2).

In an embodiment of the present invention, the "aromatic polycarbonate resin (A)" is a polycarbonate resin based on an aromatic compound, and is not particularly limited as long as it can produce the aromatic polycarbonate resin composition of the present invention. Examples of such aromatic polycarbonate resins include polymers obtained by the phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or the ester exchange method in which a dihydroxydiaryl compound is reacted with a carbonate ester such as diphenyl carbonate. Representative examples include polycarbonate resins produced from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A).

In addition to bisphenol A, the dihydroxydiaryl compounds include, for example, bis(hydroxyaryl)alkanes such as bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxyphenyl-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; Examples of the cycloalkanes include bis(hydroxyaryl)cycloalkanes such as bis(4-hydroxyphenyl)cyclopentane and 1,1-bis(4-hydroxyphenyl)cyclohexane; dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; and dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone. These can be used alone or in combination. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, etc. can be used in combination.

Furthermore, the dihydroxydiaryl compound may be used in combination with, for example, the following trivalent or higher aromatic compounds.

Examples of the trivalent or higher phenolic compounds include phloroglucin, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptene, 2,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane, and 2,2-bis-[4,4-(4,4'-dihydroxydiphenyl)-cyclohexyl]-propane.

The viscosity average molecular weight of the aromatic polycarbonate resin (A) is preferably 10,000 to 100,000, and more preferably 12,000 to 30,000. When producing such an aromatic polycarbonate resin (A), a molecular weight regulator, a catalyst, etc. can be used as necessary. Commercially available products can be used as such aromatic polycarbonate resins.

In an embodiment of the present invention, the colorant (B) containing a pigment having a maximum absorption wavelength of less than 1200 nm contains a pigment having a maximum absorption wavelength of less than 1200 nm, and the pigment can be selected from, for example, dyes (organic, inorganic), pigments (organic, inorganic), etc., and is not particularly limited as long as the aromatic polycarbonate resin composition of the present invention can be obtained. As such a pigment, either a dye or a pigment can be used, but since dyes usually do not easily cause diffuse reflection of light on the surface of the particles, it is more preferable to use a dye. These colorants (B) containing pigments can be used alone or in combination of two or more.

Examples of the dye-based dyes include anthraquinone-based dyes, perinone-based dyes, perylene-based dyes, methine-based dyes, azo-based dyes, quinoline-based dyes, phthalocyanine-based dyes, and heterocyclic dyes. Oil-soluble dyes are preferred because they can be more easily and uniformly dispersed in the resin composition. Dyes are made of smaller particles than pigments, so they can be more uniformly mixed into the resin composition, which is preferable because it allows the molded body to have a smaller cloudiness (haze value). Dyes are more preferred for Lidar.

Examples of the pigment-based dyes include organic dyes such as azo dyes (soluble azo dyes, insoluble azo dyes), condensation dyes, threne pigments, quinacridone dyes, dioxazine dyes, and isoindoline dyes, as well as inorganic dyes such as titanium oxide, iron oxide, chromium oxide, carbon black, ultramarine blue, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, titanium black, and synthetic iron black.

The colorant (B) preferably includes a colorant (B1) containing a dye having a maximum absorption wavelength of less than 700 nm, and/or a colorant (B2) containing a dye having a maximum absorption wavelength of 700 nm or more and less than 1000 nm.

In an embodiment of the present invention, the colorant (B1) containing a dye having a maximum absorption wavelength of less than 700 nm preferably contains at least one selected from an anthraquinone dye, a perinone dye, a perylene dye, and a methine dye. The colorant (B1) preferably contains an anthraquinone dye.

The colorant (B1) may further contain at least one selected from the group consisting of phthalocyanine dyes and heterocyclic dyes.

In the resin composition according to the embodiment of the present invention, in addition to the anthraquinone-based dye, a combination of multiple other dyes can be used as the colorant (B1). For example, a combination of a pigment and a pigment, a combination of a pigment and a dye, or a combination of a dye and a dye may be used, but it is preferable to use a combination of a dye and a dye. Using an anthraquinone-based dye in combination with another dye is preferable because it can suppress or block light of various wavelengths and has good light transmittance in various wavelength ranges.

As long as the composition according to the embodiment of the present invention can be obtained, the above-mentioned dyes are not particularly limited, but specifically, the following dyes can be used:

The anthraquinone dye preferably includes at least one selected from the group consisting of Solvent Yellow 163, Disperse Violet 28, Solvent Blue 97, Solvent Green 28, Solvent Green 3, and Disperse Blue 60.

Examples of perinone dyes include those commercially available with color indexes such as Solvent Orange 60, Solvent Orange 78, Solvent Orange 90, Solvent Violet 29, Solvent Red 135, Solvent Red 162, and Solvent Red 179.

Examples of perylene-based pigments include pigments commercially available with color indexes such as Solvent Green 3, Solvent Green 5, Solvent Orange 55, Vat Red 15, Vat Orange 7, F Orange 240, F Red 305, F Red 339, F Yellow 83, and Solvent Red 179.

Methine dyes include those commercially available under the color index such as Solvent Orange 80, Solvent Yellow 93, Disperse Yellow 201, etc.
Quinoline dyes include those commercially available under the color indexes Solvent Yellow 33, Solvent Yellow 98, Solvent Yellow 157, Disperse Yellow 54, Disperse Yellow 201, and the like.

In an embodiment of the present invention, the colorant (B2) containing a dye having a maximum absorption wavelength in the range of 700 nm or more and less than 1000 nm preferably contains at least one dye selected from the group consisting of phthalocyanine dyes, anthraquinone dyes, and heterocyclic dyes.

The colorant (B2) preferably contains a phthalocyanine dye, and examples of such phthalocyanine dyes include FDN-002, FDN-023, and FDN-024, which are commercially available from Yamada Chemical Co., Ltd.

The colorant (B2) preferably contains a heterocyclic dye, and examples of such heterocyclic dyes include SDO-C8, which is commercially available from Arimoto Chemical Industry Co., Ltd.

The colorant (B2) preferably contains an anthraquinone-based dye, and examples of such an anthraquinone-based dye include SDO-C33, which is commercially available from Arimoto Chemical Industry Co., Ltd.

The resin composition according to an embodiment of the present invention preferably contains 0.001 to 2.0 parts by mass, more preferably 0.005 to 1.5 parts by mass, and even more preferably 0.006 to 1.0 parts by mass of a colorant (B) containing a pigment having a maximum absorption wavelength of less than 1200 nm, per 100 parts by mass of aromatic polycarbonate resin (A). The lower limit of the content of colorant (B) may be 0.02 parts by mass or 0.025 parts by mass.

In an embodiment of the present invention, the phosphate ester compound or phosphoric acid (C) is not particularly limited as long as the resin composition of the embodiment of the present invention can be obtained, but it is preferable that the compound contains at least one selected from the group consisting of phosphate ester compounds represented by the following general formula (I) and phosphoric acid.

Formula (I): O=P(OH) _n (OR) _3-n
[In formula (I), R is an alkyl group or an aryl group, which may be the same or different, and n is an integer of 0 to 3.]

In the above general formula (I), R is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and more preferably an alkyl group having 2 to 25 carbon atoms. Also, n is preferably 1 or 2.

Examples of the phosphate ester compounds of formula (I) include mono- or di-stearyl acid phosphate, and mixed stearyl phosphate esters (a mixture of approximately 50 mol% monostearyl phosphate and approximately 50 mol% distearyl phosphate (product name "AX-71" manufactured by Asahi Denka Co., Ltd.) are known.

Phosphoric acid is a non-volatile weak acid, and commercially available products can be used. Examples include, but are not limited to, phosphoric acid manufactured by Nacalai Tesque and phosphoric acid manufactured by Wako Pure Chemical Industries.

The resin composition according to an embodiment of the present invention preferably contains 0.005 to 0.3 parts by mass of the phosphate ester compound (C1), more preferably 0.007 to 0.1 parts by mass, and even more preferably 0.009 to 0.08 parts by mass of the phosphate ester compound or phosphoric acid (C), relative to 100 parts by mass of the aromatic polycarbonate resin (A). Alternatively, the resin composition preferably contains 0.0001 to 0.004 parts by mass of the phosphoric acid (C2), more preferably 0.0001 to 0.001 parts by mass, more preferably 0.0003 to 0.0008 parts by mass, and even more preferably 0.0004 to 0.0006 parts by mass of the phosphoric acid (C2).

The aromatic polycarbonate resin composition of the present invention may further contain a phosphorus-based antioxidant (D).

The phosphorus-based antioxidant is not particularly limited as long as it can provide the aromatic polycarbonate resin composition of the present invention, but it is preferable for the antioxidant to contain a phosphite compound having the following phosphite structure.

In the wavelength-selectively transparent polycarbonate resin composition according to an embodiment of the present invention, the phosphorus-based antioxidant (D) preferably contains at least one compound selected from a phosphite ester compound represented by the following formula (1), a phosphite ester compound represented by the following formula (2), a phosphite ester compound represented by the following formula (3), and a phosphite ester compound represented by the following formula (4).

The phosphorus-based antioxidant (D) preferably contains, for example, a compound represented by the following formula (1):

（式中、Ｒ^１は、炭素数１～２０のアルキル基を示し、ａは、０～３の整数を示す。） Formula (1):

(In the formula, ^R1 represents an alkyl group having 1 to 20 carbon atoms, and a represents an integer of 0 to 3.)

In the formula (1), R ¹ is an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.

Examples of the compound represented by formula (1) include triphenyl phosphite, tricresyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, and trisnonylphenyl phosphite. Among these, tris(2,4-di-t-butylphenyl) phosphite is particularly suitable, and is commercially available, for example, as Irgafos 168 manufactured by BASF (Irgafos is a registered trademark of BASF Societas Europea).

The phosphorus-based antioxidant (D) preferably contains, for example, a compound represented by the following formula (2):

（式中、Ｒ^２、Ｒ^３、Ｒ^５及びＲ^６は、それぞれ独立して、水素原子、炭素数１～８のアルキル基、炭素数５～８のシクロアルキル基、炭素数６～１２のアルキルシクロアルキル基、炭素数７～１２のアラルキル基又はフェニル基を示す。Ｒ^４は、水素原子又は炭素数１～８のアルキル基を示す。Ｘは、単結合、硫黄原子又は式：－ＣＨＲ^７－（ここで、Ｒ^７は、水素原子、炭素数１～８のアルキル基又は炭素数５～８のシクロアルキル基を示す）で表される基を示す。Ａは、炭素数１～８のアルキレン基又は式：＊－ＣＯＲ^８－（ここで、Ｒ^８は、単結合又は炭素数１～８のアルキレン基を示し、＊は、酸素側の結合手であることを示す）で表される基を示す。Ｙ及びＺは、いずれか一方がヒドロキシル基、炭素数１～８のアルコキシ基又は炭素数７～１２のアラルキルオキシ基を示し、もう一方が水素原子又は炭素数１～８のアルキル基を示す。） Formula (2):

(In the formula, R ² , R ³ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group. R ⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. X represents a single bond, a sulfur atom, or a group represented by the formula: -CHR ⁷ - (wherein R ⁷ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms). A represents an alkylene group having 1 to 8 carbon atoms or a group represented by the formula: *-COR ⁸ - (wherein R ⁸ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond on the oxygen side. Either Y or Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

In formula (2), R ² , R ³ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or a phenyl group.

Here, examples of alkyl groups having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, t-pentyl, i-octyl, t-octyl, and 2-ethylhexyl groups. Examples of cycloalkyl groups having 5 to 8 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of alkylcycloalkyl groups having 6 to 12 carbon atoms include 1-methylcyclopentyl, 1-methylcyclohexyl, and 1-methyl-4-i-propylcyclohexyl groups. Examples of aralkyl groups having 7 to 12 carbon atoms include benzyl, α-methylbenzyl, and α,α-dimethylbenzyl groups.

It is preferable that R ² , R ³ and R ⁵ are each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms or an alkylcycloalkyl group having 6 to 12 carbon atoms. In particular, it is preferable that R ² and R ⁵ are each independently a t-alkyl group such as a t-butyl group, a t-pentyl group or a t-octyl group, a cyclohexyl group or a 1-methylcyclohexyl group. In particular, it is preferable that R ³ is an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group or a t-pentyl group, and it is more preferable that R 3 is a methyl group, a t-butyl group or a t-pentyl group.

The ^R6 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms, and more preferably a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, or a t-pentyl group.

In formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include the alkyl groups exemplified in the description of R ² , R ³ , R ⁵ , and R ^6. In particular, R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In formula (2), X represents a single bond, a sulfur atom, or a group represented by the formula -CHR ⁷ -. Here, R ⁷ in the formula -CHR ⁷ - represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 5 to 8 carbon atoms include the alkyl groups and cycloalkyl groups exemplified in the explanation of R ² , R ³ , R ⁵ , and R ⁶ , respectively. In particular, X is preferably a single bond, a methylene group, or a methylene group substituted with a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, or the like, and more preferably a single bond.

In formula (2), A represents an alkylene group having 1 to 8 carbon atoms or a group represented by the formula *-COR ⁸ -. Examples of the alkylene group having 1 to 8 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a 2,2-dimethyl-1,3-propylene group, and the like, with a propylene group being preferred. Furthermore, R ⁸ in the formula *-COR ⁸ - represents a single bond or an alkylene group having 1 to 8 carbon atoms. Examples of the alkylene group having 1 to 8 carbon atoms represented by R ⁸ include the alkylene groups exemplified in the above description of A. ^{R 8} is preferably a single bond or an ethylene group. Furthermore, * in the formula *-COR ⁸ - represents a bond on the oxygen side, and indicates that the carbonyl group is bonded to the oxygen atom of the phosphite group.

In formula (2), one of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a t-butoxy group, and a pentyloxy group. Examples of the aralkyloxy group having 7 to 12 carbon atoms include a benzyloxy group, an α-methylbenzyloxy group, and an α,α-dimethylbenzyloxy group. Examples of the alkyl group having 1 to 8 carbon atoms include the alkyl groups exemplified in the explanation of R ² , R ³ , R ^5, and R ⁶ above.

Examples of compounds represented by formula (2) include 2,4,8,10-tetra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine, 6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepine, 6 -[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, and 6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin. Among these, when the resulting aromatic polycarbonate resin composition is to be used in fields where optical properties are particularly required, 2,4,8,10-tetra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine is suitable, and is commercially available, for example, as Sumilizer GP (Sumilizer is a registered trademark) manufactured by Sumitomo Chemical Co., Ltd.

The phosphorus-based antioxidant (D) preferably contains, for example, a compound represented by the following formula (3):

（式中、Ｒ^９及びＲ^１０は、それぞれ独立して、炭素数１～２０のアルキル基又はアルキル基で置換されていてもよいアリール基を示し、ｂ及びｃは、それぞれ独立して、０～３の整数を示す。） Formula (3):

(In the formula, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group, and b and c each independently represent an integer of 0 to 3.)

Examples of compounds represented by formula (3) include bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite and phenyl bisphenol A pentaerythritol diphosphite. Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite is commercially available under the trade name "ADEKA STAB PEP-24G" manufactured by ADEKA Corporation. Adeka STAB PEP-36 ("ADEKA STAB" is a registered trademark) manufactured by ADEKA Corporation is commercially available.

The phosphorus-based antioxidant (D) preferably contains, for example, a compound represented by the following formula (4):

Formula (4):

(In the formula, R ¹¹ to R ¹⁸ each independently represent an alkyl group or alkenyl group having 1 to 3 carbon atoms. R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ , and R ¹⁷ and R ¹⁸ may be bonded to each other to form a ring. ^{R 19} to R ²² each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. d to g each independently represent an integer of 0 to 5. ^{X 1} to X ⁴ each independently represent a single bond or a carbon atom. When X ¹ to X ⁴ are single bonds, among R ¹¹ to R ²² , the functional group linked to the single bond is excluded from formula (4).)

A specific example of the compound represented by formula (4) is bis(2,4-dicumylphenyl)pentaerythritol diphosphite, which is commercially available under the trade name "Doverphos (registered trademark) S-9228" manufactured by Dover Chemical Co., and under the trade name "ADEKA STAB PEP-45" (bis(2,4-dicumylphenyl)pentaerythritol diphosphite) manufactured by ADEKA Corporation.

Further examples of the phosphorus-based antioxidant (D) include [1,1'-biphenyl]-4,4'-diylbis[bis(2,4-di-t-butylphenoxy)phosphine], which are commercially available under the trade name Irgaphos P-EPQ manufactured by BASF and HOSTANOX P-EPQ manufactured by Clariant Chemicals.

The above-mentioned aromatic polycarbonate resin composition preferably satisfies at least one selected from the following:
The phosphite compound represented by the formula (1) contains tris(2,4-di-t-butylphenyl)phosphite;
The phosphite compound represented by the formula (2) contains 2,4,8,10-tetra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine;
The phosphite compound represented by the formula (3) contains 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane; and The phosphite compound represented by the formula (4) contains bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

The amount of phosphorus-based antioxidant (D) is preferably up to 0.5 parts by mass, and more preferably 0.02 to 0.2 parts by mass, per 100 parts by mass of aromatic polycarbonate resin (A).

The wavelength-selectively transparent polycarbonate resin composition according to an embodiment of the present invention may further contain a dye (E) that includes a phthalocyanine compound having a maximum absorption wavelength in the range of 1000 nm to 1200 nm. When the wavelength-selectively transparent polycarbonate resin composition contains the dye (E), it absorbs light with wavelengths of 1000 to 1200 nm, and therefore the transmission wavelength range can be shifted to the longer wavelength side.

［式中、Ｒ^３１は、同一でも異なってもよく、水素原子又は置換基を有してよいアルキル基を示す。
Ｒ^３２及びＲ^３３は、同一でも異なってもよく、ハロゲン原子、ＯＲ^３４基、ＳＲ^３５基又はＮＲ^３６又はＲ^３７基を示す。
Ｘ^１１は、同一でも異なってもよく、酸素原子又は硫黄原子を示す。
Ｒ^３４及びＲ^３５基は、同一でも異なっていてもよく、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいヘテロアリール基を示す。
Ｒ^３６及びＲ^３７基は、同一または異なっていてもよい、水素原子、置換基を有していてもよいアルキル基、又は置換基を有していてもよいアリール基を示す。
Ｒ^３６とＲ^３７とは、これらが結合する窒素原子とともに、他の窒素原子、酸素原子もしくは硫黄原子を介して又は介することなく互いに結合して５～１０員の飽和又は不飽和複素環を形成していてもよい。該５～１０員の飽和又は不飽和複素環は、１個以上の置換基を有していてもよい。
Ｍは、２個の１価金属原子、２価金属原子、３価又は４価金属化合物を示す。］ The dye (E) preferably contains a compound represented by the following general formula (II).
Formula (II):

In the formula, R ³¹ may be the same or different and represents a hydrogen atom or an alkyl group which may have a substituent.
R ³² and R ³³ may be the same or different and each represents a halogen atom, an OR ³⁴ group, an SR 35 group, ^{an NR 36 group} or an R ³⁷ group.
^X11 may be the same or different and represents an oxygen atom or a sulfur atom.
R ³⁴ and R ³⁵ groups may be the same or different and represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
R ³⁶ and R ³⁷ groups may be the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
R ³⁶ and R ³⁷ may be bonded together with the nitrogen atom to which they are bonded to form a 5- to 10-membered saturated or unsaturated heterocycle with or without another nitrogen atom, oxygen atom, or sulfur atom. The 5- to 10-membered saturated or unsaturated heterocycle may have one or more substituents.
M represents two monovalent metal atoms, a divalent metal atom, or a trivalent or tetravalent metal compound.

［式中、Ｒ^３１は、同一でも異なってもよく、水素原子又は置換基を有してよいアルキル基を示す。
Ｘ^１１、Ｘ^１２及びＸ^１３は、同一でも異なってもよく、酸素原子又は硫黄原子を示す。
Ｒ^３４及びＲ^３５基は、同一でも異なっていてもよく、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいヘテロアリール基を示す。
Ｍは、２個の１価金属原子、２価金属原子、３価又は４価金属化合物を示す。］ The phthalocyanine compound represented by the above general formula (II) is preferably a compound represented by the following general formula (III).
Formula (III):

In the formula, R ³¹ may be the same or different and represents a hydrogen atom or an alkyl group which may have a substituent.
X ¹¹ , X ¹² and X ¹³ may be the same or different and each represents an oxygen atom or a sulfur atom.
R ³⁴ and R ³⁵ groups may be the same or different and represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
M represents two monovalent metal atoms, a divalent metal atom, or a trivalent or tetravalent metal compound.

Examples of "halogen atoms" include fluorine, chlorine, bromine and iodine.

Examples of "alkyl groups" include linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 3 to 12 carbon atoms. Specific examples include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, s-butyl groups, t-butyl groups (hereinafter also referred to as t-Bu), n-pentyl groups, 2-methylbutyl groups, group, 1-methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclopentyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1-ethyl-2-methylpropyl group, cyclohexyl group, n-heptyl group, 2-methyl Examples of such groups include an ethylhexyl group, a 3-methylhexyl group, a 4-methylhexyl group, a 5-methylhexyl group, a 2,4-dimethylpentyl group, an n-octyl group, a 2-ethylhexyl group, a 2,5-dimethylhexyl group, a 2,4,4-trimethylpentyl group, a 2,4-dimethylhexyl group, a 2,2,4-trimethylpentyl group, a t-octyl group, an n-nonyl group, a 3,5,5-trimethylhexyl group, an n-decyl group, a 4-ethyloctyl group, a 4-ethyl-4,5-dimethylhexyl group, an n-undecyl group, an n-dodecyl group, a 1,3,5,7-tetramethyloctyl group, and a 4-butyloctyl group. Preferred are linear alkyl groups having 1 to 8 carbon atoms, branched alkyl groups having 3 to 8 carbon atoms, or cyclic alkyl groups having 3 to 8 carbon atoms, and particularly preferred are methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, and t-octyl groups.

Examples of "aryl groups" include monocyclic and polycyclic (e.g., bicyclic or tricyclic) aryl groups. Specific examples include phenyl, naphthyl, and anthryl groups. Monocyclic or bicyclic aryl groups are preferred, with phenyl and naphthyl groups being particularly preferred.

Examples of "heteroaryl groups" include monocyclic and polycyclic (e.g., bicyclic or tricyclic) heteroaryl groups. Specific examples include pyridyl, pyrimidine, indolyl, quinoline, benzimidazole, furanyl, thienyl, benzofuran, and 1,3,4-thiadiazole groups. Monocyclic or bicyclic heteroaryl groups are particularly preferred.

The substituents on the alkyl chain, aryl ring, or heteroaryl ring of the above-mentioned alkyl group which may have a substituent, aryl group which may have a substituent, and heteroaryl group which may have a substituent (groups which may be substituted on the alkyl chain, aryl ring, or heteroaryl ring) include, for example, alkyl groups, haloalkyl groups, hydroxyalkyl groups, alkoxy groups, alkylthio groups, alkylamino groups, dialkylamino groups, cyclic amino groups, halogen atoms, acyl groups, alkoxycarbonyl groups, ureido groups, sulfamoyl groups, carbamoyl groups, alkylcarbamoyl groups, alkylsulfonyl groups, arylsulfonyl groups, alkoxysulfonyl groups, aryloxysulfonyl groups, cyano groups, and nitro groups. The number of such substituents (groups which may be substituted on the alkyl chain, aryl ring, or heteroaryl ring, hereinafter referred to as substituents) on the alkyl chain, aryl ring, or heteroaryl ring may be 1 to 5.

For example, when the alkyl group which may have a substituent is an "alkyl group having a substituent," specific examples of the alkyl group having a substituent include a 2-chloroethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a benzyl group, a phenethyl group, a 2-phenylethyl group, a 3-phenylethyl group, a 4-hydroxybutyl group, a 2-methoxyethyl group, a 3-methoxypropyl group, a 2-isopropoxyethyl group, and an ethyl butanoate group.

When the aryl group which may have a substituent is an "aryl group having a substituent", examples of the aryl group having a substituent include, specifically, a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 2,3-dichlorophenyl group, a 2,4-dichlorophenyl group, a 2,5-dichlorophenyl group, a 2,6-dichlorophenyl group, a 2,4,6-trichlorophenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,3-difluorophenyl group, a 2,4-difluorophenyl group, a 2,5-difluorophenyl group, a 2,6-difluorophenyl group, a 2,4,6-trifluorophenyl group, Examples include phenyl group, pentafluorophenyl group, N,N-dimethylaminophenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-ethylphenyl group, 4-t-butylphenyl group, 4-biphenyl group, 4-hydroxyphenyl group, 2-methoxyphenyl group, 4-methylthiophenyl group, 4-(trifluoromethyl)phenyl group, 4-phenoxyphenyl group, 4-acetylphenyl group, and 4-methoxycarbonylphenyl group.

When the heteroaryl group which may have a substituent is a "heteroaryl group having a substituent", specific examples of the heteroaryl group having a substituent include a 2-methylpyridyl group, a 2-chloropyridyl group, a 6-fluorobenzothiazole group, a 6-chlorobenzothiazole group, a 6-methylbenzothiazole group, a 6-methoxybenzothiazole group, a 5-methyl-1,3,4-thiadiazole group, a 5-methylthio-1,3,4-thiadiazole group, and a 5-trifluoromethyl-1,3,4-thiadiazole group.

Examples of divalent metals represented by M include metal atoms belonging to groups 3 to 15 of the periodic table. Specific examples include Cu, Zn, Fe, Co, Ni, Ru, Pb, Rh, Pd, Pt, Mn, Sn, and Pb.

Examples of trivalent or tetravalent metal compounds represented by M include halides, hydroxides, and oxides of metals belonging to groups 3 to 15 of the periodic table. Specific examples include AlCl, AlOH, InCl, FeCl, MnOH, SiCl ₂ , SnCl ₂ , GeCl ₂ , Si(OH) ₂ , Si(OCH ₃ ) ₂ , Si(OPh) ₂ , Si(OSiCH ₃ ) ₂ , Sn(OH) ₂ , Ge(OH) ₂ , VO, and TiO. In addition, Ph represents a phenyl group.

The phthalocyanine compound is preferably a phthalocyanine dye having a central metal selected from oxovanadium, copper, aluminum, cobalt, and zinc.

The dye (E) preferably contains at least one of the phthalocyanine compounds represented by the following formulas:

The dye (E) containing a phthalocyanine compound having a maximum absorption wavelength of 1000 nm or more and 1200 nm or less is preferably contained in an amount of 0.001 to 0.2 parts by mass, more preferably 0.002 to 0.18 parts by mass, even more preferably 0.004 to 0.16 parts by mass, particularly preferably 0.005 to 0.15 parts by mass, and even more particularly preferably 0.01 to 0.1 parts by mass, relative to 100 parts by mass of the aromatic polycarbonate resin (A).

When the dye (E) containing a phthalocyanine compound with a maximum absorption wavelength of 1000 nm or more and 1200 nm or less is contained in an amount of 0.001 to 0.2 parts by mass per 100 parts by mass of the aromatic polycarbonate resin (A), the wavelength-selective transparent polycarbonate resin composition and its molded article are superior because they can block light with longer wavelengths.

The dye (E) containing a phthalocyanine compound having a maximum absorption wavelength in the range of 1000 nm to 1200 nm can be a commercially available product. For example, FDN-010 (product name) manufactured by Yamada Chemical Industry Co., Ltd. can be used.

In addition to the above components, for example, an ultraviolet absorber, which is a component that further improves the weather resistance of the resulting aromatic polycarbonate resin composition, can be appropriately used in the aromatic polycarbonate resin composition according to the embodiment, depending on the application of the molded product obtained by molding the aromatic polycarbonate resin composition.

As the ultraviolet absorbing agent, for example, ultraviolet absorbing agents that are usually blended with polycarbonate resins, such as benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, and anilide oxalate-based compounds, can be used alone or in combination of two or more kinds.

Benzotriazole compounds include, for example, 2-(2-hydroxy-5-t-octylphenyl)benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)-2H-benzotriazole, and 2-(2H-benzotriazole-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl). phenol, 2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 2-[2'-hy droxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2'-Methylenbis[6-(2H-benzotriazol-2-yl)4-(1,1,3,3-te tramethylbutyl)phenol] and the like. Among these, 2-(2-hydroxy-5-t-octylphenyl)benzotriazole is particularly suitable, and commercially available examples include TINUVIN 329 (TINUVIN is a registered trademark) manufactured by BASF, Seesorb 709 manufactured by Shipro Kasei Co., Ltd., and Chemisorb 79 manufactured by Chemipro Kasei Co., Ltd.

Examples of triazine compounds include 2,4-diphenyl-6-(2-hydroxyphenyl-4-hexyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol. Commercially available examples include TINUVIN 1577 manufactured by BASF.

Examples of commercially available oxalic acid anilide compounds include Sanduvor VSU manufactured by Clariant Japan Co., Ltd.

Examples of benzophenone compounds include 2,4-dihydroxybenzophenone and 2-hydroxy-4-n-octoxybenzophenone.

The amount of the ultraviolet absorber is 0 to 1.0 part by mass, and preferably 0 to 0.5 parts by mass, per 100 parts by mass of the aromatic polycarbonate resin (A). If the amount of the ultraviolet absorber exceeds 1.0 part by mass, the initial hue of the resulting aromatic polycarbonate resin composition may be deteriorated. Furthermore, if the amount of the ultraviolet absorber is 0.1 parts by mass or more, the effect of further improving the weather resistance of the aromatic polycarbonate resin composition is particularly significant.

Furthermore, the aromatic polycarbonate resin composition according to the embodiment may be appropriately blended with various additives such as heat stabilizers, other antioxidants, release agents (e.g., Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.), softeners, antistatic agents, and impact modifiers, and polymers other than the aromatic polycarbonate resin (A), within the scope that does not impair the effects of the present invention.

The aromatic polycarbonate resin composition of the embodiment of the present invention can be produced by mixing an aromatic polycarbonate resin (A), a colorant (B), and a phosphoric acid ester compound or phosphoric acid (C), and, if necessary, mixing a phosphorus-based antioxidant (D), a dye (E), the various additives, and a polymer other than the aromatic polycarbonate resin (A). As long as the aromatic polycarbonate resin composition of the present invention can be obtained, the production method is not particularly limited, and the type and amount of each component can be appropriately adjusted. The method of mixing the components is also not particularly limited, and examples include a method of mixing in a known mixer such as a tumbler or ribbon blender, and a method of melt kneading in an extruder. Pellets of the aromatic polycarbonate resin composition can be easily obtained by these methods.

There are no particular limitations on the shape and size of the pellets of the aromatic polycarbonate resin composition obtained as described above, and they may be of the same shape and size as general resin pellets. For example, the shape of the pellets may be an elliptical cylinder, a cylindrical shape, etc. The pellet size is preferably about 2 to 8 mm in length, and in the case of an elliptical cylinder, the major axis of the cross-sectional ellipse is preferably about 2 to 8 mm, and the minor axis is preferably about 1 to 4 mm, and in the case of a cylindrical shape, the diameter of the cross-sectional circle is preferably about 1 to 6 mm. Note that each of the obtained pellets may be of this size, or all of the pellets forming the pellet aggregate may be of this size, or the average value of the pellet aggregate may be of this size, and there are no particular limitations.

The thermal stability of the resin composition according to the embodiment of the present invention is preferably such that the Δ after the molded article is left in the mold for 10 minutes is 200 nm or less, more preferably such that the Δ after the molded article is left in the mold for 30 minutes is 200 nm or less, and even more preferably such that the Δ after the molded article is left in the mold for 60 minutes is 200 nm or less. The thermal stability of the resin composition can be measured by the method described in the Examples.

The reliability of the resin composition according to the embodiment of the present invention is preferably such that the molecular weight of the molded product is 16,000 or more after being left to stand for 240 hours under conditions of 85°C and 95% RH, and more preferably such that the molecular weight of the molded product is 16,000 or more after being left to stand for 240 hours under conditions of 120°C. The reliability of the resin composition can be measured by the method described in the examples.

The molded article according to the embodiment of the present invention can be obtained by molding the aromatic polycarbonate resin composition described above, and can be suitably used for sensors, filters, etc.

As long as the molded article of the present invention can be obtained, the method for producing the molded article is not particularly limited. For example, the method may be a method for molding an aromatic polycarbonate resin composition by a known injection molding method, compression molding method, or the like.

The molded article of the present invention is suitable, for example, as a sensor cover for Lidar.

As described above, the embodiments have been described as examples of the present invention. However, the technology of the present invention is not limited to these, and can be applied to embodiments in which modifications, substitutions, additions, omissions, etc. are made as appropriate.

The present invention will be described in detail below with reference to examples and comparative examples. However, these examples are merely one aspect of the present invention, and the present invention is not limited to these examples.

The components used in this example are shown below.
(A) Aromatic polycarbonate resin (a1) Polycarbonate resin synthesized from bisphenol A and carbonyl chloride Viscosity average molecular weight: 18,800, SD Polyca 200-20 (product name) manufactured by Sumika Polycarbonate Co., Ltd., "SD Polyca" is a registered trademark of Sumika Polycarbonate Co., Ltd.

(B) Dye having a maximum absorption wavelength of less than 1200 nm (b1) Anthraquinone dye (Solvent Blue 97)
Macrolex Blue RR (product name) manufactured by Bayer AG, maximum absorption wavelength: 630 nm

(b2) Anthraquinone dye (Solvent Green 28)
Bayer AG Macrolex Green G (trade name), maximum absorption wavelength: 690 nm

(b3) Anthraquinone dyes (SD-3, mixtures)
Manufactured by Kenei Kogyo Co., Ltd., maximum absorption wavelength: 630 nm

(b4) Anthraquinone dye (Solvent Green 3)
Mitsui PS Green B (product name) manufactured by Mitsui Fine Chemicals Co., Ltd. Maximum absorption wavelength: 640 nm

(b5) Methine dye (Disperse Yellow 201)
Bayer AG Macrolex Yellow 6G (product name), maximum absorption wavelength: 440 nm

(b6) Perylene dye (Solvent Red 179)
Bayer AG Macrolex Red E2G (trade name), maximum absorption wavelength: 480 nm

(b7) Phthalocyanine dye (product name: FDN-001)
Manufactured by Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 754 nm
(b8) Phthalocyanine dye (product name: FDN-002)
Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 807 nm
(b9) Phthalocyanine dye (product name: FDN-023)
Manufactured by Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 790 nm

(b10) Phthalocyanine dye (product name: FDN-024)
Manufactured by Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 830 nm

(b11) Anthraquinone dye (product name: SDO-C33)
Arimoto Chemical Industry Co., Ltd., maximum absorption wavelength: 846 nm
(b12) Heterocyclic dye (SDO-C8 product name)
Manufactured by Arimoto Chemical Industry Co., Ltd., maximum absorption wavelength: 785 nm

(b13) Phthalocyanine dye (FDN-004 product name)
Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 880 nm
(b14) Phthalocyanine dye (product name: FDN-006)
Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 927 nm

（ｃ２）リン酸
ナカライテスク社製リン酸（Ｈ_３ＰＯ_４） (C) Phosphoric acid or phosphoric acid ester compound (c1) Phosphoric acid ester compound Mixed stearyl phosphate ester (a mixture of about 50 mol% monostearyl phosphate and about 50 mol% distearyl phosphate; Adeka STAB "AX-71 (product name)" manufactured by ADEKA CORPORATION)

(c2) Phosphoric acid: Phosphoric acid (H ₃ PO ₄ ) manufactured by Nacalai Tesque

(D) Phosphorus-based antioxidant (d1) Phosphorus-based antioxidant HOSTANOX P-EPQ (trade name) manufactured by Clariant Chemicals
[1,1'-biphenyl]-4,4'-diylbis[bis(2,4-di-t-
Butylphenoxy)phosphine
Additives

(E) A dye having a maximum absorption wavelength of 1000 nm or more and 1200 nm or less (e1) A phthalocyanine dye (product name: FDN-010)
Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 1014 nm

(X) Release agent (x1) RIKEMAR S-100A (product name) manufactured by Riken Vitamin Co., Ltd.

These components were mixed in the mass ratios shown in Tables 1 to 3 to produce the polycarbonate compositions of Examples 1 to 18 and Comparative Examples 1 to 4.

Each of the polycarbonate compositions of Examples 1 to 18 and Comparative Examples 1 to 4 was evaluated by the following evaluation methods.
(1) Thermal Stability To evaluate thermal stability, the polycarbonate resin composition was molded using a J100 E2P manufactured by Japan Steel Works, Ltd. at a cylinder temperature of 320°C and a mold temperature of 100°C, and then allowed to remain in the cylinder (320°C) for 10, 30, and 60 minutes to obtain a molded product (1 mm). The optical spectrum of the molded product was evaluated using a UH4150 manufactured by Hitachi High-Tech Science, Ltd., as a transmission spectrum, and the change in optical properties was quantified as follows.

The transmittance was measured every 2 nm from 1200 nm to 500 nm, and the difference between the wavelength where the transmittance started to decrease (hereinafter referred to as the decrease start wavelength) and the wavelength where the transmittance had completely decreased (hereinafter referred to as the decrease completion wavelength) was measured. A product was deemed to be good when the decrease start wavelength - decrease completion wavelength (Δ) was 200 nm or less. A product was deemed to be defective when it was 200 nm or more. Note that for specific wavelength selection filters, it is preferable for the optical spectrum to be steep, and a large difference in wavelengths, i.e., when the above Δ is 200 nm or more (when it is not steep), is not preferred as it may cause problems as a filter.

(2) Reliability Each of the polycarbonate resin compositions of Examples 1 to 18 and Comparative Examples 1 to 4 was evaluated by the following evaluation method.

The polycarbonate resin composition was molded using a J100 E2P manufactured by Japan Steel Works at a cylinder temperature of 320°C and a mold temperature of 100°C, and the molded product was left to stand for 240 hours under conditions of 85°C 95% RH and 120°C for heat aging evaluation, to obtain a sample (for evaluation). The weight average molecular weight of the molded product was measured. A weight average molecular weight of 16,000 or more was considered to be a good product, and a weight average molecular weight of less than 16,000 was considered to be a bad product. The weight average molecular weight was measured using an Alliance HPLC system manufactured by Japan Waters as a GPC device. A PLgel 5μm MiniMIX-C manufactured by Agilent Technologies was used as the GPC column. The sample was dissolved in dichloromethane as a solvent to prepare a solution. The solution was passed through the column at 40°C and a flow rate of 0.3mL/min using THF as an eluent, and the measured value was obtained. A calibration curve for gel permeation chromatography (GPC) was created using a sample with a known weight average molecular weight (monodisperse polystyrene), and the measured values were calibrated to obtain the desired weight average molecular weight.

The polycarbonate resin compositions of Examples 1 to 18 contain an aromatic polycarbonate resin (A), a colorant (B) containing a dye with a maximum absorption wavelength of less than 1200 nm, and a phosphate ester compound or phosphoric acid (C), and contain 0.001 to 2.0 parts by mass of the colorant (B) per 100 parts by mass of the aromatic polycarbonate resin (A), and the phosphoric acid or phosphate ester compound (C) contains 0.005 to 0.3 parts by mass of the phosphate ester compound (C1) or 0.0001 to 0.04 parts by mass of the phosphoric acid (C2).

The polycarbonate resin compositions of Examples 1 to 18 have excellent thermal stability and reliability, and are suitable as wavelength-selectively transparent polycarbonate resin compositions for filters.

The molded products of Comparative Examples 1 and 2 have a large wavelength range from the wavelength at which the transmittance starts to decrease to the wavelength at which the decrease is complete, and therefore cannot adequately transmit the 850-950 nm near-infrared light used in Lidar. This may result in a decrease in the detection ability of Lidar. In contrast, in the case of Examples 1 to 18, which use the phosphate ester compound of the present invention or phosphoric acid, the wavelength at which the transmittance starts to decrease and the wavelength range do not change significantly even after a residence time of 60 minutes, making it possible to adequately transmit near-infrared light of 850 nm to 950 nm, and it is clear that these are excellent wavelength selection filters.

When an excessive amount of phosphate ester or phosphoric acid is blended, as in Comparative Examples 3 and 4, the molecular weight is significantly reduced after reliability testing, and the impact resistance required of polycarbonate resin is impaired. When used as a Lidar cover, there is a risk of problems such as the cover being damaged when it hits pebbles on the road. In contrast, when an appropriate amount of phosphate ester and phosphoric acid is added, no significant molecular weight reduction is observed, and it is clear that the properties of the polycarbonate resin can be maintained.

The polycarbonate resin composition of the embodiment of the present invention can be molded using a conventional device to produce a molded article, and the optical properties do not change substantially during the molding process. Therefore, the polycarbonate resin composition of the embodiment of the present invention can provide a molded article that has appropriate wavelength selectivity and does not substantially change in optical properties. The molded article can be suitably used for Lidar applications.

Claims (23)

The composition comprises an aromatic polycarbonate resin (A), a colorant (B) containing a pigment having a maximum absorption wavelength of less than 1200 nm, and phosphoric acid (C 2 );
The polymer component comprises an aromatic polycarbonate resin (A),
Relative to 100 parts by mass of the aromatic polycarbonate resin (A),
The colorant (B) is contained in an amount of 0.001 to 2.0 parts by mass,
A wavelength selectively transmitting polycarbonate resin composition comprising the phosphoric acid (C2) in an amount of 0.0001 to 0.004 parts by mass. The wavelength-selectively transparent polycarbonate resin composition according to claim 1, wherein the colorant (B) includes a colorant (B1) containing a dye having a maximum absorption wavelength of less than 700 nm, and/or a colorant (B2) containing a dye having a maximum absorption wavelength of 700 nm or more and less than 1000 nm. The wavelength-selectively transparent polycarbonate resin composition according to claim 1 or 2, wherein the colorant (B) contains at least one selected from anthraquinone dyes, perinone dyes, perylene dyes, methine dyes, azo dyes, quinoline dyes, phthalocyanine dyes, and heterocyclic dyes. The wavelength-selectively transparent polycarbonate resin composition according to claim 2, wherein the colorant (B1) containing a dye having a maximum absorption wavelength of less than 700 nm contains at least one selected from anthraquinone dyes, perinone dyes, perylene dyes, and methine dyes. The wavelength-selectively transparent polycarbonate resin composition according to claim 2 or 4, wherein the colorant (B1) containing a dye having a maximum absorption wavelength of less than 700 nm contains an anthraquinone-based dye. The wavelength-selectively transparent polycarbonate resin composition according to claim 5, wherein the anthraquinone dye comprises at least one selected from the group consisting of Solvent Yellow 163, Disperse Violet 28, Solvent Blue 97, Solvent Green 28, Solvent Green 3, and Disperse Blue 60. The wavelength-selectively transparent polycarbonate resin composition according to any one of claims 2 and 4 to 6, wherein the colorant (B2) containing a dye having a maximum absorption wavelength in the range of 700 nm or more and less than 1000 nm contains at least one dye selected from the group consisting of phthalocyanine dyes, anthraquinone dyes, and heterocyclic dyes. The composition comprises an aromatic polycarbonate resin (A), a colorant (B) containing a pigment having a maximum absorption wavelength of less than 1200 nm, and a phosphate ester compound or phosphoric acid (C),
The polymer component comprises an aromatic polycarbonate resin (A),
The colorant (B) contains an anthraquinone colorant,
The phosphate ester compound or phosphoric acid (C) includes at least one selected from the group consisting of phosphate ester compounds or phosphoric acids represented by the following general formula (I):
Formula (I):
O=P(OH) _n (OR) _3-n
[In general formula (I), R is an alkyl group or an aryl group, and n is an integer of 2.]
Relative to 100 parts by mass of the aromatic polycarbonate resin (A),
The colorant (B) is contained in an amount of 0.29 to 2.0 parts by mass,
The wavelength selectively transmitting polycarbonate resin composition contains, with respect to the phosphate ester compound or phosphoric acid (C), 0.005 to 0.3 parts by mass of a phosphate ester compound (C1) or 0.0001 to 0.004 parts by mass of phosphoric acid (C2). 9. The wavelength-selective polycarbonate resin composition according to claim 8, wherein the colorant (B) further comprises a colorant (B1) containing a dye having a maximum absorption wavelength of less than 700 nm, and/or a colorant (B2) containing a dye having a maximum absorption wavelength in the range of 700 nm or more and less than 1000 nm. 10. The wavelength-selective transmitting polycarbonate resin composition according to claim 8 or 9, wherein the colorant (B) further comprises at least one selected from the group consisting of perinone dyes, perylene dyes, methine dyes, azo dyes, quinoline dyes, phthalocyanine dyes, and heterocyclic dyes. 10. The wavelength-selective transmitting polycarbonate resin composition according to claim 9, wherein the colorant (B1) containing a dye having a maximum absorption wavelength of less than 700 nm further contains at least one dye selected from the group consisting of perinone dyes, perylene dyes, and methine dyes. The wavelength-selective transmitting polycarbonate resin composition according to any one of claims 8 to 11, wherein the anthraquinone dye comprises at least one selected from the group consisting of Solvent Yellow 163, Disperse Violet 28, Solvent Blue 97, Solvent Green 28, Solvent Green 3, and Disperse Blue 60. 13. The wavelength-selective polycarbonate resin composition according to claim 9, 11, or 12, wherein the colorant (B2) containing a dye having a maximum absorption wavelength in the range of 700 nm or more and less than 1000 nm further contains at least one dye selected from the group consisting of a phthalocyanine dye and a heterocyclic dye. The wavelength selectively transmitting polycarbonate resin composition according to any one of claims 8 to 13 , wherein the compound represented by the general formula (I) includes monostearyl acid phosphate. The wavelength selective transmitting polycarbonate resin composition according to any one of claims 8 to 14 , wherein the compound represented by the general formula (I) comprises a mixture of monostearyl acid phosphate and distearyl acid phosphate. The wavelength-selective polycarbonate resin composition according to any one of claims 1 to 15 , further comprising a dye (E) containing a phthalocyanine compound having a maximum absorption wavelength in the range of 1000 nm to 1200 nm. The wavelength-selective polycarbonate resin composition according to claim 16 , wherein the dye (E) is represented by the following general formula (II):
Formula (II):

In the formula, R ³¹ may be the same or different and represents a hydrogen atom or an alkyl group which may have a substituent.
R ³² and R ³³ may be the same or different and each represents a halogen atom, an OR ³⁴ group, an SR 35 group, ^{an NR 36 group} or an R ³⁷ group.
^X11 may be the same or different and represents an oxygen atom or a sulfur atom.
R ³⁴ and R ³⁵ groups may be the same or different and represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
R ³⁶ and R ³⁷ groups may be the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
R ³⁶ and R ³⁷ may be bonded together with the nitrogen atom to which they are bonded to form a 5- to 10-membered saturated or unsaturated heterocycle with or without another nitrogen atom, oxygen atom, or sulfur atom. The 5- to 10-membered saturated or unsaturated heterocycle may have one or more substituents.
M represents two monovalent metal atoms, a divalent metal atom, or a trivalent or tetravalent metal compound. The wavelength-selective polycarbonate resin composition according to claim 16 , wherein the dye (E) is represented by the following general formula (III):
Formula (III):

In the formula, R ³¹ may be the same or different and represents a hydrogen atom or an alkyl group which may have a substituent.
X ¹¹ , X ¹² and X ¹³ may be the same or different and each represents an oxygen atom or a sulfur atom.
R ³⁴ and R ³⁵ groups may be the same or different and represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
M represents two monovalent metal atoms, a divalent metal atom, or a trivalent or tetravalent metal compound. The wavelength-selective polycarbonate resin composition according to any one of claims 16 to 18 , wherein the phthalocyanine compound is a phthalocyanine dye having a central metal selected from oxovanadium, copper, aluminum, cobalt, and zinc. The wavelength selective transmitting polycarbonate resin composition according to any one of claims 1 to 19, further comprising at least one selected from the group consisting of a heat stabilizer, an antioxidant, a release agent, an ultraviolet absorber, a colorant, a softener, an antistatic agent, an impact modifier, and a spreading agent. A wavelength-selectively transparent polycarbonate resin molded article comprising the wavelength-selectively transparent polycarbonate resin composition according to any one of claims 1 to 20 . The wavelength-selectively transmissive polycarbonate resin molded article according to claim 21 , which is a Lidar cover. A method for producing a wavelength selectively transmitting polycarbonate resin molded article, comprising molding the resin composition according to any one of claims 1 to 20 .