JP2022087945A - Wavelength selective transmissive polycarbonate resin composition - Google Patents

Abstract

To provide a polycarbonate resin composition having wavelength selective transmissivity without causing a substantial change in optical properties even when molded at high temperature, and a molding thereof.SOLUTION: A wavelength selective transmissive polycarbonate resin composition includes: an aromatic polycarbonate resin (A); a colorant (B) including dye having the maximum absorbance wavelength of less than 1200 nm; and a phosphoric ester based compound or phosphoric acid (C). The colorant (B) of 0.001-2.0 pts.mass and the phosphoric ester based compound (C1) of 0.005-0.3 pts.mass or the phosphoric acid (C2) of 0.0001-0.004 pts.mass in the phosphoric ester based compound or phosphoric acid (C) are included to 100 pts.mass of the aromatic polycarbonate resin (A).SELECTED DRAWING: None

Description

The present invention relates to a wavelength selective transmissive polycarbonate resin composition, and more particularly to a polycarbonate resin composition having wavelength selective transmissivity, which does not transmit visible light but transmits infrared rays.

One of the remote sensing technologies using light is LIDAR (Light Detection and Ranging), which measures scattered light from laser irradiation that emits light in a pulsed manner and analyzes the distance to an object at a long distance and the properties of the object. Laser Imaging Detection and Ranging, also known as "light detection and ranging" or "laser image detection and ranging", "rider"). This technique is similar to radar, replacing radar radio waves with light. The distance to the target is obtained from the time until the reflected light is received after light emission. Riders use electromagnetic waves with wavelengths much shorter than radar, typically ultraviolet, visible, and near-infrared.

In recent years, autonomous driving technology for automobiles has been rapidly developing. In order to support level 3 which is conditional automatic driving and levels 4 to 5 which are not premised on driving by a driver, a function for safely autonomous driving on expressways and general roads is required. Therefore, in addition to cameras and millimeter-wave radars, riders are attracting attention in order to ensure sensing redundancy. In order to support autonomous driving, it is necessary to improve the accuracy of Lidar, and it is required to develop a wavelength selection filter having better performance.

Patent Document 1 is used in Lidar because an epoxy resin cured product containing an azoanthraquinone-based mixture or the like has an average transmittance of 0% in the wavelength range of 380 nm and a light transmittance of 80% or more at a wavelength of 900 nm. It is disclosed that it can be preferably used when the wavelength of the laser light to be used is in the range of 850 to 950 nm (see Patent Document 1, Examples 1 to 2, [0050], and [FIG. 1]). Further, in Patent Document 1, the cured epoxy resin containing an azoanthraquinone-based mixture or the like has an average transmittance of 0% in the wavelength range of 380 nm and a light transmittance of 80% or more at a wavelength of 1550 nm. Therefore, Lidar Discloses that it can be preferably used when the laser light wavelength used in the above is in the range of 1500 to 1600 nm (see Patent Document 1, Examples 1 to 3, [0050], and [FIG. 1]).

Japanese Unexamined Patent Publication No. 2017-167484

Patent Document 1 discloses a cured product of an epoxy resin, but the cured product of an epoxy resin is not always suitable for being provided in large quantities at low cost. Considering the future development of Lidar, it is necessary to provide a composition and a molded product thereof that can be manufactured in large quantities at a lower cost.

The present inventors have focused on a polycarbonate molded product having excellent transparency and mechanical strength, but since polycarbonate has a high molding temperature, the transmittance decreases during molding of the polycarbonate resin composition at a high temperature. / Or noticed that it could be increased, i.e., the transmittance (optical properties) could change. Changes in optical characteristics may cause malfunction. Therefore, an object of the present invention is to provide a polycarbonate resin composition and a molded product thereof, which have wavelength selective transparency and do not substantially change the optical properties even when molded at a high temperature.

As a result of diligent studies, the present inventors have found that a polycarbonate resin composition containing a colorant (for example, anthraquinone-based dye) containing a dye having a maximum absorption wavelength of less than 1200 nm and a phosphoric acid or a phosphoric acid ester-based compound has been obtained. It has been found that a polycarbonate resin composition and a molded product thereof, which do not substantially change the optical properties even when molded at a high temperature and have wavelength selective transparency, are provided. Furthermore, they have found that such resin compositions and molded products can be suitably used for Lidar applications, and have completed the present invention.

The wavelength selective permeable polycarbonate resin molded product according to 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 phosphoric acid ester compound or phosphoric acid (C). The colorant (B) is contained in an amount of 0.001 to 2.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A), and the phosphoric acid or the phosphoric acid ester compound (C) contains a phosphoric acid. The ester compound (C1) is contained in an amount of 0.005 to 0.3 parts by mass, or the phosphoric acid (C2) is contained in an amount of 0.0001 to 0.004 parts by mass.

The wavelength-selective transmissive polycarbonate resin molded product according to the present invention contains the above-mentioned wavelength-selective transmissive aromatic polycarbonate resin composition.

The method for producing a wavelength selective transmissive polycarbonate resin molded product according to the present invention includes molding the above resin composition.

The polycarbonate resin composition of the embodiment of the present invention can be molded by using an ordinary apparatus to produce a molded product, and the optical properties are not substantially changed during the molding. Therefore, the polycarbonate resin composition of the embodiment of the present invention can provide a molded product having appropriate wavelength selectivity and substantially no change in optical characteristics. The molded product can be suitably used for Lidar applications.

The wavelength selective permeable polycarbonate resin composition of the embodiment of 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 a phosphate ester compound or phosphoric acid ( C) is contained, and the colorant (B) is contained in an amount of 0.001 to 2.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). The phosphate ester compound (C1) is contained in an amount of 0.005 to 0.3 parts by mass, or the phosphoric acid (C2) is contained in an amount of 0.0001 to 0.004 parts by mass.

In the embodiment of the present invention, the "aromatic polycarbonate resin (A)" is a polycarbonate resin based on an aromatic compound, and is particularly limited as long as the aromatic polycarbonate resin composition of the present invention can be obtained. There is no such thing. Examples of such aromatic polycarbonate resins include polymers obtained by a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or an ester exchange method in which a dihydroxydiaryl compound is reacted with a carbonic acid ester such as diphenyl carbonate. can. Representative examples include polycarbonate resins made from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

As the dihydroxydiaryl compound, in addition to bisphenol A, for example, 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-Third Butylphenyl) Propane, 2,2-Bis (4-hydroxy-3-bromophenyl) Propane, 2,2-Bis (4-Hydroxy-3,5-Dibromophenyl) Propane, 2,2-Bis Bis (hydroxyaryl) alkanes such as (4-hydroxy-3,5-dichlorophenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane and the like. Bis (hydroxyaryl) cycloalkhans; dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; dihydroxydiaryl such as 4,4'-dihydroxydiphenylsulfide Fraxides; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide; 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy- Examples of dihydroxydiarylsulfones such as 3,3'-dimethyldiphenylsulfone can be exemplified. These can be used alone or in combination. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like can be used in combination.

Further, the dihydroxydiaryl compound may be used in combination with, for example, a trivalent or higher valent aromatic compound shown below.

Examples of the trivalent or higher valent phenol compound include fluoroglucin, 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) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis -[4,4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like can be exemplified.

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

In the embodiment of the present invention, the colorant (B) containing a dye having a maximum absorption wavelength of less than 1200 nm includes a dye having a maximum absorption wavelength of less than 1200 nm, and the dye is, for example, a dye (organic, inorganic) or a pigment. It can be selected from (organic, inorganic) and the like, and is not particularly limited as long as the aromatic polycarbonate resin composition of the present invention can be obtained. As such a dye, either a dye or a pigment can be used, but it is more preferable to use a dye because it is difficult for the dye to diffusely reflect light on the surface of the particles. The colorant (B) containing these dyes 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. Since the dye is made of particles smaller than the pigment, the dye can be uniformly mixed with the resin composition, and the haze value of the molded product can be made smaller, which is preferable. Dyes are more preferred for Lidar.

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

The colorant (B) preferably contains 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 the embodiment of the present invention, the colorant (B1) containing a dye having a maximum absorption wavelength of less than 700 nm may contain at least one selected from anthraquinone-based dyes, perylene-based dyes, perylene-based dyes, and methine-based dyes. preferable. The colorant (B1) preferably contains an anthraquinone-based dye.

The colorant (B1) can further contain at least one selected from phthalocyanine dyes and heterocyclic dyes.

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

As long as the composition of the embodiment of the present invention can be obtained, the above-mentioned dye is not particularly limited, but specifically, the following can be used.

The anthraquinone dye preferably contains 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 the perinone-based dye include dyes commercially available in 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 the perylene dye include 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, Solvent Red 17 and the like. Examples include dyes that have been used.

Examples of the methine-based dye include dyes commercially available with a color index such as Solvent Orange 80, Solvent Yellow 93, and Disperse Yellow 201.
Examples of the quinoline dye include dyes commercially available with color indexes such as Solvent Yellow 33, Solvent Yellow 98, Solvent Yellow 157, Disperse Yellow 54, and Disperse Yellow 201.

In the embodiment of the present invention, the colorant (B2) containing a dye having a maximum absorption wavelength of 700 nm or more and less than 1000 nm may contain at least one selected from phthalocyanine dyes, anthraquinone dyes and heterocyclic dyes. preferable.

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

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

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

The resin composition of the embodiment of the present invention contains 0.001 to 2.0 parts by mass of a colorant (B) containing a dye having a maximum absorption wavelength of less than 1200 nm with respect to 100 parts by mass of the aromatic polycarbonate resin (A). It is preferably contained, more preferably 0.005 to 1.5 parts by mass, still more preferably 0.006 to 1.0 parts by mass. The lower limit of the content of the colorant (B) may be 0.02 parts by mass or 0.025 parts by mass.

In the embodiment of the present invention, the phosphoric acid ester compound or the phosphoric acid (C) is not particularly limited as long as the resin composition of the embodiment of the present invention can be obtained, but the following general formula (I) can be used. It is preferable to contain at least one selected from the group consisting of the represented phosphoric acid ester-based compound and phosphoric acid.

Equation (I): O = P (OH) _n (OR) _3-n
[In the formula (I), R is an alkyl group or an aryl group, each of which may be the same or different, and n represents 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. be. Further, n is preferably 1 or 2.

Examples of the phosphoric acid ester-based compound of the formula (I) include mono or di-stearyl acid phosphate, which is a mixture of a stearyl phosphate mixed ester (about 50 mol% monostearyl phosphate and about 50 mol% distearyl phosphate). (Product name "AX-71" manufactured by Asahi Denka Co., Ltd.) is known.

Phosphoric acid is a non-volatile weak acid, and commercially available products can be used, and examples thereof include phosphoric acid manufactured by Nakaraitesk Co., Ltd. and phosphoric acid manufactured by Wako Pure Chemical Industries, Ltd.

The resin composition of the embodiment of the present invention contains 0.005 of the phosphoric acid ester-based compound (C1) with respect to the phosphoric acid ester-based compound or the phosphoric acid (C) with respect to 100 parts by mass of the aromatic polycarbonate resin (A). It is preferably contained in an amount of about 0.3 parts by mass, more preferably 0.007 to 0.1 parts by mass, and even more preferably 0.009 to 0.08 parts by mass. Alternatively, phosphoric acid (C2) is preferably contained in an amount of 0.0001 to 0.004 parts by mass, preferably by 0.0001 to 0.001 parts by mass, and preferably by 0.0003 to 0.0008 parts by mass. More preferably, it is contained in an amount of 0.0004 to 0.0006 parts by mass.

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

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

In the wavelength selective permeable polycarbonate resin composition of the embodiment of the present invention, the phosphorus-based antioxidant (D) is represented by a subphosphate ester compound represented by the following formula (1) and the following formula (2). It may contain at least one compound selected from a subphosphate ester compound represented by the following formula (3), a subphosphate ester compound represented by the following formula (4), and a subphosphate ester compound represented by the following formula (4). preferable.

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。） Equation (1):

(In the formula, R ¹ 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 the formula (1) include triphenylphosphine, tricresylphosphine, tris (2,4-di-t-butylphenyl) phosphite, trisnonylphenylphosphite and the like. .. Among these, Tris (2,4-di-t-butylphenyl) phosphite is particularly suitable, and for example, it is commercially available as Irgafos 168 manufactured by BASF (“Irgafos” is a registered trademark of BASF Societyus Europe). It is available at.

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。） Equation (2):

(In the formula, R ² , R ³ , R ⁵ and R ⁶ each have a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and 6 to 12 carbon atoms, respectively. Alkylcycloalkyl group, aralkyl group or phenyl group having 7 to 12 carbon atoms. R ⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. X is a single bond, a sulfur atom or a formula: -CHR. ^7- (Here, R ⁷ indicates a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms). A indicates a group having 1 to 8 carbon atoms. Alkylene group or formula: * -COR ^8- (where R ⁸ indicates a single bond or an alkylene group having 1 to 8 carbon atoms, and * indicates a bond on the oxygen side). Y and Z indicate 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 has a hydrogen atom or 1 to 8 carbon atoms. Indicates an alkyl group.)

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

Here, examples of the alkyl group having 1 to 8 carbon atoms include 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 and a t-butyl group. Examples thereof include a group, a t-pentyl group, an i-octyl group, a t-octyl group, a 2-ethylhexyl group and the like. Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include a 1-methylcyclopentyl group, a 1-methylcyclohexyl group, a 1-methyl-4-i-propylcyclohexyl group and the like. Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, an α-methylbenzyl group, an α, α-dimethylbenzyl group and the like.

It is preferable that R ² , R ³ and R ⁵ are independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms or an alkyl cycloalkyl group having 6 to 12 carbon atoms. .. In particular, it is preferable that R ² and R ⁵ are independently t-alkyl groups such as t-butyl group, t-pentyl group and t-octyl group, cyclohexyl group or 1-methylcyclohexyl group, respectively. In particular, R ³ has the number of carbon atoms of 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, a t-pentyl group and the like. It is preferably an alkyl group of 1 to 5, more preferably 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 is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an i-propyl group. , N-Butyl group, i-butyl group, sec-butyl group, t-butyl group, t-pentyl group and the like, more preferably an alkyl group having 1 to 5 carbon atoms.

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 above-mentioned explanations of R ² , R ³ , R ⁵ and R ⁶ . In particular, ^R4 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 group and the cycloalkyl group exemplified in the description of R ² , R ³ , R ⁵ and R ⁶ , respectively. Be done. In particular, X is 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. It is preferably present, and more preferably a single bond.

In the 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, a 2,2-dimethyl-1,3-propylene group and the like. , Which is preferably a propylene group. Further, R ⁸ in the formula: * -COR ^8- indicates a single bond or an alkylene group having 1 to 8 carbon atoms. Examples of the alkylene group having 1 to 8 carbon atoms showing R ⁸ include the alkylene group exemplified in the above description of A. ^R8 is preferably a single bond or an ethylene group. Further, * in the formula: * -COR ^8- indicates that the bond is on the oxygen side and the carbonyl group is bonded to the oxygen atom of the phosphite group.

In the 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 is a hydrogen atom or 1 to 8 carbon atoms. The alkyl group of is shown. 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, a pentyloxy group and the like. Examples of the aralkyloxy group having 7 to 12 carbon atoms include a benzyloxy group, an α-methylbenzyloxy group, an α, α-dimethylbenzyloxy group and the like. Examples of the alkyl group having 1 to 8 carbon atoms include the alkyl groups exemplified in the above-mentioned explanations of R ² , R ³ , R ⁵ and R ⁶ .

Examples of the compound represented by the 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, 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 and the like can be mentioned. .. Among these, when the obtained aromatic polycarbonate resin composition is used in a field 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 for example, Sumitomo Chemical Co., Ltd.'s Sumilyzer GP ("" "Sumilyzer" is commercially available as a registered trademark).

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。） Equation (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 are independently 0. Indicates an integer of ~ 3.)

Examples of the compound represented by the formula (3) include bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite and the like. 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).

Equation (4):

(In the formula, R ¹¹ to R ¹⁸ each independently represent an alkyl group or an 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 respectively. R ¹⁸ may be bonded to each other to form a ring. R ¹⁹ to R ²² independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. D to g are independent of each other. Then, it is an integer of 0 to 5. X ¹ to X ⁴ independently indicate 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 the formula (4).)

Specific examples of the compound represented by the formula (4) include bis (2,4-dicumylphenyl) pentaerythritol diphosphite. This is manufactured by Dover Chemical, trade name "Doverphos (registered trademark) S-9228", manufactured by ADEKA Corporation, trade name "ADEKA STAB PEP-45" (bis (2,4-dikumilphenyl) pentaerythritol diphos). It is commercially available as Fight).

Further, as the phosphorus-based antioxidant (D), for example, [1,1'-biphenyl] -4,4'-diylbis [bis (2,4-di-t-butylphenoxy) phosphine] and the like can be mentioned. For example, Irgafos P-EPQ (trade name) manufactured by BASF and HOSTANOX P-EPQ (trade name) manufactured by Clariant Chemicals are commercially available.

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

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

The wavelength selective transmissive polycarbonate resin composition of the embodiment of the present invention may further contain a dye (E) containing a phthalocyanine compound having a maximum absorption wavelength of 1000 nm or more and 1200 nm or less. When the wavelength selective transmissive polycarbonate resin composition contains the dye (E), it absorbs light having a wavelength of 1000 to 1200 nm, so that the transmitted wavelength range can be shifted to the long 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).
Equation (II):

[In the formula, R ³¹ represents an alkyl group which may be the same or different and may have a hydrogen atom or a substituent.
R ³² and R ³³ may be the same or different and represent halogen atoms, OR ³⁴ , SR ³⁵ or NR ³⁶ or R ³⁷ .
X ¹¹ may be the same or different and represents an oxygen atom or a sulfur atom.
The R ³⁴ and R ³⁵ groups may be the same or different, and may have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Shows a heteroaryl group.
The R ³⁶ and R ³⁷ groups represent hydrogen atoms, alkyl groups which may have substituents, or aryl groups which may have substituents, which may be the same or different.
R ³⁶ and R ³⁷ , together with the nitrogen atom to which they are bonded, bond with each other with or without other nitrogen atoms, oxygen atoms or sulfur atoms to form a 5- to 10-membered saturated or unsaturated heterocycle. You may be doing it. The 5- to 10-membered saturated or unsaturated heterocycle may have one or more substituents.
M represents two monovalent metal atoms, divalent metal atoms, trivalent or tetravalent metal compounds. ]

［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 general formula (II) is preferably a compound represented by the following general formula (III).
Equation (III):

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

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

As the "alkyl group", for example, a linear alkyl group having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms can be exemplified. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group (hereinafter, also referred to as t-Bu), n- Pentyl group, 2-methylbutyl 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, To 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- Butyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethyl Hexyl group, 2,4,4-trimethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, t-octyl group, n-nonyl group, 3,5,5-trimethylhexyl group , N-decyl group, 4-ethyloctyl group, 4-ethyl-4,5-dimethylhexyl group, n-undecyl group, n-dodecyl group, 1,3,5,7-tetramethyloctyl group, 4-butyl The octyl group and the like can be mentioned. It is preferably a linear alkyl group having 1 to 8 carbon atoms, a branched chain having 3 to 8 carbon atoms, or a cyclic alkyl group having 3 to 8 carbon atoms, and particularly preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. Group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, t-octyl group.

As the "aryl group", for example, a monocyclic or polycyclic (for example, 2 or 3 ring) aryl group can be exemplified. Specifically, a phenyl group, a naphthyl group, an anthryl group and the like can be exemplified. A monocyclic or bicyclic aryl group is preferable, and a phenyl group and a naphthyl group are particularly preferable.

As the "heteroaryl group", for example, a monocyclic or polycyclic (for example, bicyclic or tricyclic) heteroaryl group can be exemplified. Specific examples thereof include a pyridyl group, a pyrimidine group, an indolyl group, a quinoline group, a benzimidazole group, a furanyl group, a thienyl group, a benzofuran group, a 1,3,4-thiadiazole group and the like. In particular, monocyclic or bicyclic heteroaryl groups are preferred.

On an alkyl chain, an aryl ring or a heteroaryl ring of an alkyl group which may have a substituent, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent. Substituents (groups that can be substituted on an alkyl chain, aryl ring or heteroaryl ring) include, for example, an alkyl group, a haloalkyl group, a hydroxyalkyl group, an alkoxy group, an alkylthio group, an alkylamino group, a dialkylamino group, a cyclic amino group. , Halogen atom, acyl group, alkoxycarbonyl group, ureido group, sulfamoyl group, carbamoyl group, alkylcarbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkoxysulfonyl group, aryloxysulfonyl group, cyano group, nitro group and the like. .. Even if the substituent (a group capable of substituting on an alkyl chain, an aryl ring or a heteroaryl ring, hereinafter referred to as a substituent) has 1 to 5 on the alkyl chain, the aryl ring or the heteroaryl ring. good.

For example, when the alkyl group which may have the above-mentioned substituent is an "alkyl group having a substituent", the alkyl group having a substituent is, for example, specifically, 2-chloroethyl group, 2, 2,2-Trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, benzyl group, phenethyl group, 2-phenylethyl group, 3-phenylethyl group, 4-hydroxybutyl group, 2- Examples thereof include a methoxyethyl group, a 3-methoxypropyl group, a 2-isopropoxyethyl group, an ethyl butanoate group and the like.

When the aryl group which may have the above substituent is an "aryl group having a substituent", the aryl group having a substituent is, for example, specifically, 2-chlorophenyl group or 3-chlorophenyl. Group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 2,4,6-trichlorophenyl group, 2-fluorophenyl group , 3-Fluorophenyl group, 4-Fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 2,4,6 -Trifluorophenyl 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) Examples thereof include a phenyl group, a 4-phenoxyphenyl group, a 4-acetylphenyl group, a 4-methoxycarbonylphenyl group and the like.

When the heteroaryl group which may have the above-mentioned substituent is a "heteroaryl group having a substituent", the heteroaryl group having a substituent is, for example, specifically, a 2-methylpyridyl group. 2-Chloropyridyl group, 6-fluorobenzothiazole group, 6-chlorobenzothiazole group, 6-methylbenzothiazole group, 6-methoxybenzothiazole group, 5-methyl-1,3,4-thiadiazol group, 5-methylthio Examples thereof include a -1,3,4-thiadiazol group, a 5-trifluoromethyl-1,3,4-thiadiazol group and the like.

As the divalent metal represented by M, for example, a metal element belonging to the 3rd to 15th groups of the periodic table can be exemplified. For example, specifically, Cu, Zn, Fe, Co, Ni, Ru, Pb, Rh, Pd, Pt, Mn, Sn, Pb and the like can be exemplified.

Examples of the trivalent or tetravalent metal compound represented by M include halides, hydroxides and oxides of metals belonging to Groups 3 to 15 of the Periodic Table. Specifically, 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, TiO and the like can be mentioned. The 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 formula.

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 with respect to 100 parts by mass of the aromatic polycarbonate resin (A). It is more preferably contained in an amount of 0.002 to 0.18 parts by mass, further preferably contained in an amount of 0.004 to 0.16 parts by mass, particularly preferably contained in an amount of 0.005 to 0.15 parts by mass, and 0. It is even more preferably contained in an amount of 0.01 to 0.1 parts by mass.

When the dye (E) containing a phthalocyanine compound having 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 with respect to 100 parts by mass of the aromatic polycarbonate resin (A), the wavelength is selected. The transmissive polycarbonate resin composition and its molded product are more excellent because they can block light having a longer wavelength.

As the dye (E) containing a phthalocyanine compound having a maximum absorption wavelength of 1000 nm or more and 1200 nm or less, a commercially available product can be used. For example, FDN-010 (trade name) manufactured by Yamada Chemical Co., Ltd. can be exemplified, and it can be used.

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

As the ultraviolet absorber, for example, an ultraviolet absorber usually blended in a polycarbonate resin such as a benzotriazole-based compound, a triazine-based compound, a benzophenone-based compound, and a oxalic acid anilides-based compound may be used alone or in combination of two or more. Can be used.

Examples of the benzotriazole-based compound include 2- (2-hydroxy-5-t-octylphenyl) benzotriazole and 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-. Benzotriazole, 2- (3,5-di-tert-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2H-benzotriazole-2-yl) -4-methyl-6- (3,4,5,6) -Tetrazydrophydlymylmethyl) phenol, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole -Di (1,1-dimethylbenzyl) phenol] -2H-benzotriazole, 2,2'-Methylenbis [6- (2H-benzotriazole-2-yl) 4- (1,1,3,3-tetramethylbutyl) phenol], etc. Can be mentioned. Of these, 2- (2-hydroxy-5-t-octylphenyl) benzotriazole and the like are particularly suitable. For example, TINUVIN 329 manufactured by BASF (TINUVIN is a registered trademark) and Seasorb manufactured by Cipro Chemical Co., Ltd. 709, Chemisorb 79 manufactured by Chemipro Kasei Co., Ltd., etc. are commercially available.

Examples of the triazine-based compound include 2,4-diphenyl-6- (2-hydroxyphenyl-4-hexyloxyphenyl) 1,3,5-triazine and 2- [4,6-bis (2,4-dimethyl). Phenyl) -1,3,5-triazine-2-yl] -5- (octyloxy) phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[((4,6-diphenyl-1,3,5-triazine-2-yl) -5-[( Hexyl) oxy] phenol and the like, for example, TINUVIN 1577 manufactured by BASF and the like are commercially available.

As the oxalic acid anilide compound, for example, Sanduvor VSU manufactured by Clariant Japan Co., Ltd. is commercially available.

Examples of the benzophenone compound 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 part by mass with respect to 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 obtained aromatic polycarbonate resin composition may be deteriorated. Further, when the amount of the ultraviolet absorber is 0.1 part by mass or more, the effect of further improving the weather resistance of the aromatic polycarbonate resin composition is particularly exhibited.

Further, the aromatic polycarbonate resin composition according to the embodiment may contain, for example, a heat stabilizer, another antioxidant, or a mold release agent (for example, manufactured by Riken Vitamin Co., Ltd.) as long as the effect in the present invention is not impaired. Riquemar S-100A and the like), various additives such as softeners, antistatic agents and impact improving agents, polymers other than the aromatic polycarbonate resin (A) and the like may be appropriately blended.

The aromatic polycarbonate resin composition of the embodiment of the present invention is a mixture of an aromatic polycarbonate resin (A), a colorant (B), and a phosphoric acid ester compound or phosphoric acid (C), and if necessary, phosphorus. Examples of a production method in which a polymer other than the antioxidant (D), the dye (E), the various additives, and the aromatic polycarbonate resin (A) are mixed can be exemplified. As long as the aromatic polycarbonate resin composition of the present invention can be obtained, the production method thereof 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 thereof include a method of mixing with a known mixer such as a tumbler and a ribbon blender, and a method of melt-kneading with an extruder. By these methods, pellets of the aromatic polycarbonate resin composition can be easily obtained.

The shape and size of the pellets of the aromatic polycarbonate resin composition obtained as described above are not particularly limited, and may be any shape and size of general resin pellets. For example, examples of the shape of the pellet include an elliptical columnar shape and a columnar shape. The size of the pellet is preferably about 2 to 8 mm in length, and in the case of an elliptical columnar shape, it is preferable that the major axis of the cross-sectional ellipse is about 2 to 8 mm and the minor axis is about 1 to 4 mm. In the case of a columnar shape, it is preferable that the diameter of the cross-sectional circle is about 1 to 6 mm. It should be noted that each of the obtained pellets may have such a size, and all the pellets forming the pellet aggregate may have such a size, and the average value of the pellet aggregate is this. The size may be such that there is no particular limitation.

Regarding the thermal stability of the resin composition of the embodiment of the present invention, it is preferable that the Δ after 10 minutes residence of the molded product is 200 nm or less, and the Δ after 30 minutes residence of the molded product is 200 nm or less. It is more preferable that Δ after staying in the molded product for 60 minutes is 200 nm or less. The thermal stability of the resin composition can be measured by the method described in Examples.

Regarding the reliability of the resin composition of the embodiment of the present invention, it is preferable that the molded product has a molecular weight of 16000 or more after being allowed to stand at 85 ° C. and 95% RH for 240 hours, and the molded product is stored under the condition of 120 ° C. It is more preferable that the molecular weight after standing for 240 hours is 16000 or more. The reliability of the resin composition can be measured by the method described in Examples.

The molded product of the embodiment of the present invention can be obtained by molding the above-mentioned aromatic polycarbonate resin composition, and can be suitably used for sensors, filters, and the like.

As long as the molded product intended by the present invention can be obtained, the method for producing the molded product is not particularly limited, and for example, an aromatic polycarbonate resin composition is molded by a known injection molding method, compression molding method, or the like. There is a way to do it.

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

As described above, an embodiment has been described as an example of the present invention. However, the technique of the present invention is not limited to this, and can be applied to embodiments in which changes, replacements, additions, omissions, etc. are made as appropriate.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but 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 Viscous average molecular weight: 18800, SD Polycarbonate 200-20 (trade name) manufactured by Sumika Polycarbonate Co., Ltd., "SD Polycarbonate" Is a registered trademark of Sumika Polycarbonate Co., Ltd.

(B) Dye with maximum absorption wavelength less than 1200 nm (b1) Anthraquinone dye (Solvent Blue 97)
Bayer AG Macrolex Blue RR (trade name), 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 dye (SD-3, mixture)
Manufactured by Kenei Kogyo Co., Ltd., maximum absorption wavelength: 630 nm

(B4) Anthraquinone dye (Solvent Green 3)
Mitsui PS Green B (trade name) manufactured by Mitsui Chemical Fine Co., Ltd., maximum absorption wavelength: 640 nm

(B5) Methine dye (Disperse Yellow 201)
Bayer AG Macrolex Yellow 6G (trade 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 (FDN-001 product name)
Made by Yamada Chemical Co., Ltd., Maximum absorption wavelength: 754 nm
(B8) Phthalocyanine dye (FDN-002 product name)
Made by Yamada Chemical Co., Ltd., Maximum absorption wavelength: 807 nm
(B9) Phthalocyanine dye (FDN-023 product name)
Made by Yamada Chemical Co., Ltd., Maximum absorption wavelength: 790 nm

(B10) Phthalocyanine dye (FDN-024 trade name)
Made by Yamada Chemical Co., Ltd., Maximum absorption wavelength: 830 nm

(B11) Anthraquinone dye (SDO-C33 product name)
Arimoto Chemical Industry Co., Ltd., Maximum absorption wavelength: 846 nm
(B12) Heterocyclic dye (SDO-C8 trade name)
Made by Arimoto Chemical Industry Co., Ltd., Maximum absorption wavelength: 785 nm

(B13) Phthalocyanine dye (FDN-004 trade name)
Made by Yamada Chemical Co., Ltd., Maximum absorption wavelength: 880 nm
(B14) Phthalocyanine dye (FDN-006 product name)
Made by Yamada Chemical 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-based compound (c1) Phosphoric acid ester-based compound Phosphoric acid stearyl mixed ester (mixture of about 50 mol% monostearyl phosphate and about 50 mol% distearyl phosphate; manufactured by ADEKA Co., Ltd. Adekastab "AX-71 (trade name)"

(C2) Phosphoric acid Phosphoric acid manufactured by Nacalai Tesque (H ₃ PO ₄ )

(D) Phosphorus-based Antioxidant (d1) Phosphorus-based Antioxidant HOSTANOX P-EPQ (trade name) manufactured by Clariant Chemicals, Inc.
[1,1'-biphenyl] -4,4'-diylbis [bis (2,4-di-t-)
Butylphenoxy) Phosphin]
Additive

(E) Dye with maximum absorption wavelength of 1000 nm or more and 1200 nm or less (e1) Phthalocyanine dye (FDN-010 trade name)
Made by Yamada Chemical Co., Ltd., Maximum absorption wavelength: 1014 nm

(X) Release agent (x1) Riken Vitamin Co., Ltd. Rikemar S-100A (trade name)

These components were blended 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 In order to evaluate thermal stability, a polycarbonate resin composition is molded using J100 E2P manufactured by Japan Steel Works at a cylinder temperature of 320 ° C and a mold temperature of 100 ° C, and then molded in the cylinder (320). The mixture was allowed to stay at (° C.) for 10, 30 and 60 minutes to obtain a molded product (1 mm). The optical spectrum of the molded product was evaluated by using UH4150 manufactured by Hitachi High-Tech Science, and the change in optical characteristics was quantified as follows.

The transmittance was measured every 2 nm from 1200 nm to 500 nm, and the difference between the wavelength at which the transmittance began to decrease (hereinafter referred to as the decrease start wavelength) and the wavelength at which the transmittance had completely decreased (hereinafter referred to as the decrease completion wavelength) was measured. .. The case where the reduction start wavelength-decrease completion wavelength (Δ) is 200 nm or less is regarded as a non-defective product. If it is 200 nm or more, it is regarded as defective. In the specific wavelength selection filter, it is preferable that the optical spectrum is steep, and when the difference in wavelength is large, that is, when the above Δ is 200 nm or more (when it is not steep), a problem may occur as a filter. Therefore, it is not preferable.

(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 methods.

The polycarbonate resin composition was molded using 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 molded under the conditions of 85 ° C. 95% RH and heat aging resistance evaluation 120 ° C. Each was allowed to stand for 240 hours to obtain a sample (for evaluation). The weight average molecular weight of it was measured. When the weight average molecular weight was 16000 or more, it was regarded as a good product, and when it was less than 16000, it was regarded as a defective product. The weight average molecular weight was measured using an Alliance HPLC system manufactured by Japan Waters Corp. as a GPC apparatus. As the column for GPC, PLgel 5 μm MiniMIX-C manufactured by Agilent Technologies was used. A solution was prepared by dissolving the sample using dichloromethane as a solvent. The solution was passed through a column at 40 ° C. and a flow rate of 0.3 mL / min using THF as an eluent to obtain measurements. Using a sample having a known weight average molecular weight (monodisperse polystyrene), a calibration curve for gel permeation chromatography (GPC) was prepared and the measured values were calibrated to obtain the desired weight average molecular weight.

The polycarbonate resin compositions of Examples 1 to 18 include an aromatic polycarbonate resin (A), a 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 colorant (B) is contained in an amount of 0.001 to 2.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A), and the phosphoric acid or the phosphoric acid ester-based compound (C) is a phosphoric acid ester-based compound. The compound (C1) is contained in an amount of 0.005 to 0.3 parts by mass, or the phosphoric acid (C2) is contained in an amount of 0.0001 to 0.04 parts by mass.

The polycarbonate resin compositions of Examples 1 to 18 are excellent in thermal stability and reliability, and are suitable as wavelength selective transmissive polycarbonate resin compositions for fitters.

Since the molded products of Comparative Examples 1 and 2 have a large wavelength width from the wavelength at which the transmittance decreases to the wavelength at which the decrease is completed, the near infrared rays of 850 to 950 nm used in Lidar cannot be appropriately transmitted. Therefore, the detection ability of Lidar may decrease. On the other hand, in the case of Examples 1 to 18 using the phosphoric acid ester compound of the present invention or phosphoric acid, no significant change was observed in the transmittance reduction start wavelength and the wavelength width even when the residence time was 60 minutes. , 850 nm-950 nm near infrared rays can be appropriately transmitted, and it is clear that it is excellent as a wavelength selection filter.

When an excess amount of phosphoric acid ester or phosphoric acid is blended as in Comparative Examples 3 and 4, the molecular weight decreases significantly after the reliability test, and the impact resistance required for the polycarbonate resin is impaired. When used as a lidar cover, it may collide with pebbles on the road surface and cause problems such as damage to the cover. On the other hand, when an appropriate amount of phosphoric acid ester and phosphoric acid was added, no significant decrease in molecular weight was observed, and it can be seen that the characteristics of the polycarbonate resin can be maintained.

The polycarbonate resin composition of the embodiment of the present invention can be molded by using an ordinary apparatus to produce a molded product, and the optical properties do not substantially change during the molding. Therefore, the polycarbonate resin composition of the embodiment of the present invention can provide a molded product having appropriate wavelength selectivity and substantially no change in optical characteristics. The molded product can be suitably used for Lidar applications.

Claims (17)

It contains an aromatic polycarbonate resin (A), a 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).
With respect 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, and the colorant (B) is contained in an amount of 0.001 to 2.0 parts by mass.
Regarding the phosphoric acid ester compound or phosphoric acid (C), the phosphoric acid ester compound (C1) is contained in an amount of 0.005 to 0.3 parts by mass, or the phosphoric acid (C2) is contained in an amount of 0.0001 to 0.004 parts by mass. A wavelength selective permeable polycarbonate resin composition comprising. The colorant (B) 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 of 700 nm or more and less than 1000 nm. 1 The wavelength selective permeable polycarbonate resin composition according to 1. The colorant (B) contains at least one selected from anthraquinone-based dyes, perinone-based dyes, perylene-based dyes, methine-based dyes, azo-based dyes, quinoline-based dyes, phthalocyanine-based dyes, and heterocyclic dyes. , The wavelength selective permeable polycarbonate resin composition according to claim 1 or 2. The wavelength according to claim 2, wherein the colorant (B1) containing a dye having a maximum absorption wavelength of less than 700 nm includes at least one selected from anthraquinone-based dye, perylene-based dye, perylene-based dye, and methine-based dye. Selective permeable polycarbonate resin composition. The wavelength selective transmissive 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 selection 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. Permeable polycarbonate resin composition. Claims 2 and 4 to 6 include the colorant (B2) containing a dye having a maximum absorption wavelength of 700 nm or more and less than 1000 nm, which comprises at least one selected from a phthalocyanine dye, an anthraquinone dye and a heterocyclic dye. The wavelength selective permeable polycarbonate resin composition according to any one of the above items. Any of claims 1 to 7, wherein the phosphoric acid ester compound or phosphoric acid (C) contains at least one selected from the group consisting of the phosphoric acid ester compound or phosphoric acid represented by the following general formula (I). The wavelength selective permeable polycarbonate resin composition according to Item 1.
Equation (I):
O = P (OH) _n (OR) _3-n
[In the general formula (I), R is an alkyl group or an aryl group, each of which may be the same or different, and n represents an integer of 0 to 3. ] The wavelength selective permeable polycarbonate resin composition according to claim 8, wherein the compound represented by the general formula (I) contains a mixture of monostearyl acid phosphate and disstearyl acid phosphate. The wavelength selective transmissive polycarbonate resin composition according to any one of claims 1 to 9, further comprising a dye (E) containing a phthalocyanine compound having a maximum absorption wavelength of 1000 nm or more and 1200 nm or less. The wavelength selective transmissive polycarbonate resin composition according to claim 10, wherein the dye (E) is represented by the following general formula (II).
Equation (II):

[In the formula, R ³¹ represents an alkyl group which may be the same or different and may have a hydrogen atom or a substituent.
R ³² and R ³³ may be the same or different and represent halogen atoms, OR ³⁴ , SR ³⁵ or NR ³⁶ or R ³⁷ .
X ¹¹ may be the same or different and represents an oxygen atom or a sulfur atom.
The R ³⁴ and R ³⁵ groups may be the same or different, and may have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Shows a heteroaryl group.
The R ³⁶ and R ³⁷ groups represent hydrogen atoms, alkyl groups which may have substituents, or aryl groups which may have substituents, which may be the same or different.
R ³⁶ and R ³⁷ , together with the nitrogen atom to which they are bonded, bond with each other with or without other nitrogen atoms, oxygen atoms or sulfur atoms to form a 5- to 10-membered saturated or unsaturated heterocycle. You may be doing it. The 5- to 10-membered saturated or unsaturated heterocycle may have one or more substituents.
M represents two monovalent metal atoms, divalent metal atoms, trivalent or tetravalent metal compounds. ] The wavelength selective transmissive polycarbonate resin composition according to claim 10, wherein the dye (E) is represented by the following general formula (III).
Equation (III):

[In the formula, R ³¹ represents an alkyl group which may be the same or different and may have a hydrogen atom or a substituent.
X ¹¹ , X ¹² and X ¹³ may be the same or different, indicating an oxygen atom or a sulfur atom.
The R ³⁴ and R ³⁵ groups may be the same or different, and may have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Shows a heteroaryl group.
M represents two monovalent metal atoms, divalent metal atoms, trivalent or tetravalent metal compounds. ] The wavelength selective transmissive polycarbonate resin composition according to any one of claims 10 to 12, wherein the phthalocyanine compound is a phthalocyanine dye having a central metal selected from oxovanadium, copper, aluminum, cobalt and zinc. thing. Further contains at least one selected from the group containing a heat stabilizer, an antioxidant, a mold release agent, an ultraviolet absorber, a colorant, a softener, an antistatic agent, an impact improving agent and a spreading agent. The wavelength selective transmissive polycarbonate resin composition according to any one of claims 1 to 13. A wavelength-selective transmissive polycarbonate resin molded product containing the wavelength-selective transmissive polycarbonate resin composition according to any one of claims 1 to 14. The wavelength selective transmissive polycarbonate resin molded product according to claim 15, which is a lidar cover. A method for producing a wavelength selective transmissive polycarbonate resin molded product, which comprises molding the resin composition according to any one of claims 1 to 14.