TW202113022A - Wavelength-selective transmissive polycarbonate resin composition - Google Patents

Abstract

This wavelength-selective transmissive polycarbonate resin composition contains an aromatic polycarbonate resin (A), a colorant (B) containing a pigment with a maximum absorption wavelength of less than 900 nm, and a phosphate ester compound or phosphoric acid (C). Relative to 100 parts by mass of the aromatic polycarbonate resin (A), the colorant (B) is contained in an amount of 0.01-2.0 parts by mass. For the phosphate ester compound or phosphoric acid (C), 0.005-0.3 parts by mass of a phosphate ester compound (C1) or 0.0001-0.004 parts by mass of phosphoric acid (C2) is included.

Description

Wavelength selective transmission polycarbonate resin composition

The present invention relates to a wavelength selective and transparent polycarbonate resin composition. More specifically, it relates to a wavelength selective and transparent polycarbonate resin composition that is not transparent to visible light but transparent to infrared.

As one of the telemetry technologies that use light, LIDAR (Light Detection and Ranging, Laser Imaging Detection and Ranging, also known as "Light Detection and Ranging" or "Laser Image Detection and Ranging", "Laser Radar") It is known to measure the scattered light irradiated by a pulsed laser and analyze the distance to a distant object or the properties of the object. This technique is similar to radar in that the radio waves of radar are replaced with light. The distance to the object is calculated based on the time from when the light is emitted to when the reflected light is received. Laser radar uses electromagnetic waves with a wavelength much shorter than radar. Typically, it uses ultraviolet, visible light, and near-infrared rays.

In recent years, auto-driving technology for automobiles is developing rapidly. In order to cope with level 3 of conditional autonomous driving and levels 4 to 5 that do not presuppose driving by the driver, it must have the function of driving safely and autonomously on expressways and ordinary roads. Therefore, in order to ensure the redundancy of sensing, in addition to cameras and millimeter wave radars, laser radars have also received attention. In order to support automatic driving, it is necessary to further improve the accuracy of Lidar, and it is required to develop a wavelength selection filter with better performance.

Patent Document 1 discloses the following: an epoxy resin cured body containing an azoanthraquinone mixture, etc. has an average transmittance of 0% in a wavelength range of 380 nm, and a light transmittance of 80% or more at a wavelength of 900 nm. When the wavelength of the laser light used in Lidar is in the range of 850 to 950 nm, the epoxy resin cured body can be preferably used (refer to Examples 1 to 2, [0050], [Figure 1] of Patent Document 1). Patent Document 1 further discloses the following: The average transmittance of a cured epoxy resin containing an azoanthraquinone mixture and the like in the wavelength range of 380 nm is 0%, and the light transmittance at a wavelength of 1550 nm is 80% or more. Therefore, when the wavelength of the laser light used in Lidar is in the range of 1500 to 1600 nm, the epoxy resin cured body can be preferably used (refer to Patent Document 1, Examples 1 to 3, [0050], [Figure 1]) . [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-167484

[The problem to be solved by the invention]

Although Patent Document 1 discloses a hardened epoxy resin, the hardened epoxy resin is not necessarily suitable for inexpensive and large-scale supply. Considering the development of Lidar in the future, it is necessary to provide a composition and its molded product that can be manufactured more cheaply and in large quantities.

The inventors of the present invention have focused on polycarbonate molded products with excellent transparency and mechanical strength. However, they have found that since the molding temperature of polycarbonate is relatively high, the transmittance of the polycarbonate resin composition during molding at high temperatures is It may decrease and/or increase, that is, the transmittance (optical characteristics) may change. Changes in optical characteristics may cause malfunctions. Therefore, the object of the present invention is to provide a polycarbonate resin composition and a molded product thereof that do not substantially change the optical characteristics even if the molding process is performed at a high temperature, and has wavelength-selective transmittance. [Technical means to solve the problem]

The inventors of the present invention have conducted intensive research and found that a polycarbonate resin composition containing a coloring agent (such as an anthraquinone-based dye) containing a pigment with a maximum absorption wavelength of less than 900 nm and phosphoric acid or a phosphate-based compound provides an even A polycarbonate resin composition with wavelength-selective transmittance and a molded product thereof that does not substantially change the optical properties even when it is molded at a high temperature. Furthermore, it was found that this resin composition and molded article can be preferably used for lidar applications, and the present invention has been completed.

This manual includes the following forms. 1. A wavelength-selective and transparent aromatic polycarbonate resin composition, characterized by comprising an aromatic polycarbonate resin (A), a coloring agent (B) containing a pigment with a maximum absorption wavelength of less than 900 nm, and phosphoric acid The ester compound or phosphoric acid (C) contains 0.01 to 2.0 parts by mass of the coloring agent (B) relative to 100 parts by mass of the aromatic polycarbonate resin (A), and the phosphoric acid or phosphoric acid ester compound (C) contains 0.005 to 0.3 parts by mass of phosphoric acid ester compound (C1) or 0.0001 to 0.004 parts by mass of phosphoric acid (C2). 2. The wavelength selective transmission aromatic polycarbonate resin composition as described in 1 above, wherein the colorant (B) contains a colorant (B1) and/or a colorant (B2), and the colorant (B1) contains For pigments that absorb maximum wavelengths of less than 700 nm, the above colorant (B2) contains pigments that have maximum absorption wavelengths in the range of 700 nm or more and less than 900 nm. 3. The wavelength-selective and transparent aromatic polycarbonate resin composition as described in 1 or 2, wherein the coloring agent (B) containing a pigment with a maximum absorption wavelength of less than 900 nm contains a pigment selected from the group consisting of anthraquinone pigments and pyrenone At least one of a pigment, a perylene pigment, a methine pigment, an azo pigment, a quinoline pigment, a phthalocyanine pigment, and a heterocyclic pigment. 4. The wavelength-selective and transparent aromatic polycarbonate resin composition as described in 2 above, wherein the coloring agent (B1) containing a pigment with a maximum absorption wavelength of less than 700 nm contains selected from the group consisting of anthraquinone-based pigments and pyrene-based pigments At least one of pigments, perylene-based pigments, and methine-based pigments. 5. The wavelength selective transmission aromatic polycarbonate resin composition as described in 2 or 4 above, wherein the coloring agent (B1) containing a pigment having a maximum absorption wavelength of less than 700 nm contains an anthraquinone-based pigment. 6. The wavelength-selective and transparent aromatic polycarbonate resin composition as described in 5 above, wherein the anthraquinone-based dye contains selected from the group consisting of Solvent Yellow 163, Disperse Violet 28, Solvent Blue 97, Solvent Green 28, Solvent Green 3. At least one of the group consisting of Disperse Blue 60. 7. The wavelength-selectively transparent aromatic polycarbonate resin composition as described in any one of 2 and 4 to 6 above, which contains the coloring of a pigment having a maximum absorption wavelength in the range of 700 nm or more and less than 900 nm The agent (B2) contains at least one selected from the group consisting of phthalocyanine dyes, anthraquinone dyes, and heterocyclic dyes. 8. The wavelength-selectively transparent aromatic polycarbonate resin composition as described in any one of 1 to 7 above, wherein the phosphoric acid ester compound or phosphoric acid (C) is selected from those represented by the following general formula (I) At least one of the phosphoric acid ester compound or phosphoric acid, formula (I): O=P(OH) _n (OR) _3-n [In the general formula (1), R is an alkyl group or an aryl group, They may be the same or different, and n represents an integer of 0-2]. 9. The wavelength selective transmission aromatic polycarbonate resin composition as described in 8 above, wherein the compound represented by the general formula (I) comprises a mixture of monostearyl acid phosphate and distearyl acid phosphate. 10. The wavelength-selective and transparent aromatic polycarbonate resin composition as described in any one of 1 to 9 above, which further contains selected from the group consisting of heat stabilizers, antioxidants, mold release agents, ultraviolet absorbers, and softeners , At least one of the group of antistatic agents and impact modifiers. 11. A wavelength-selectively transparent aromatic polycarbonate resin molded article containing the wavelength-selectively transparent aromatic polycarbonate resin composition as described in any one of 1 to 10 above. 12. The wavelength selective transmission aromatic polycarbonate resin molded article described in 11 above, which is a lidar cover. 13. A method for producing a wavelength-selectively transparent aromatic polycarbonate resin molded article, which includes the step of molding the resin composition as described in any one of 1 to 10 above. [Effects of Invention]

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

The wavelength selective transmission polycarbonate resin composition of the embodiment of the present invention includes an aromatic polycarbonate resin (A), a coloring agent (B) containing a pigment with a maximum absorption wavelength of less than 900 nm, and a phosphate compound or phosphoric acid (C), With respect to 100 parts by mass of aromatic polycarbonate resin (A), Contains 0.01 to 2.0 parts by mass of coloring agent (B), and Regarding the phosphoric acid or the phosphate compound (C), 0.005 to 0.3 parts by mass of the phosphate compound (C1) or 0.0001 to 0.004 parts by mass of phosphoric acid (C2) is contained.

In the embodiments of the present invention, the "aromatic polycarbonate resin (A)" is a polycarbonate resin based on an aromatic compound. As long as the present invention can obtain the target aromatic polycarbonate resin composition, it is not particularly limited . As such an aromatic polycarbonate resin, for example, a phosgene method in which a dihydroxydiaryl compound and phosgene are reacted, or a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are produced. Various polymers obtained by reaction transesterification method. Representative examples include polycarbonate resins made from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A).

As the above-mentioned dihydroxydiaryl compound, in addition to bisphenol A, for example, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bisphenol A (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(hydroxyaryl)alkanes such as bis(4-hydroxy-3,5-dibromophenyl)propane and 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; 1,1 -Bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane and other bis(hydroxyaryl)cycloalkanes; 4,4'-dihydroxydiphenyl ether, Dihydroxy diaryl ethers such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide; 4 ,4'-dihydroxydiphenyl sulfene, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfene and other dihydroxy diaryl sulfenes; 4,4'-dihydroxy Dihydroxydiaryl gangue, 4,4'-dihydroxy-3,3'-dimethyldiphenyl gangue, etc. These can be used alone or in combination. In addition to these, piperidine, dipiperidyl hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, etc. can also be used in combination.

Furthermore, the above-mentioned dihydroxydiaryl compound can also be used in combination with, for example, an aromatic compound having a valence of three or more shown below.

As the above-mentioned trivalent or higher phenol compound, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-heptene, 2,4,6- Dimethyl-2,4,6-tris(4-hydroxyphenyl)-heptane, 1,3,5-tris(4-hydroxyphenyl)-benzene, 1,1,1-tris(4-hydroxyl Phenyl)-ethane and 2,2-bis[4,4-(4,4'-dihydroxydiphenyl)-cyclohexyl]-propane, etc.

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. In addition, when manufacturing such an aromatic polycarbonate resin (A), a molecular weight regulator, a catalyst, etc. may be used as needed. As such an aromatic polycarbonate resin, commercially available products can be used.

In the embodiments of the present invention, the so-called coloring agent (B) containing a pigment with a maximum absorption wavelength of less than 900 nm refers to a coloring agent (B) containing a pigment with a maximum absorption wavelength of less than 900 nm, and the pigment may be selected from dyes (organic, Inorganic), pigments (organic, inorganic), etc., are not particularly limited as long as the target aromatic polycarbonate resin composition can be obtained in the present invention. As such a pigment, either a dye or a pigment can be used, but in general, the dye is not easy to diffusely reflect light on the particle surface, so it is more preferable to use a dye. The coloring agent (B) containing these pigments can be used alone or in combination of two or more.

Examples of the above-mentioned dye-based dyes include: anthraquinone-based dyes, pyrenone-based dyes, perylene-based dyes, methine-based dyes, azo-based dyes, quinoline-based dyes, phthalocyanine-based dyes, heterocyclic dyes, etc. . Since the oil-soluble dye can be more easily and uniformly dispersed in the resin composition, it is preferred. Since the dye is composed of particles smaller than the pigment, the dye can be more uniformly mixed in the resin composition, and therefore, the haze (Haze value) of the molded body can be reduced, which is preferable. The dye is more preferably used for Lidar applications.

Examples of the above-mentioned pigment-based pigments include: azo-based (soluble azo-based, insoluble azo-based) pigments, condensed-based pigments, anthracene-based pigments, quinacridone-based pigments, dimethicone-based pigments, and isoindole Organic pigments such as morpholine pigments; or inorganic pigments such as titanium oxide, iron oxide, chromium oxide, carbon black, ultramarine, barium sulfate, calcium carbonate, zinc white, lead sulfate, titanium black, synthetic iron black, etc.

The coloring agent (B) preferably contains a coloring agent (B1) and/or a coloring agent (B2), wherein the coloring agent (B1) contains a pigment that absorbs a maximum wavelength of less than 700 nm, and the coloring agent (B2) contains more than 700 nm And it has a pigment with a maximum absorption wavelength in the range of less than 900 nm.

In the embodiment of the present invention, the coloring agent (B1) containing a pigment with a maximum absorption wavelength of less than 700 nm is preferably selected from the group consisting of anthraquinone-based pigments, pyrenone-based pigments, perylene-based pigments, and methine-based pigments At least one of them. The coloring agent (B1) preferably contains an anthraquinone-based dye.

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

In the resin composition of the embodiment of the present invention, as the coloring agent (b1), in addition to the anthraquinone-based dye, a plurality of other dyes may be used in combination. For example, it may be a combination of a pigment and a pigment, a combination of a pigment and a dye, a combination of a dye and a dye, but it is preferable to use a combination of a dye and a dye. In terms of being able to suppress or block light of various wavelengths and having good light transmittance in various wavelength regions, it is preferable to use an anthraquinone-based dye in combination with other dyes.

As long as the composition of the embodiment of the present invention can be obtained, the above-mentioned coloring matter is not particularly limited, and specifically, those described below can be used.

The anthraquinone-based 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 pyrenone-based pigments include pigments commercially available with color indices 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 pigments 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 179, etc. Commercially available pigments.

Examples of methine-based dyes include dyes that are commercially available with a color index such as Solvent Orange 80, Solvent Yellow 93, and Disperse Yellow 201. In addition, as quinoline-based dyes, dyes that are commercially available with a color index such as Solvent Yellow 33, Solvent Yellow 98, Solvent Yellow 157, Disperse Yellow 54, and Disperse Yellow 201 can be cited.

In the embodiment of the present invention, the coloring agent (B2) containing a pigment having a maximum absorption wavelength in the range of 700 nm or more and less than 900 nm preferably includes a pigment selected from the group consisting of phthalocyanine-based pigments, anthraquinone-based pigments, and heterocycles. At least one of the pigments.

(B2) The coloring agent preferably contains a phthalocyanine-based dye. Examples of such a phthalocyanine-based dye include FDN-002, FDN-023, FDN-024, etc. commercially available from Yamada Chemical Industry Co., Ltd.

(B2) The coloring agent preferably contains a heterocyclic dye. Examples of such a heterocyclic dye include SDO-C8, which is commercially available from Moto Chemical Co., Ltd., and the like.

(B2) The coloring agent preferably contains an anthraquinone-based dye. Examples of such an anthraquinone-based dye include SDO-C33, which is commercially available from Omoto Chemical Industry Co., Ltd., and the like.

The resin composition of the embodiment of the present invention preferably contains 0.01 to 2.0 parts by mass of a coloring agent (B) containing a pigment having a maximum absorption wavelength of less than 900 nm with respect to 100 parts by mass of the aromatic polycarbonate resin (A), It is more preferably 0.012 to 1.5 parts by mass, and still more preferably 0.014 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 phosphate 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 preferably contains one selected from the following general formula ( At least one of the group consisting of the phosphoric acid ester compound and phosphoric acid represented by I).

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 represents an integer from 0 to 2].

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. Furthermore, m is preferably 1 or 2. As the phosphate compound of the formula (I), for example, monostearyl acid phosphate or distearyl acid phosphate, stearyl phosphate mixed ester (monostearyl phosphate approximately 50 mole% It is a mixture of about 50 mole% with distearyl phosphate, trade name "AX-71" manufactured by Adeka Co., Ltd.), etc.

Phosphoric acid is a non-volatile weak acid. Commercially available products can be used without special restrictions. Examples include phosphoric acid manufactured by Nacalai Tesque, and phosphoric acid manufactured by Wako Pure Chemical Industries, Ltd., etc.

In the resin composition of the embodiment of the present invention, the phosphate compound or phosphoric acid (C) preferably contains 0.005 to 0.3 parts by mass of the phosphate compound with respect to 100 parts by mass of the aromatic polycarbonate resin (A) The compound (C1) is more preferably contained in 0.007 to 0.1 parts by mass, and still more preferably contained in 0.009 to 0.08 parts by mass. Or it is preferable to include 0.0001 to 0.004 parts by mass of phosphoric acid (C2), preferably 0.0001 to 0.001 parts by mass, more preferably 0.0003 to 0.0008 parts by mass, and still more preferably 0.0004 to 0.0006 parts by mass.

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

Regarding the phosphorus antioxidant, as long as the target aromatic polycarbonate resin composition can be obtained in the present invention, it is not particularly limited, but preferably contains a phosphite compound having the following phosphite structure. [化1]

In the aromatic polycarbonate resin composition of the embodiment of the present invention, the phosphorus antioxidant (D) preferably contains a phosphite compound represented by the following formula (11), and the following formula (12) At least one compound of the phosphite compound represented, the phosphite compound represented by the following formula (13), and the phosphite compound represented by the following formula (14).

The phosphorus antioxidant (D) preferably contains, for example, a compound represented by the following formula (11).

(式中，R¹ 表示碳數1～20之烷基，a表示0～3之整數)Formula (11): [化2]

(In the formula, R ¹ represents an alkyl group with 1 to 20 carbon atoms, and a represents an integer of 0 to 3)

In the above formula (11), R ¹ is an alkyl group having 1 to 20 carbons, and more preferably an alkyl group having 1 to 10 carbons.

As the compound represented by formula (11), for example, triphenyl phosphite, tricresyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, trinonylbenzene phosphite Ester etc. Among them, tris(2,4-di-tert-butylphenyl) phosphite is particularly preferred. For example, Irgafos 168 manufactured by BASF Corporation ("Irgafos" is a registered trademark of BASF Societas Europaea) is commercially available.

The phosphorus antioxidant (D) preferably contains, for example, a compound represented by the following formula (12).

(式中，R² 、R³ 、R⁵ 及R⁶ 分別獨立地表示氫原子、碳數1～8之烷基、碳數5～8之環烷基、碳數6～12之烷基環烷基、碳數7～12之芳烷基或苯基；R⁴ 表示氫原子或碳數1～8之烷基；X表示單鍵、硫原子或式：-CHR⁷ -所表示之基(其中，R⁷ 表示氫原子、碳數1～8之烷基或碳數5～8之環烷基)；A表示碳數1～8之伸烷基或式：∗-COR⁸ -所表示之基(其中，R⁸ 表示單鍵或碳數1～8之伸烷基，∗表示氧側之鍵結鍵)；Y及Z中任一者表示羥基、碳數1～8之烷氧基或碳數7～12之芳烷氧基，另一者表示氫原子或碳數1～8之烷基)Formula (12): [化3]

(In the formula, R ² , R ³ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group with 1 to 8 carbons, a cycloalkyl group with 5 to 8 carbons, and an alkyl ring with 6 to 12 carbons. An alkyl group, an aralkyl group having 7 to 12 carbons or a phenyl group; R ⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbons; 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 with 1 to 8 carbons or a cycloalkyl group with 5 to 8 carbons); A represents an alkylene with 1 to 8 carbons or the formula: ∗-COR ^8- Group (where R ⁸ represents a single bond or an alkylene group with 1 to 8 carbons, ∗ represents a bonding bond on the oxygen side); any of Y and Z represents a hydroxyl group, an alkoxy group with 1 to 8 carbons or Aralkyloxy with 7-12 carbons, the other represents a hydrogen atom or alkyl with 1-8 carbons)

In formula (12), R ² , R ³ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group with 1 to 8 carbons, a cycloalkyl group with 5 to 8 carbons, and a group with 6 to 12 carbons. Alkylcycloalkyl, C7-12 aralkyl or phenyl.

Here, as the C1-C8 alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, first Tripentyl, isooctyl, tertiary octyl, 2-ethylhexyl, etc. Examples of the cycloalkyl group having 5 to 8 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 1-methylcyclopentyl, 1-methylcyclohexyl, and 1-methyl-4-isopropylcyclohexyl. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and the like.

Preferably, the above-mentioned R ² , R ³ and R ⁵ are each independently an alkyl group having 1 to 8 carbons, a cycloalkyl group having 5 to 8 carbons, or an alkylcycloalkyl group having 6 to 12 carbons. Particularly ^{preferably, R 2} and R ⁵ are each independently a tertiary alkyl group such as tertiary butyl, tertiary pentyl, and tertiary octyl, cyclohexyl, or 1-methylcyclohexyl. Particularly ^{preferably, R 3} is an alkane with 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, tertiary pentyl, etc. ^{R 3} is more preferably a methyl group, a tertiary butyl group or a tertiary pentyl group.

The above-mentioned R ^{6 is} preferably a hydrogen atom, an alkyl group having 1 to 8 carbons or a cycloalkyl group having 5 to 8 carbons, and more preferably a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a normal C1-C5 alkyl groups such as butyl, isobutyl, second butyl, tertiary butyl, and tertiary pentyl.

In the formula (12), 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 description of ^{R 2} , R ³ , R ⁵ and R ^6. R ^{4 is} particularly 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 the formula (12), X represents a single bond, a sulfur atom or a group represented by the ^{formula: -CHR 7 -. Wherein, R 7} in the formula: -CHR ⁷ -represents a hydrogen atom, an alkyl group with 1 to 8 carbons, or a cycloalkyl group with 5 to 8 carbons. 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 description of ^{R 2} , R ³ , R ⁵ and R ^{6 above, respectively.} X is particularly preferably a single bond, a methylene group, or a methylene group substituted with methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc., and more preferably single bond.

In the formula (12), 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: methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, 2,2- Dimethyl-1,3-propylene group and the like are preferably propylene group. ^{In addition, 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 description of A above.} R ^{8 is} preferably a single bond or an ethylene group. In addition, in the formula: ∗-COR ⁸ -, ∗ is the bonding bond on the oxygen side, which means that the carbonyl group is bonded to the oxygen atom of the phosphite group.

In the formula (12), any one of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbons or an aralkoxy group having 7 to 12 carbons, and the other represents a hydrogen atom or a carbon number of 1-8的alkyl. As a C1-C8 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a tert-butoxy group, a pentyloxy group, etc. are mentioned, for example. Examples of the aralkoxy having 7 to 12 carbon atoms include benzyloxy, α-methylbenzyloxy, α,α-dimethylbenzyloxy, and the like. Examples of the alkyl group having 1 to 8 carbon atoms include the alkyl groups exemplified in the above description of ^{R 2} , R ³ , R ⁵ and R ^6.

As the compound represented by the formula (12), for example, 2,4,8,10-tetra-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butylbenzene) Yl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphole, 6-[3-(3,5-di-tert-butyl-4-hydroxybenzene Yl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphorine, 6-[3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propoxy]-4,8-di-tert-butyl-2,10-dimethyl-12H-dibenzo[d,g][ 1,3,2] dioxaphosphacyclic, 6-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-4,8-di-tert-butyl -2,10-Dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphate, etc. Among them, particularly when the obtained aromatic polycarbonate resin composition is used in a field requiring optical properties, 2,4,8,10-tetra-tert-butyl-6-[3- (3-Methyl-4-hydroxy-5-tert-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphene, for example, commercially available Purchased Sumilizer GP ("Sumilizer" is a registered trademark) manufactured by Sumitomo Chemical Co., Ltd.

The phosphorus antioxidant (D) preferably contains, for example, a compound represented by the following formula (13).

(式中，R⁹ 及R¹⁰ 分別獨立地表示碳數1～20之烷基或可經烷基取代之芳基，b及c分別獨立地表示0～3之整數)Formula (13): [化4]

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

As a compound represented by Formula (13), bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, etc. are mentioned, for example. Regarding bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, the trade name "Adekastab PEP-24G" manufactured by ADEKA Corporation (stock) is commercially available. Commercially available Adekastab PEP-36 ("Adekastab" is a registered trademark) manufactured by ADEKA Corporation (stock).

The phosphorus antioxidant (D) preferably contains, for example, a compound represented by the following formula (14).

Formula (14): [化5]

(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 , R ¹⁷ and R ¹⁸ can be mutually Bond to form a ring; R ¹⁹ to R ²² each independently represent a hydrogen atom or an alkyl group with 1 to 20 carbon atoms; d to g are each independently 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, the functional groups in R 11} to R ²² that are connected to the single bond are excluded from the general formula (14)).

As a specific example of the compound represented by formula (14), for example, bis(2,4-dicumylphenyl) pentaerythritol diphosphite can be cited. Regarding this compound, the trade name "Doverphos (registered trademark) S-9228" manufactured by Dover Chemical Company, and the trade name "Adekastab PEP-45" manufactured by ADEKA Company (stock) (double (2,4-二异) Propylphenylphenyl) pentaerythritol diphosphite).

Phosphorus antioxidants (D) may further include, for example, [1,1'-biphenyl]-4,4'-diylbis[bis(2,4-di-tertiarybutylphenoxy)phosphine] and the like, For example, Irgafos P-EPQ (trade name) manufactured by BASF and HOSTANOX P-EPQ (trade name) manufactured by Clariant Chemicals are commercially available.

Preferably, it is the above-mentioned aromatic polycarbonate resin composition which satisfies at least one selected from the following conditions: The phosphite compound represented by the above formula (11) includes tris(2,4-di-tert-butylphenyl) phosphite; The phosphite compound represented by the above formula (12) contains 2,4,8,10-tetra-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butylphenyl) )Propoxy]dibenzo[d,f][1,3,2]dioxaphosphene; The phosphite compound represented by the above formula (13) includes 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 above formula (14) includes bis(2,4-dicumylphenyl) pentaerythritol diphosphite.

The amount of the phosphorus antioxidant (D) is preferably 0.5 parts by mass or less, and more preferably 0.02 to 0.2 parts by mass relative to 100 parts by mass of the aromatic polycarbonate resin (A).

In addition to the above-mentioned components, depending on the application of the molded article obtained by molding the aromatic polycarbonate resin composition, for example, an ultraviolet absorber may be suitably used in the aromatic polycarbonate resin composition of the embodiment. The agent is a component that further improves the weather resistance of the obtained aromatic polycarbonate resin composition.

As the ultraviolet absorber, for example, a benzotriazole-based compound, a tris-based compound, a benzophenone-based compound, an oxalic acid aniline-based compound, and other ultraviolet absorbers usually formulated in polycarbonate resins can be used. They can be used alone or Combine 2 or more types.

Examples of benzotriazole-based compounds include 2-(2-hydroxy-5-tert-octylphenyl) benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methyl) Phenyl)-5-chloro-2H-benzotriazole, 2-(3,5-di-thirdpentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2H-benzo Triazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthaliminomethyl)phenol, 2-(2-hydroxy-4-octyloxy) Phenyl)-2H-benzotriazole, 2-(2-hydroxy-5-third octylphenyl)-2H-benzotriazole, 2-[2'-hydroxy-3,5-bis( 1,1-Dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)4-(1, 1,3,3-Tetramethylbutyl)phenol] and so on. Among them, 2-(2-hydroxy-5-tertiary octylphenyl) benzotriazole and the like are particularly preferred. For example, TINUVIN 329 manufactured by BASF (TINUVIN is a registered trademark), SHIPRO KASEI (shares ) SEESORB 709 manufactured by CHEMIPRO KASEI, Chemisorb 79 manufactured by CHEMIPRO KASEI, etc.

Examples of tris-based compounds include 2,4-diphenyl-6-(2-hydroxyphenyl-4-hexyloxyphenyl) 1,3,5-tris, 2-[4,6 -Bis(2,4-dimethylphenyl)-1,3,5-tris-2-yl)-5-(octyloxy)phenol, 2-(4,6-diphenyl-1, 3,5-tris-2-yl)-5-[(hexyl)oxy]phenol, etc., for example, TINUVIN 1577 manufactured by BASF Corporation, etc. are commercially available.

As the oxalanilide compound, for example, Sanduvor VSU manufactured by Clariant Japan Co., Ltd. and the like are commercially available.

As a benzophenone type compound, 2, 4- dihydroxy benzophenone, 2-hydroxy-4-n-octyloxy benzophenone, etc. are mentioned, for example.

The amount of the ultraviolet absorber is 0 to 1.0 parts by mass relative to 100 parts by mass of the aromatic polycarbonate resin (A), preferably 0 to 0.5 parts by mass. When the amount of the ultraviolet absorber exceeds 1.0 part by mass, the initial hue of the obtained aromatic polycarbonate resin composition may decrease. In addition, when 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 can be greatly exhibited.

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

Regarding the aromatic polycarbonate resin composition of the embodiment of the present invention, the following production method can be exemplified: mixing an aromatic polycarbonate resin (A), a colorant (B), a phosphate compound or phosphoric acid (C), If necessary, phosphorus-based antioxidant (D), various additives mentioned above, and polymers other than aromatic polycarbonate resin (A) are mixed. As long as the target aromatic polycarbonate resin composition can be obtained in the present invention, its production method is not particularly limited, and the type and amount of each component can be appropriately adjusted. The mixing method of the components is also not particularly limited. For example, a method of mixing with a known mixer such as a drum and a belt mixer; or a method of melting and kneading with an extruder can be exemplified. By these methods, particles of the aromatic polycarbonate resin composition can be easily obtained.

The shape and size of the particles of the aromatic polycarbonate resin composition obtained as described above are not particularly limited, as long as they are the shape and size of general resin particles. For example, as the shape of the particles, elliptical columnar shape, cylindrical shape, etc. can be cited. As for the particle size, the length is preferably about 2-8 mm. In the case of an elliptical cylinder, the long diameter of the cross-sectional ellipse is preferably about 2-8 mm and the short diameter is about 1-4 mm. In the case of a shape, it is preferable that the diameter of the cross-sectional circle is about 1 to 6 mm. Furthermore, each of the obtained particles can be of this size, and all the particles forming the particle assembly can be of this size, and the average value of the particle assembly can be of this size. limited.

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

Regarding the reliability of the resin composition of the embodiment of the present invention, it is preferable that the molded article is allowed to stand for 240 hours under the conditions of 85°C and 95% RH, and its molecular weight is 16000 or more, and it is more preferable that the molded article is kept at 120°C. After standing for 240 hours under the conditions, its molecular weight is more than 16000. The reliability of the resin composition can be measured by the method described in the 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 preferably used for sensor applications, filter applications, and the like.

As long as the target molded product can be obtained in the present invention, the manufacturing method of the molded product is not particularly limited. For example, a method of molding an aromatic polycarbonate resin composition by a known injection molding method, a compression molding method, or the like can be mentioned.

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

The embodiment has been described above as an illustration of the present invention. However, the technology in the present invention is not limited to this, and can also be applied to embodiments with appropriate changes, substitutions, additions, omissions, and the like. [Example]

Hereinafter, the present invention will be described specifically and in detail through examples and comparative examples, but these examples are only one form of the present invention, and the present invention is not limited by these examples in any way.

The ingredients used in this example are as follows. (A) Aromatic polycarbonate resin (a1) Polycarbonate resin synthesized from bisphenol A and carbon chloride Viscosity average molecular weight: 18800, SD POLYCA 200-20 (trade name) manufactured by Sumika Polycarbonate (stock), "SD POLYCA" is a registered trademark of Sumika Polycarbonate (stock)

(B) Pigment with maximum absorption wavelength less than 900 nm (b1) Anthraquinone pigment (Solvent Blue 97) Macrolex Blue RR (trade name) manufactured by Bayer AG, maximum absorption wavelength: 630 nm [化6]

(b2) Anthraquinone pigment (Solvent Green 28) Macrolex Green G (trade name) manufactured by Bayer AG, maximum absorption wavelength: 690 nm [Chemical 7]

(b3) Anthraquinone pigments (SD-3, mixture) manufactured by Kenrong Industrial Co., Ltd., maximum absorption wavelength: 630 nm (b4) Anthraquinone pigments (Solvent Green 3) manufactured by Mitsui Fine Chemicals Co., Ltd. Mitsui PS Green B (trade name), maximum absorption wavelength: 640 nm [Chemical 8]

(b5) Methylene-based pigment (Disperse Yellow 201) Macrolex Yellow 6G (trade name) manufactured by Bayer AG, maximum absorption wavelength: 440 nm [Chemical 9]

(b6) Perylene pigment (Solvent Red 179) Macrolex Red E2G (trade name) manufactured by Bayer AG, maximum absorption wavelength: 480 nm [Chem. 10]

(b7) Phthalocyanine pigments (FDN-002 trade name) Manufactured by Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 807 nm (b8) Phthalocyanine pigment (FDN-023 trade name) Manufactured by Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 790 nm

(b9) Phthalocyanine pigments (FDN-024 trade name) Manufactured by Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 830 nm

(b10) Anthraquinone pigments (SDO-C33 trade name) Arimoto Chemical Industry Co., Ltd., maximum absorption wavelength: 846 nm

(b11) Heterocyclic dyes (SDO-C8 trade name) Manufactured by Arimoto Chemical Industry Co., Ltd., maximum absorption wavelength: 785 nm

(c2)磷酸 Nacalai Tesque公司製造之磷酸(H₃ PO₄ )(C) Phosphoric acid or phosphate ester compound (c1) Phosphate ester compound stearyl phosphate mixed ester (a mixture of about 50 mol% of monostearyl phosphate and about 50 mol% of distearyl phosphate; ADEKA company ( Stock) manufactured by Adekastab "AX-71 (trade name)") [化11]

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

(D) Phosphorus antioxidants (d1) Phosphorus antioxidants HOSTANOX P-EPQ (trade name) manufactured by Clariant Chemicals [1,1'-Biphenyl]-4,4'-diylbis[bis(2,4-di-tert-butylphenoxy)phosphine] additive

(x1) Release agent Riken Vitamin (stock) Rikenal S-100A (trade name)

These components were blended in the mass ratios shown in Tables 1 to 3, and the polycarbonate compositions of Examples 1 to 13 and Comparative Examples 1 to 4 were produced.

Each of the polycarbonate compositions of Examples 1 to 13 and Comparative Examples 1 to 4 was evaluated by the following evaluation method. (1) Thermal stability In order to evaluate the thermal stability, the polycarbonate resin composition was molded using J100 E2P manufactured by Nippon Steel Co., Ltd. at a cylinder temperature of 320°C and a mold temperature of 100°C. Next, it was retained in the cylinder (320°C) 10, 30 and 60 minutes to obtain a molded product (1 mm). For the optical spectrum of the molded product, the transmission spectrum was evaluated using UH4150 manufactured by Hitachi High-Tech Science, and the change in optical characteristics was quantified as follows. The transmittance is measured every 2 nm from 1050 nm to 500 nm, and the difference between the wavelength at which the transmittance begins to decrease (hereinafter referred to as the decrease start wavelength) and the wavelength at which the transmittance decrease ends (hereinafter referred to as the decrease end wavelength) is measured. The case where the decrease start wavelength-decrease end wavelength (Δ) is 200 nm or less is regarded as a good product. The case where Δ is 200 nm or more is regarded as bad. Furthermore, in a specific wavelength selective filter, it is expected that the optical spectrum is steep. When the difference in wavelength is large, that is, when the above-mentioned Δ is 200 nm or more (not steep), there may be abnormalities in the filter. So it's not good.

(2) Reliability Each of the polycarbonate resin compositions of Examples 1 to 13 and Comparative Examples 1 to 4 was evaluated by the following evaluation methods. Using J100 E2P manufactured by Japan Steel Corporation, the polycarbonate resin composition was molded at a cylinder temperature of 320°C and a mold temperature of 100°C. The molded product was subjected to 85°C, 95% RH, and thermal aging resistance evaluation at 120°C. Each was left to stand for 240 hours to obtain (evaluation) samples. Determine its weight average molecular weight. The case where the weight average molecular weight is 16000 or more is regarded as a good product, and the case where the weight average molecular weight is less than 16000 is regarded as a bad product. The Alliance HPLC system manufactured by Nihon Waters was used as the GPC device to measure the weight average molecular weight. As the column for GPC, PLgel 5 μm MiniMIX-C manufactured by Agilent Technologies was used. Use dichloromethane as a solvent to dissolve the sample and prepare a solution. THF (Tetrahydrofuran) was used as the eluent, and the solution was circulated through the column at a flow rate of 0.3 mL/min at 40°C to obtain a measured value. A sample with a known weight average molecular weight (monodisperse polystyrene) is used to make a gel permeation chromatography (GPC) calibration curve, and the measured value is corrected to obtain the target weight average molecular weight.

[Table 1] Table 1 Example 1 2 3 4 5 6 7 8 (A) (a1) 100 100 100 100 100 100 100 100 (B) (b1) 0.5 0.5 0.5 0.5 0.11 0.11 (b2) 0.22 0.22 0.22 0.22 0.22 0.22 (b3) 0.29 0.29 (b4) 0.07 0.07 (b5) 0.008 0.008 (b6) 0.074 0.074 (C) (c1) 0.05 0.01 0.05 0.05 (c2) 0.0005 0.0001 0.0005 0.0005 (D) (d1) 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 (X) (x1) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Decrease the starting wavelength (after 60 minutes of residence) 828 nm 848 nm 830 nm 854 nm 778 nm 778 nm 800 nm 798 nm Thermal stability Benchmark 114 nm 114 nm 110 nm 112 nm 100 nm 100 nm 110 nm 110 nm Stay for 10 minutes 108 nm 112 nm 110 nm 120 nm 100 nm 100 nm 108 nm 110 nm Stay for 30 minutes 110 nm 126 nm 114 nm 136 nm 104 nm 104 nm 110 nm 112 nm Stay for 60 minutes 108 nm 134 nm 122 nm 148 nm 102 nm 108 nm 110 nm 118 nm judgment ○ ○ ○ ○ ○ ○ ○ ○ reliability Benchmark 23000 23000 23000 23000 23000 23000 23000 23000 85℃ 95% RH 18000 18000 18000 18000 18000 18000 18000 18000 120℃ 0% RH 21000 21000 21000 21000 21000 21000 21000 21000 judgment ○ 〇 ○ 〇 ○ ○ ○ ○

[Table 2] Table 2 Example 9 10 11 12 13 (A) (a1) 100 100 100 100 100 (B) (b1) 0.5 0.5 0.5 0.5 0.5 (b2) 0.22 0.22 0.22 0.22 0.22 (b3) (b4) (b5) (b6) (b7) 0.04 (b8) 0.04 (b9) 0.04 (b10) 0.04 (b11) 0.04 (C) (c1) (c2) 0.001 0.001 0.001 0.001 0.001 (D) (d1) 0.05 0.05 0.05 0.05 0.05 (X) (x1) 0.1 0.1 0.1 0.1 0.1 Decrease the starting wavelength (after 60 minutes of residence) 898 nm 861 nm 900 nm 846 nm 935 nm Thermal stability Benchmark 130 nm 118 nm 108 nm 120 nm 130 nm Stay for 10 minutes 132 nm 120 nm 110 nm 120 nm 128 nm Stay for 30 minutes 130 nm 120 nm 108 nm 120 nm 128 nm Stay for 60 minutes 134 nm 120 nm 108 nm 122 nm 130 nm judgment ○ ○ ○ ○ ○ reliability Benchmark 23000 23000 23000 23000 23000 85℃ 95% RH 18000 18000 18000 18000 18000 120℃ 0% RH 21000 21000 21000 21000 21000 judgment ○ 〇 ○ 〇 ○

[table 3] table 3 Comparative example 1 2 3 4 (A) (a1) 100 100 100 100 (B) (b1) 0.5 0.11 0.5 0.5 (b2) 0.22 0.22 0.22 0.22 (b3) (b4) 0.07 (b5) 0.008 (b6) 0.074 (C) (c1) 0.5 (c2) 0.005 (D) (d1) 0.05 0.05 0.05 0.05 (X) (x1) 0.1 0.1 0.1 0.1 Decrease the starting wavelength (after 60 minutes of residence) 1040 nm 984 nm 830 nm 828 nm Thermal stability Benchmark 122 nm 114 nm 108 nm 110 nm Stay for 10 minutes 274 nm 282 nm 110 nm 110 nm Stay for 30 minutes 366 nm 370 nm 108 nm 110 nm Stay for 60 minutes 380 nm 376 nm 108 nm 112 nm judgment X X ○ ○ reliability Benchmark 23000 23000 19000 19000 85℃ 95% RH 18000 18000 11000 11000 120℃ 0% RH 21000 21000 15000 15000 judgment 〇 〇 X X

The polycarbonate resin composition of Examples 1-13 includes an aromatic polycarbonate resin (A), a coloring agent (B) containing a pigment with a maximum absorption wavelength of less than 900 nm, and a phosphate compound or phosphoric acid (C) , Relative to 100 parts by mass of aromatic polycarbonate resin (A), containing 0.01 to 2.0 parts by mass of coloring agent (B), and regarding phosphoric acid or phosphate compound (C), containing 0.005 to 0.3 parts by mass of phosphate ester The compound (C1) or phosphoric acid (C2) containing 0.0001 to 0.04 parts by mass. The polycarbonate resin compositions of Examples 1 to 13 are excellent in thermal stability and reliability, and are suitable as wavelength-selective and transparent polycarbonate resin compositions for filters.

In the molded products of Comparative Examples 1 and 2, the start wavelength of the transmittance reduction shifts to the longer wavelength side, and the wavelength width from the start wavelength of the transmittance reduction to the end wavelength of the reduction is large, so the near infrared rays of 850-950 nm used in Lidar cannot be used. Appropriate penetration. Therefore, the detection ability of Lidar may be reduced. In contrast, in the case of Examples 1 to 13 in which the phosphoric acid ester compound or phosphoric acid of the present invention is used, even if the residence time is 60 minutes, the start wavelength and wavelength width of the transmittance decrease did not change significantly. Near-infrared rays from 850 nm to 950 nm are transmitted properly and are excellent as a wavelength selective filter.

In the case where an excessive amount of phosphoric acid ester or phosphoric acid is formulated as in Comparative Examples 3 and 4, the molecular weight after the reliability test is significantly reduced, and the impact resistance required for the polycarbonate resin is impaired. When used as a lidar cover, it may collide with stones on the road surface, etc., which may cause abnormalities such as damage to the cover. In contrast, it can be seen that when appropriate amounts of phosphoric acid ester and phosphoric acid are added, there is no significant reduction in molecular weight, and the characteristics of the polycarbonate resin can be maintained. [Industrial availability]

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

Related applications This application is based on Article 4 of the Paris Convention and is based on the application number 2019-146366 filed in Japan on August 8, 2019 and the application number 2020-077493 filed in Japan on April 24, 2020. priority. The contents of these basic applications are incorporated into this manual by reference.

Claims (13)

A wavelength-selective and transparent aromatic polycarbonate resin composition, characterized in that it comprises an aromatic polycarbonate resin (A), a coloring agent (B) containing a pigment with a maximum absorption wavelength of less than 900 nm, and a phosphoric acid ester series Compound or phosphoric acid (C), With respect to 100 parts by mass of aromatic polycarbonate resin (A), Contains 0.01 to 2.0 parts by mass of coloring agent (B), and Regarding the phosphoric acid or the phosphate compound (C), 0.005 to 0.3 parts by mass of the phosphate compound (C1) or 0.0001 to 0.004 parts by mass of phosphoric acid (C2) is contained. The wavelength selective transmission aromatic polycarbonate resin composition of claim 1, wherein the colorant (B) contains a colorant (B1) and/or a colorant (B2), and the colorant (B1) contains a maximum absorption wavelength For pigments below 700 nm, the above-mentioned colorant (B2) contains pigments with a maximum absorption wavelength in the range of 700 nm or more and below 900 nm. For example, the wavelength selective transmission aromatic polycarbonate resin composition of claim 1 or 2, wherein the coloring agent (B) containing a pigment having a maximum absorption wavelength of less than 900 nm contains selected from the group consisting of anthraquinone-based pigments, pyrenone-based pigments, At least one of perylene pigments, methine pigments, azo pigments, quinoline pigments, phthalocyanine pigments, and heterocyclic pigments. The wavelength-selective and transparent aromatic polycarbonate resin composition according to claim 2, wherein the coloring agent (B1) containing a pigment with a maximum absorption wavelength of less than 700 nm includes selected from the group consisting of anthraquinone-based pigments, pyrenone-based pigments, and perylene At least one of methine-based pigments and methine-based pigments. The wavelength selective transmission aromatic polycarbonate resin composition of claim 2 or 4, wherein the coloring agent (B1) containing a pigment with a maximum absorption wavelength of less than 700 nm contains an anthraquinone-based pigment. The wavelength-selective and transparent aromatic polycarbonate resin composition according to claim 5, wherein the anthraquinone-based pigment is 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 At least one of the group formed. Such as the wavelength selective transmission aromatic polycarbonate resin composition of any one of Claims 2 and 4 to 6, which contains a coloring agent (B2 ) Contains at least one selected from the group consisting of phthalocyanine dyes, anthraquinone dyes, and heterocyclic dyes. The wavelength-selectively transparent aromatic polycarbonate resin composition according to any one of claims 1 to 7, wherein the phosphoric acid ester compound or phosphoric acid (C) comprises phosphoric acid esters selected from the group consisting of the following general formula (I) At least one of the group consisting of a compound or phosphoric acid, formula (I): O=P(OH) _n (OR) _3-n [In the general formula (1), R is an alkyl group or an aryl group, which may be the same respectively It may be different, and n represents an integer of 0-2]. The wavelength selective transmission aromatic polycarbonate resin composition according to claim 8, wherein the compound represented by the general formula (I) comprises a mixture of monostearyl acid phosphate and distearyl acid phosphate. The wavelength selective transmission aromatic polycarbonate resin composition according to any one of claims 1 to 9, which further contains selected from the group consisting of heat stabilizers, antioxidants, mold release agents, ultraviolet absorbers, softeners, and antistatic At least one of the group of agents and impact modifiers. A wavelength-selectively transparent aromatic polycarbonate resin molded article containing the wavelength-selectively transparent aromatic polycarbonate resin composition according to any one of claims 1 to 10. For example, the wavelength selective transmission aromatic polycarbonate resin molded article of claim 11 is a lidar cover. A method for manufacturing a wavelength-selectively transparent aromatic polycarbonate resin molded article, which includes a step of molding the resin composition according to any one of claims 1 to 10.