TW202231828A - 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 Transmittance Polycarbonate Resin Composition

The present invention relates to a polycarbonate resin composition with wavelength selective transmittance, and more specifically, relates to a polycarbonate resin composition with wavelength selective transmittance that cannot transmit visible light but can transmit infrared rays.

LIDAR (Light Detection and Ranging, Laser Imaging Detection and Ranging, also known as "Light Detection and Ranging" or "Laser Image Detection and Ranging", "Ladar") It is known to measure scattered light from a pulsed emitting laser and to analyze the distance to a distant object or the properties of the object. Similar to radar, this technique replaces the radar's radio waves with light. The distance to the object is calculated based on the time from emitting light to receiving reflected light. Lidar uses electromagnetic waves with much shorter wavelengths than radar, typically ultraviolet, visible, and near-infrared.

In recent years, the autonomous driving technology of automobiles is developing rapidly. In order to cope with Level 3 of conditional autonomous driving and Levels 4 to 5 that do not require the driving of a driver, it is necessary to have the function of safe autonomous driving on expressways and ordinary roads. Therefore, in order to ensure the redundancy of sensing, besides cameras and millimeter-wave radars, lidars have also received attention. In order to support autonomous driving, it is necessary to further improve the accuracy of Lidar, and it is required to develop a wavelength selective filter with better performance.

Patent Document 1 discloses that the cured epoxy resin containing an azoanthraquinone-based mixture or the like 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 the lidar is in the range of 850-950 nm, the epoxy resin cured body can be preferably used (refer to Examples 1-2 of Patent Document 1, [0050], [FIG. 1]). Patent Document 1 further discloses that the cured epoxy resin containing azoanthraquinone-based mixture or the like 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 1550 nm. 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], [Fig. 1]) . [Prior Art Literature] [Patent Literature]

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

[Problems to be Solved by Invention]

Although patent document 1 discloses the hardened body of an epoxy resin, the hardened body of an epoxy resin is not necessarily suitable to be provided cheaply and in large quantities. Considering the development of lidar in the future, there is a need to provide a composition and a molded product thereof that can be produced more cheaply and in large quantities.

The inventors of the present invention have paid attention to a polycarbonate molded product having excellent transparency and excellent mechanical strength, but found that since the molding temperature of polycarbonate is high, the transmittance during molding of the polycarbonate resin composition at a high temperature increases. It may decrease and/or increase, ie the transmittance (optical properties) may change. Changes in optical properties may cause malfunctions. Therefore, an object of the present invention is to provide a polycarbonate resin composition and a molded article thereof which have wavelength selective transmittance without substantially changing optical properties even when molded at a high temperature. [Technical means to solve problems]

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

This specification includes the following forms. 1. A wavelength selective transmittance aromatic polycarbonate resin composition, characterized in that: comprising an aromatic polycarbonate resin (A), a colorant (B) containing a pigment whose maximum absorption wavelength is 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 colorant (B) 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 0.005-0.3 mass part of phosphoric acid ester compound (C1) or 0.0001-0.004 mass part of phosphoric acid (C2). 2. The wavelength selective transmittance aromatic polycarbonate resin composition according to the above 1, wherein the colorant (B) contains a colorant (B1) and/or a colorant (B2), and the colorant (B1) contains For pigments whose absorption maximum wavelength is less than 700 nm, the above colorant (B2) contains pigments with maximum absorption wavelengths in the range of 700 nm or more and less than 900 nm. 3. The wavelength-selective transmissive aromatic polycarbonate resin composition as described in 1 or 2 above, wherein the colorant (B) containing a pigment having a maximum absorption wavelength of less than 900 nm comprises an anthraquinone-based pigment, a pyrene ketone At least one type of dyes, perylene-based dyes, methine-based dyes, azo-based dyes, quinoline-based dyes, phthalocyanine-based dyes, and heterocyclic dyes. 4. The wavelength selective transmittance aromatic polycarbonate resin composition according to the above 2, wherein the colorant (B1) containing a dye having a maximum absorption wavelength of less than 700 nm comprises an anthraquinone-based dye, a pyrenone-based dye At least one of pigments, perylene-based pigments, and methine-based pigments. 5. The wavelength-selective transmissive aromatic polycarbonate resin composition according to 2 or 4 above, wherein the colorant (B1) containing a dye having a maximum absorption wavelength of less than 700 nm contains an anthraquinone-based dye. 6. The wavelength-selective transmissive aromatic polycarbonate resin composition as described in 5 above, wherein the anthraquinone-based pigment comprises a compound 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 selective transmission aromatic polycarbonate resin composition according to any one of the above 2 and 4 to 6, which contains a pigment having a maximum absorption wavelength within a 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-based dyes, anthraquinone-based dyes, and heterocyclic-based dyes. 8. The wavelength-selective transmissive aromatic polycarbonate resin composition according to any one of the above 1 to 7, wherein the phosphoric acid ester-based compound or the phosphoric acid (C) contains a compound selected from the group consisting of those represented by the following general formula (I). At least one of the group consisting of phosphoric acid ester compounds or phosphoric acid, Formula (I): O=P(OH) _n (OR) _3-n [In 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 to 2]. 9. The wavelength-selective transmissive aromatic polycarbonate resin composition according to the above 8, wherein the compound represented by the general formula (I) comprises a mixture of acid monostearate phosphate and acid distearate phosphate. 10. The wavelength-selective transmissive aromatic polycarbonate resin composition according to any one of 1 to 9 above, further comprising a composition selected from the group consisting of a thermal stabilizer, an antioxidant, a mold release agent, an ultraviolet absorber, and a softener , at least one of the group of antistatic agents and impact modifiers. 11. A wavelength-selective transmissive aromatic polycarbonate resin molded article comprising the wavelength-selective transmissive aromatic polycarbonate resin composition according to any one of 1 to 10 above. 12. The wavelength-selective transmissive aromatic polycarbonate resin molded article according to 11 above, which is a lidar cover. 13. A method for producing a wavelength-selective transmissive aromatic polycarbonate resin molded article, comprising the step of molding the resin composition according to any one of 1 to 10 above. [Effect of invention]

The polycarbonate resin composition of the embodiment of the present invention can be molded using a conventional apparatus to manufacture 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 article which suitably has wavelength selectivity and does not substantially change in optical properties. This molded product can be preferably used for lidar applications.

The wavelength-selective transmissive polycarbonate resin composition according to the embodiment of the present invention includes an aromatic polycarbonate resin (A), a colorant (B) containing a dye having a maximum absorption wavelength of less than 900 nm, and a phosphoric acid ester compound or phosphoric acid (C), With respect to 100 parts by mass of the aromatic polycarbonate resin (A), contains 0.01 to 2.0 parts by mass of a colorant (B), and The phosphoric acid or the phosphoric acid ester compound (C) contains 0.005 to 0.3 parts by mass of the phosphoric acid ester compound (C1) or 0.0001 to 0.004 parts by mass of phosphoric acid (C2).

In the embodiment of the present invention, the "aromatic polycarbonate resin (A)" is a polycarbonate resin based on an aromatic compound, and is not particularly limited as long as the target aromatic polycarbonate resin composition can be obtained in the present invention . 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 can be exemplified. Various polymers obtained by the transesterification method of the reaction. 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-bis (4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)benzenemethane, 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, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; 1,1 -Bis(hydroxyaryl)cycloalkanes such as bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane; 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether and other dihydroxydiaryl ethers; 4,4'-dihydroxydiphenyl sulfide and other dihydroxydiaryl sulfides; 4 ,4'-Dihydroxydiphenylene, 4,4'-dihydroxy-3,3'-dimethyldiphenylene and other dihydroxydiarylidene; 4,4'-dihydroxy Dihydroxy diaryl bismuths such as diphenyl bismuth and 4,4'-dihydroxy-3,3'-dimethyldiphenyl bismuth. These and the like may be used alone or in combination. In addition to these, piperidine, dipiperidinyl hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, etc. may be used in combination.

Furthermore, the above-mentioned dihydroxydiaryl compound can also be used in combination with, for example, a trivalent or higher-valent aromatic compound shown below.

Examples of the above trivalent or higher phenol compound include 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-hydroxy 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 producing such an aromatic polycarbonate resin (A), a molecular weight regulator, a catalyst, etc. may be used as needed. As such an aromatic polycarbonate resin, a commercial item can be used.

In the embodiment of the present invention, the so-called coloring agent (B) containing a pigment whose absorption maximum wavelength is less than 900 nm refers to a coloring agent containing a pigment whose maximum absorption wavelength is less than 900 nm, and the pigment can be selected from, for example, dyes (organic, Inorganic), pigments (organic, inorganic), etc., are not particularly limited as long as the present invention can obtain the target aromatic polycarbonate resin composition. As such a dye, either a dye or a pigment can be used, but in general, it is difficult for a dye to diffusely reflect light on the particle surface, so it is more preferable to use a dye. The coloring agent (B) containing these pigments may 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, 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 composed of particles smaller than that of 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 dyes are more preferably used for Lidar applications.

Examples of the above-mentioned pigment-based dyes include azo-based (soluble azo-based, insoluble azo-based) dyes, condensation-based dyes, anthracene-based dyes, quinacridone-based dyes, bismuth-based dyes, and isoindole-based dyes. Organic pigments such as morphine 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, and synthetic iron black.

The colorant (B) preferably comprises a colorant (B1) and/or a colorant (B2), wherein the colorant (B1) contains a pigment whose absorption maximum wavelength is less than 700 nm, and the colorant (B2) contains a colorant above 700 nm And pigments with maximum absorption wavelength within the range of less than 900 nm.

In the embodiment of the present invention, the coloring agent (B1) containing a pigment whose absorption maximum wavelength is 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 colorant (B1) preferably contains an anthraquinone-based dye.

(B1) The colorant 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 colorant (b1), in addition to the anthraquinone-based dye, a plurality of other dyes may be used in combination. For example, it can be a combination of pigment and pigment, a combination of pigment and dye, and a combination of dye and dye, but it is preferable to use a combination of dye and dye. It is preferable to use an anthraquinone-based dye in combination with other dyes in terms of being able to suppress or block light of various wavelengths and to have good light transmittance in various wavelength regions.

The above-mentioned dyes are not particularly limited as long as the composition of the embodiment of the present invention can be obtained, and specifically, the following ones 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.

As the pyreneone-based dye, commercially available dyes such as Solvent Orange 60, Solvent Orange 78, Solvent Orange 90, Solvent Violet 29, Solvent Red 135, Solvent Red 162, and Solvent Red 179 can be mentioned.

Examples of perylene-based dyes 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.

As the methine-based dye, commercially available dyes with color indices such as Solvent Orange 80, Solvent Yellow 93, and Disperse Yellow 201 are exemplified. Moreover, as a quinoline type dye, the pigment|dye marketed by the color index, such as Solvent Yellow 33, Solvent Yellow 98, Solvent Yellow 157, Disperse Yellow 54, and Disperse Yellow 201, can be mentioned.

In the embodiment of the present invention, the coloring agent (B2) containing a pigment with a maximum absorption wavelength in the range of 700 nm or more and less than 900 nm preferably contains 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, and examples of such a phthalocyanine-based dye include FDN-002, FDN-023, and FDN-024 commercially available from Yamada Chemical Industry Co., Ltd.

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

The coloring agent (B2) preferably contains an anthraquinone-based dye, and examples of such an anthraquinone-based dye include SDO-C33 commercially available from our chemical industry company.

The resin composition of the embodiment of the present invention preferably contains 0.01 to 2.0 parts by mass of a colorant (B) containing a dye 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 preferable to contain 0.012-1.5 mass parts, and it is still more preferable to contain 0.014-1.0 mass parts. The lower limit of the content of the colorant (B) may be 0.02 part by mass or 0.025 part by mass.

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

Formula (I): O=P(OH) _n (OR) _3-n [In formula (I), R is an alkyl group or an aryl group, which may be the same or different, and n represents an integer of 0-2].

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, more preferably an alkyl group having 2 to 25 carbon atoms. Moreover, m is preferably 1 or 2. Examples of the phosphate-based compound of the formula (I) include monostearyl acid phosphate and distearate acid phosphate, and stearyl phosphate mixed ester (about 50 mol% of monostearyl phosphate) is known. A mixture with about 50 mol% of distearyl phosphate, trade name "AX-71" manufactured by Adeka Co., Ltd.) and the like.

Phosphoric acid is a nonvolatile weak acid, and commercially available products can be used without particular limitation, and examples thereof include phosphoric acid manufactured by Nacalai Tesque, phosphoric acid manufactured by Wako Pure Chemical Industries, and the like.

In the resin composition of the embodiment of the present invention, the phosphoric acid ester compound or phosphoric acid (C) preferably contains 0.005 to 0.3 parts by mass of the phosphoric acid ester based on 100 parts by mass of the aromatic polycarbonate resin (A). It is more preferable to contain 0.007-0.1 mass part of compound (C1), and it is still more preferable to contain 0.009-0.08 mass part. Or it is preferable to contain 0.0001-0.004 mass part of phosphoric acid (C2), Preferably it contains 0.0001-0.001 mass part, More preferably, it contains 0.0003-0.0008 mass part, More preferably, it contains 0.0004-0.0006 mass part.

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

The phosphorus-based antioxidant is not particularly limited as long as the present invention can obtain the target aromatic polycarbonate resin composition, but it is preferable to include a phosphite compound having the following phosphite structure. [hua 1]

In the aromatic polycarbonate resin composition according to the embodiment of the present invention, the phosphorus-based antioxidant (D) preferably contains a phosphite compound represented by the following formula (11), the following formula (12) At least one or more compounds among the phosphite compound represented by the phosphite compound represented by the following formula (13), and the phosphite ester compound represented by the following formula (14).

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

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

(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 above formula (11), R ¹ is an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms.

Examples of the compound represented by the formula (11) include triphenyl phosphite, tricresyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and trinonylbenzene phosphite. esters, etc. Among them, tris(2,4-di-tert-butylphenyl) phosphite is particularly preferred, for example, Irgafos 168 (“Irgafos” is a registered trademark of BASF Societas Europaea) can be obtained commercially.

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

(式中，R ²、R ³、R ⁵及R ⁶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；R ⁴表示氫原子或碳數1～8之烷基；X表示單鍵、硫原子或式：-CHR ⁷-所表示之基(其中，R ⁷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：∗-COR ⁸-所表示之基(其中，R ⁸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): [Chemical 3]

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

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

Here, examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, th Tripentyl, isooctyl, third octyl, 2-ethylhexyl and the like. As a C5-C8 cycloalkyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group etc. are mentioned, for example. Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 1-methylcyclopentyl, 1-methylcyclohexyl, 1-methyl-4-isopropylcyclohexyl, 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.

Preferably, the above-mentioned R ² , R ³ and R ⁵ are each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl group having 6 to 12 carbon atoms. More preferably, R ² and R ⁵ are each independently a tertiary alkyl group such as a tertiary butyl group, a tertiary pentyl group, and a tertiary octyl group, a cyclohexyl group, or a 1-methylcyclohexyl group. It is especially preferred that R ³ is an alkane having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and tert-pentyl group, more preferably R ³ is methyl, tertiary butyl or tertiary pentyl.

The above R ⁶ is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, and more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-propyl An alkyl group having 1 to 5 carbon atoms such as butyl, isobutyl, sec-butyl, tert-butyl, and tert-pentyl.

In 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 description of the above 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, more preferably a hydrogen atom or a methyl group.

In 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 having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 5 to 8 carbon atoms include the alkyl groups and cycloalkyl groups exemplified in the descriptions of the above R ² , R ³ , R ⁵ and R ⁶ , 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 formula (12), A represents an alkylene group having 1 to 8 carbon atoms or a group represented by the formula: ∗-COR ⁸ -. Examples of alkylene groups having 1 to 8 carbon atoms include methylene, ethylidene, propylidene, butylene, pentamethylene, hexamethylene, octamethylene, 2,2- Dimethyl-1,3-propylidene, etc., preferably propylidene. 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 ethylidene. In addition, in the formula: ∗-COR ⁸ -, ∗ is a bond on the oxygen side, indicating that the carbonyl group is bonded to the oxygen atom of the phosphite group.

In formula (12), any one of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an aralkoxy group having 7 to 12 carbon atoms, and the other one represents a hydrogen atom or a carbon number 1 to 8. the alkyl group. 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 group having 7 to 12 carbon atoms include benzyloxy group, α-methylbenzyloxy group, 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 description of the above R ² , R ³ , R ⁵ and R ⁶ .

As a compound represented by 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]dioxaphosphetene, 6-[3-(3,5-di-tert-butyl-4-hydroxybenzene yl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphetene, 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] Dioxaphosphacyclo, 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]dioxaphosphacycle, etc. Among them, 2,4,8,10-tetra-tert-butyl-6-[3- (3-Methyl-4-hydroxy-5-tert-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphetene, e.g. Purchased Sumilizer GP ("Sumilizer" is a registered trademark) manufactured by Sumitomo Chemical Co., Ltd.

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

(式中，R ⁹及R ¹⁰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): [Chemical 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, phenylbisphenol A pentaerythritol diphosphite, etc. are mentioned, for example. Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite is commercially available under the trade name "Adekastab PEP-24G" manufactured by ADEKA Corporation. Adekastab PEP-36 (“Adekastab” is a registered trademark) manufactured by ADEKA Corporation (stock) is commercially available.

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

Formula (14): [Formula 5]

(In the formula, R ¹¹ to R ¹⁸ each independently represent an alkyl or alkenyl group having 1 to 3 carbon atoms; R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ , and R ¹⁷ and R ¹⁸ may be 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 carbon atom; when X ¹ to X ⁴ are single bonds, the functional groups in R ¹¹ to R ²² connected to the single bonds are excluded from the general formula (14).

As a specific example of the compound represented by Formula (14), bis (2, 4- dicumyl phenyl) pentaerythritol diphosphite is mentioned, for example. This compound is commercially available under the trade name "Doverphos (registered trademark) S-9228" manufactured by Dover Chemical Co., Ltd., and "Adekastab PEP-45" (bis(2,4-diiso) Propylphenyl) pentaerythritol diphosphite).

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

Preferably, the above-mentioned aromatic polycarbonate resin composition 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]dioxaphosphine; The phosphite compound represented by the above formula (13) contains 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa- 3,9-diphosphaspiro[5,5]undecane; and The phosphite compound represented by the above formula (14) includes bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

The amount of the phosphorus-based antioxidant (D) is preferably 0.5 parts by mass or less, 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, according to the application of the molded article obtained by molding the aromatic polycarbonate resin composition, for example, an ultraviolet absorber may be appropriately used in the aromatic polycarbonate resin composition of the embodiment, which absorbs ultraviolet rays. 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 triazole-based compound, a benzophenone-based compound, an oxalic acid aniline-based compound, and other ultraviolet absorbers that are usually formulated in polycarbonate resins can be used, which can be used alone or Use two or more in combination.

Examples of the benzotriazole-based compound 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-tert-pentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2H-benzotriazole Triazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidomethyl)phenol, 2-(2-hydroxy-4-octyloxy phenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-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-tert-octylphenyl) benzotriazole and the like are particularly preferred, for example, TINUVIN 329 (TINUVIN is a registered trademark) manufactured by BASF Corporation, TINUVIN 329 (TINUVIN is a registered trademark), SHIPRO KASEI (stock) ) manufactured by SEESORB 709, Chemisorb 79 manufactured by CHEMIPRO KASEI Co., Ltd., etc.

As the tris' compound, for example, 2,4-diphenyl-6-(2-hydroxyphenyl-4-hexyloxyphenyl)1,3,5-trisium, 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 and the like are commercially available.

As an oxalate aniline-based compound, for example, Sanduvor VSU etc. by Clariant Japan Co., Ltd. are commercially available.

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

The quantity of an ultraviolet absorber is 0-1.0 mass part with respect to 100 mass parts of aromatic polycarbonate resin (A), Preferably it is 0-0.5 mass part. When the amount of the ultraviolet absorber exceeds 1.0 part by mass, there is a possibility that the initial hue of the obtained aromatic polycarbonate resin composition may decrease. In addition, 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 can be greatly exerted.

Further, within the range that does not impair the effect of the present invention, in the aromatic polycarbonate resin composition of the embodiment, for example, heat stabilizers, other antioxidants, and mold release agents can be appropriately blended (for example, 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 according to the embodiment of the present invention, a production method can be exemplified by mixing an aromatic polycarbonate resin (A), a colorant (B), and a phosphoric acid ester compound or phosphoric acid (C), The phosphorus-based antioxidant (D), the above-mentioned various additives, and polymers other than the aromatic polycarbonate resin (A), etc. are mixed as necessary. The production method is not particularly limited as long as the target aromatic polycarbonate resin composition can be obtained in the present invention, and the types and amounts of each component can be appropriately adjusted. The mixing method of the components is also not particularly limited, and for example, a method of mixing with a known mixer such as a tumbler and a belt mixer, or a method of melt-kneading with an extruder can be exemplified. Particles of the aromatic polycarbonate resin composition can be easily obtained by these methods.

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 those of general resin particles. For example, the shape of the particles includes an elliptical columnar shape, a columnar shape, and the like. The particle size is preferably about 2-8 mm in length. In the case of an elliptical columnar shape, it is preferable that the long diameter of the cross-section ellipse is about 2-8 mm, and the short diameter is about 1-4 mm. In the case of the shape, the diameter of the cross-sectional circle is preferably about 1 to 6 mm. Furthermore, each particle obtained may be this size, all particles forming the particle aggregate may be this size, and the average value of the particle aggregate may be this size, and there is no particular limited.

Regarding the thermal stability of the resin composition according to the embodiment of the present invention, it is preferable that the Δ after the molded article is retained for 10 minutes is 200 nm or less, the Δ after the molded article is retained for 30 minutes is preferably 200 nm or less, and more preferably The Δ after the molded article was retained for 60 minutes was 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 according to the embodiment of the present invention, it is preferable that the molecular weight of the molded article is 16,000 or more after the molded article is allowed to stand at 85° C. and 95% RH for 240 hours, and it is more preferable that the molded article is kept at 120° C. After standing for 240 hours under the same conditions, its molecular weight is 16,000 or more. The reliability of the resin composition can be measured by the method described in the examples.

The molded article 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.

The method for producing the molded article is not particularly limited as long as the intended molded article can be obtained in the present invention, and examples thereof include a method of molding the aromatic polycarbonate resin composition by a known injection molding method, compression molding method, or the like.

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

The embodiments have been described above as exemplifications 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 by way of Examples and Comparative Examples, but these Examples are only one aspect of the present invention, and the present invention is not limited by these Examples.

The ingredients used in this example are shown below. (A) Aromatic polycarbonate resin (a1) Polycarbonate resin synthesized from bisphenol A and carbonyl chloride Viscosity-average molecular weight: 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 absorption maximum wavelength less than 900 nm (b1) Anthraquinone-based pigment (Solvent Blue 97) Macrolex Blue RR (trade name) manufactured by Bayer AG, maximum absorption wavelength: 630 nm [Chem. 6]

(b2) Anthraquinone-based dye (Solvent Green 28) Macrolex Green G (trade name) manufactured by Bayer AG, maximum absorption wavelength: 690 nm [Chem. 7]

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

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

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

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

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

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

(b11) Heterocyclic dye (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(H ₃PO ₄) (C) Phosphoric acid or phosphoric acid ester compound (c1) Phosphate compound compound stearyl phosphate (a mixture of about 50 mol% of monostearyl phosphate and about 50 mol% of distearyl phosphate; ADEKA company ( Adekastab "AX-71 (trade name)") manufactured by Co., Ltd. [Chemical 11]

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

(D) Phosphorus-based antioxidants (d1) Phosphorus-based 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 Rikemal S-100A (trade name) manufactured by Riken Vitamin (stock)

These components were prepared 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 at a cylinder temperature of 320°C and a mold temperature of 100°C using J100 E2P manufactured by Nippon Steel, and was then retained in the cylinder (320°C) for 10, For 30 and 60 minutes, a molded product (1 mm) was obtained. Regarding 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 properties was quantified as follows. The transmittance was measured every 2 nm from 1050 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 decrease ended (hereinafter referred to as the decrease end wavelength) was measured. The case where the reduction start wavelength - the reduction end wavelength (Δ) was 200 nm or less was regarded as a good product. The case where Δ was 200 nm or more was regarded as defective. Furthermore, in a specific wavelength selective filter, the optical spectrum is expected to be steep, and when the wavelength difference is large, that is, when the above-mentioned Δ is 200 nm or more (the case where it is not steep), the filter may be abnormal. So 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 method. Using J100 E2P manufactured by Nippon Steel, the polycarbonate resin composition was molded at a cylinder temperature of 320°C and a mold temperature of 100°C, and the molded product was evaluated under the conditions of 85°C, 95% RH, and 120°C for heat aging resistance. Each of the samples was left to stand for 240 hours to obtain a sample (for evaluation). Its weight average molecular weight was determined. The case where the weight average molecular weight was 16,000 or more was regarded as a good product, and the case where the weight average molecular weight was less than 16,000 was regarded as a poor product. The weight average molecular weight was measured using an Alliance HPLC system manufactured by Nihon Waters Corporation as a GPC apparatus. As a column for GPC, PLgel 5 μm MiniMIX-C manufactured by Agilent Technologies was used. Using dichloromethane as a solvent, the sample was dissolved to prepare a solution. The measured value was obtained by using THF (Tetrahydrofuran, tetrahydrofuran) as an eluent, and passing this solution through the column at a flow rate of 0.3 mL/min at 40°C. A calibration curve for gel permeation chromatography (GPC) was prepared using a sample with a known weight average molecular weight (monodispersed polystyrene), and the measured value was 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 Lower onset wavelength (after 60 minutes residence time) 828nm 848nm 830nm 854nm 778nm 778nm 800nm 798nm Thermal stability benchmark 114nm 114nm 110 nm 112nm 100 nm 100 nm 110 nm 110 nm Stay for 10 minutes 108 nm 112nm 110 nm 120nm 100 nm 100 nm 108 nm 110 nm Stay for 30 minutes 110 nm 126nm 114nm 136nm 104 nm 104 nm 110 nm 112nm Stay for 60 minutes 108 nm 134nm 122nm 148nm 102nm 108 nm 110 nm 118 nm judge ○ ○ ○ ○ ○ ○ ○ ○ 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 judge ○ 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 Lower onset wavelength (after 60 minutes residence time) 898nm 861 nm 900nm 846nm 935 nm Thermal stability benchmark 130nm 118 nm 108 nm 120nm 130nm Stay for 10 minutes 132nm 120nm 110 nm 120nm 128nm Stay for 30 minutes 130nm 120nm 108 nm 120nm 128nm Stay for 60 minutes 134nm 120nm 108 nm 122nm 130nm judge ○ ○ ○ ○ ○ reliability benchmark 23000 23000 23000 23000 23000 85℃ 95% RH 18000 18000 18000 18000 18000 120℃ 0% RH 21000 21000 21000 21000 21000 judge ○ 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 Lower onset wavelength (after 60 minutes residence time) 1040nm 984nm 830nm 828nm Thermal stability benchmark 122nm 114nm 108 nm 110 nm Stay for 10 minutes 274nm 282nm 110 nm 110 nm Stay for 30 minutes 366nm 370nm 108 nm 110 nm Stay for 60 minutes 380 nm 376nm 108 nm 112nm judge × × ○ ○ reliability benchmark 23000 23000 19000 19000 85℃ 95% RH 18000 18000 11000 11000 120℃ 0% RH 21000 21000 15000 15000 judge 〇 〇 × ×

The polycarbonate resin compositions of Examples 1 to 13 comprise an aromatic polycarbonate resin (A), a colorant (B) containing a pigment having a maximum absorption wavelength of less than 900 nm, and a phosphoric acid ester compound or phosphoric acid (C) , relative to 100 parts by mass of the aromatic polycarbonate resin (A), 0.01 to 2.0 parts by mass of the coloring agent (B), and 0.005 to 0.3 parts by mass of the phosphoric acid or phosphoric acid ester compound (C) It is a 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 the wavelength-selective transmissive polycarbonate resin compositions for filters.

In the molded articles of Comparative Examples 1 and 2, since the transmittance reduction start wavelength shifted to the long wavelength side, and the wavelength width from the transmittance reduction start wavelength to the reduction end wavelength was large, the near-infrared rays of 850-950 nm used in lidar could not be used. appropriate through. Therefore, there is a possibility that the detection capability of the lidar is lowered. On the other hand, in the case of Examples 1 to 13 using the phosphate compound of the present invention or phosphoric acid, even if the residence time was 60 minutes, the transmittance reduction starting wavelength and wavelength width did not change significantly, which clearly can be improved. Appropriately transmits near infrared rays from 850 nm to 950 nm, and is excellent as a wavelength selective filter.

When an excess amount of phosphoric acid ester or phosphoric acid was prepared as in Comparative Examples 3 and 4, the molecular weight after the reliability test was significantly reduced, and the impact resistance required for the polycarbonate resin was impaired. When used as a lidar cover, it may collide with road stones, etc., and the cover may be damaged, and other abnormalities may occur. On the other hand, when the phosphoric acid ester and phosphoric acid were added in an appropriate amount, it was found that there was no significant decrease in molecular weight, and the properties of the polycarbonate resin could be maintained. [Industrial Availability]

The polycarbonate resin composition of the embodiment of the present invention can be molded using a conventional apparatus to manufacture 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 article which suitably has wavelength selectivity and does not substantially change in optical properties. This molded product can be preferably used for lidar applications.

related applications This application is based on Article 4 of the Paris Convention, and is claimed on the basis of Application No. 2019-146366 filed in Japan on August 8, 2019 and Application No. 2020-077493 filed in Japan on April 24, 2020 priority. The contents of these basic applications are incorporated into this specification by reference.

Claims (15)

A wavelength selective transmittance aromatic polycarbonate resin composition, characterized in that it comprises an aromatic polycarbonate resin (A), a colorant (B) containing a pigment whose maximum absorption wavelength is less than 900 nm, and a phosphorus-based anti-aging agent. oxidizing agent (D), and With respect to 100 parts by mass of the aromatic polycarbonate resin (A), The coloring agent (B) is contained in 0.01-2.0 mass parts. The wavelength-selective transmissive aromatic polycarbonate resin composition according to claim 1, wherein the colorant (B) contains a colorant (B1) and/or a colorant (B2), and the colorant (B1) contains an absorption maximum wavelength The coloring agent (B2) above contains pigments with a maximum absorption wavelength in the range of 700 nm or more and less than 900 nm. As claimed in claim 1 or 2, the wavelength-selective transmissive aromatic polycarbonate resin composition, wherein the colorant (B) containing a pigment whose maximum absorption wavelength is less than 900 nm comprises anthraquinone-based pigments, pyreneone-based pigments, At least one of perylene-based dyes, methine-based dyes, azo-based dyes, quinoline-based dyes, phthalocyanine-based dyes, and heterocyclic dyes. The wavelength-selective transmissive aromatic polycarbonate resin composition according to claim 2, wherein the colorant (B1) containing a colorant with a maximum absorption wavelength of less than 700 nm comprises a colorant selected from the group consisting of anthraquinone-based coloring matter, pyreneone-based coloring matter, perylene At least one of a colorant and a methine-based colorant. The wavelength-selective transmissive aromatic polycarbonate resin composition according to claim 2 or 4, wherein the colorant (B1) containing a dye whose absorption maximum wavelength is less than 700 nm includes an anthraquinone-based dye. The wavelength-selective transmissive aromatic polycarbonate resin composition according to claim 5, wherein the anthraquinone-based pigment comprises the group consisting of Solvent Yellow 163, Disperse Violet 28, Solvent Blue 97, Solvent Green 28, Solvent Green 3, Disperse Blue 60 At least 1 species in the group formed. The wavelength-selective transmissive aromatic polycarbonate resin composition of claim 2 or 4, wherein the colorant (B2) containing a pigment with a maximum absorption wavelength in the range of 700 nm or more and less than 900 nm comprises a phthalocyanine selected from the group consisting of At least one type of dyes, anthraquinone-based dyes, and heterocyclic dyes. The wavelength-selective transmissive aromatic polycarbonate resin composition according to claim 1, 2 or 4, which contains 0.5 parts by mass or less of the phosphorus-based antioxidant ( D). The wavelength-selective transmissive aromatic polycarbonate resin composition according to claim 8, wherein the phosphorus-based antioxidant (D) comprises a phosphite compound having the following phosphite structure:

. The wavelength-selective transmissive aromatic polycarbonate resin composition according to claim 8, wherein the phosphorus-based antioxidant (D) comprises a phosphite compound represented by the following formula (11), the following formula (12) At least one compound of the phosphite compound represented by the following formula (13), the phosphite ester compound represented by the following formula (14), and the phosphite ester compound represented by the following formula (14): Formula (11):

(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, and a represents an integer of 0 to 3) Formula (12):

(In the formula, R ² , R ³ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkyl ring having 6 to 12 carbon atoms. Alkyl group, aralkyl group with 7-12 carbon atoms or phenyl group; R ⁴ represents hydrogen atom or alkyl group with 1-8 carbon number; X represents single bond, sulfur atom or group represented by formula: -CHR ⁷ -( Wherein, R ⁷ represents a hydrogen atom, an alkyl group with 1 to 8 carbon atoms or a cycloalkyl group with 5 to 8 carbon atoms); A represents an alkylene group with 1 to 8 carbon atoms or the formula: *-COR ⁸ - represented by group (wherein, R ⁸ represents a single bond or an alkylene group with 1 to 8 carbon atoms, and ∗ represents a bond on the oxygen side); any one of Y and Z represents a hydroxyl group, an alkoxy group with 1 to 8 carbon atoms, or Aralkoxy with 7 to 12 carbon atoms, and the other one represents a hydrogen atom or an alkyl group with 1 to 8 carbon atoms) Formula (13):

(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) Formula (14):

(In the formula, R ¹¹ to R ¹⁸ each independently represent an alkyl or alkenyl group having 1 to 3 carbon atoms; R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ , and R ¹⁷ and R ¹⁸ may be 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 carbon atom; when X ¹ to X ⁴ are single bonds, the functional groups in R ¹¹ to R ²² connected to the single bonds are excluded from the general formula (14). The wavelength-selective transmissive aromatic polycarbonate resin composition of claim 1, 2 or 4, further comprising a composition selected from the group consisting of heat stabilizers, antioxidants, mold release agents, ultraviolet absorbers, softeners, antistatic agents and At least one of the group of impact modifiers. The wavelength-selective transmissive aromatic polycarbonate resin composition according to claim 1, 2 or 4, which further contains a release agent. A wavelength-selective transmissive aromatic polycarbonate resin molded article comprising the wavelength-selective transmissive aromatic polycarbonate resin composition according to any one of claims 1 to 12. The wavelength-selective transmissive aromatic polycarbonate resin molded article of claim 13, which is a lidar cover. A method for producing a wavelength-selective transmissive aromatic polycarbonate resin molded article, comprising the step of molding the resin composition according to any one of claims 1 to 12.