TWI828099B - Wavelength selective transmission polycarbonate resin composition - Google Patents

Abstract

The present invention is a wavelength-selective and transparent polycarbonate resin composition, which 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 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 contains 0.005 to 0.3 parts by mass of the phosphate ester compound or phosphoric acid (C) parts of the phosphate ester compound (C1) or 0.0001 to 0.004 parts by mass of phosphoric acid (C2).

Description

Wavelength selective transmission polycarbonate resin composition

The present invention relates to a wavelength-selective transmissive polycarbonate resin composition, and more specifically, to a wavelength-selective transmissive polycarbonate resin composition that is impermeable to visible light but transmissible to infrared rays.

As one of the telemetry technologies using 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 that the method measures scattered light irradiated with pulsed laser light and analyzes the distance to a distant object or the properties of the object. This technique is similar to radar in that it replaces 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 using ultraviolet, visible light, and near-infrared rays.

In recent years, autonomous vehicle technology has been developing rapidly. In order to cope with Level 3 of conditional autonomous driving and Levels 4 to 5 that do not require driver's driving, it must have the function of safe autonomous driving on highways and ordinary roads. Therefore, in order to ensure sensing redundancy, in addition to cameras and millimeter-wave radar, lidar has also received attention. In order to support autonomous driving, the accuracy of Lidar needs to be further improved, and the development of wavelength selective filters with better performance is required.

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

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

[Problem to be solved by the invention]

Patent Document 1 discloses a cured body of epoxy resin, but the cured body of epoxy resin is not necessarily suitable for being provided in large quantities at low cost. Considering the future development of Lidar, it is necessary to provide a composition and its molded product that can be produced more cheaply and in large quantities.

The present inventors have focused on molded products of polycarbonate having excellent transparency and excellent mechanical strength. However, they have found that since the molding temperature of polycarbonate is relatively high, the transmittance decreases during molding of the polycarbonate resin composition at high temperatures. It may decrease and/or increase, that is, the transmittance (optical characteristics) may change. Changes in optical characteristics may cause malfunction. Therefore, an object of the present invention is to provide a polycarbonate resin composition and a molded article thereof that have wavelength-selective transmission properties without substantial change in optical properties even when molding is performed at high temperatures. [Technical means to solve problems]

The inventors of the present invention repeatedly conducted intensive research and found that a polycarbonate resin composition containing a colorant containing a pigment with a maximum absorption wavelength of less than 900 nm (such as an anthraquinone-based pigment) and a phosphoric acid or phosphate ester compound provides a A polycarbonate resin composition with wavelength-selective transmission properties that does not substantially change its optical properties even when molded at high temperatures, and its molded products. Furthermore, it was discovered that such a resin composition and molded article can be suitably used for lidar applications, and the present invention was completed.

This manual includes the following forms. 1. A wavelength-selective and transparent aromatic polycarbonate resin composition, characterized in that it contains an aromatic polycarbonate resin (A), a colorant (B) containing a pigment with a maximum absorption wavelength of less than 900 nm, and phosphoric acid The ester-based 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 phosphate ester-based compound (C) contains 0.005 to 0.3 parts by mass of the phosphate ester compound (C1) or 0.0001 to 0.004 parts by mass of phosphoric acid (C2). 2. The wavelength-selective 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 Pigments with maximum absorption wavelengths less than 700 nm. The above-mentioned colorant (B2) contains pigments with maximum absorption wavelengths above 700 nm and less than 900 nm. 3. The wavelength-selective aromatic polycarbonate resin composition as described in the above 1 or 2, wherein the coloring agent (B) containing a pigment with a maximum absorption wavelength of less than 900 nm is selected from the group consisting of anthraquinone pigments and pyrenones. At least one type of pigments, perylene pigments, methine pigments, azo pigments, quinoline pigments, phthalocyanine pigments and heterocyclic pigments. 4. The wavelength-selective aromatic polycarbonate resin composition as described in 2 above, wherein the colorant (B1) containing a pigment having a maximum absorption wavelength of less than 700 nm is selected from the group consisting of anthraquinone-based pigments and pyrenone-based pigments. At least one of pigments, perylene-based pigments, and methine-based pigments. 5. The wavelength-selective aromatic polycarbonate resin composition according to the above 2 or 4, wherein the colorant (B1) containing a pigment having a maximum absorption wavelength of less than 700 nm contains an anthraquinone-based pigment. 6. The wavelength-selective and transmissive aromatic polycarbonate resin composition as described in the above 5, wherein the anthraquinone-based dye contains a dye selected from the group consisting of Solvent Yellow 163, Dispersed Violet 28, Solvent Blue 97, Solvent Green 28, Solvent Green 3, At least one of the groups consisting of Scatter Blue 60. 7. The wavelength-selective aromatic polycarbonate resin composition as described in any one of 2 and 4 to 6 above, which contains 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-selective aromatic polycarbonate resin composition according to any one of 1 to 7 above, wherein the phosphate ester compound or phosphoric acid (C) is selected from the group consisting of the following general formula (I): At least one of the phosphate ester compounds or the group consisting of 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 can be the same or different, n represents an integer from 0 to 2]. 9. The wavelength-selective aromatic polycarbonate resin composition according to the above 8, wherein the compound represented by the general formula (I) contains a mixture of acid monostearyl phosphate and acid distearyl phosphate. 10. The wavelength-selective aromatic polycarbonate resin composition according to any one of the above 1 to 9, which further contains a heat stabilizer, an antioxidant, a release agent, an ultraviolet absorber, and a softener. , at least one of the group of antistatic agents and impact modifiers. 11. A wavelength-selective and transmissive aromatic polycarbonate resin molded article containing the wavelength-selective and transmissive aromatic polycarbonate resin composition according to any one of 1 to 10 above. 12. The wavelength-selective and transmissive aromatic polycarbonate resin molded article as described in 11 above, which is a lidar cover. 13. A method for producing a wavelength-selective and transmissive aromatic polycarbonate resin molded article, which includes the step of molding the resin composition according to any one of 1 to 10 above. [Effects of the invention]

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

The wavelength-selective transmissive polycarbonate resin composition according to the embodiment of the present invention 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 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 colorant (B), and The phosphoric acid or phosphate compound (C) contains 0.005 to 0.3 parts by mass of the phosphate compound (C1) or 0.0001 to 0.004 parts by mass of the phosphoric acid (C2).

In the embodiment of the present invention, "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 by the present invention. . Examples of such aromatic polycarbonate resins include the phosgene method of reacting a dihydroxydiaryl compound with phosgene, or the reaction of a dihydroxydiaryl compound with a carbonate such as diphenyl carbonate. Various polymers obtained by transesterification reaction. Representative examples include polycarbonate resin produced from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A).

Examples of the dihydroxydiaryl compound other than bisphenol A include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 2,2-bis(4-hydroxyphenyl)ethane. (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, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; 1,1 - Bis(hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane and other bis(hydroxyaryl)cycloalkanes; 4,4'-dihydroxydiphenyl ether, Dihydroxydiaryl ethers such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; dihydroxydiaryl sulfide such as 4,4'-dihydroxydiphenyl sulfide; 4 , 4'-Dihydroxydiphenylsterene, 4,4'-dihydroxy-3,3'-dimethyldiphenylsterene and other dihydroxydiarylsterenes; 4,4'-dihydroxy Dihydroxydiarylsine such as diphenylsine and 4,4'-dihydroxy-3,3'-dimethyldiphenylsine. They can be used alone or in combination. In addition to these, piperidinyl hydroquinone, dipiperidinylhydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, etc. can also be used in combination.

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

Examples of the above-mentioned trivalent or higher phenolic 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 aromatic polycarbonate resin (A), a molecular weight regulator, a catalyst, etc. may be used as needed. As such aromatic polycarbonate resin, commercially available products can be used.

In the embodiment of the present invention, the colorant (B) containing a pigment with a maximum absorption wavelength of less than 900 nm means that the colorant (B) contains a pigment with a maximum absorption wavelength of 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 target aromatic polycarbonate resin composition can be obtained by the present invention. As such pigments, either dyes or pigments can be used, but usually dyes do not easily cause light to diffusely reflect on the particle surface, so it is more preferable to use dyes. The coloring agent (B) containing these pigments can be used alone or in combination of two or more.

Examples of the dye-based pigments include anthraquinone-based pigments, pyrenone-based pigments, perylene-based pigments, methine-based pigments, azo-based pigments, quinoline-based pigments, phthalocyanine-based pigments, heterocyclic pigments, etc. . Oil-soluble dyes are preferred because they can be dispersed in the resin composition more easily and uniformly. 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 article can be reduced, which is preferable. Dyes are better suited for lidar applications.

Examples of the pigment-based dyes include azo-based dyes (soluble azo-based dyes, insoluble azo-based dyes), condensation-based dyes, anthracene-based dyes, quinacridone-based dyes, bistriol-based dyes, and isoindole-based dyes. Organic pigments such as pholine 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.

Colorant (B) preferably contains colorant (B1) and/or colorant (B2), wherein colorant (B1) contains a pigment whose absorption maximum wavelength is less than 700 nm, and colorant (B2) contains a colorant above 700 nm. And it does not have pigments with maximum absorption wavelength in the range of 900 nm.

In the embodiment of the present invention, the coloring agent (B1) containing a pigment whose maximum absorption wavelength is less than 700 nm is preferably selected from the group consisting of anthraquinone pigments, pyrenone pigments, perylene pigments, and methine pigments. At least 1 of them. The coloring agent (B1) preferably contains an anthraquinone-based pigment.

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

In the resin composition according to the embodiment of the present invention, as the coloring agent (b1), in addition to the anthraquinone-based pigment, a plurality of other pigments may be used in combination. For example, a combination of a pigment and a pigment, a combination of a pigment and a dye, or a combination of a dye and a dye is possible. However, 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 anthraquinone pigments in combination with other pigments.

The dye is not particularly limited as long as the composition according to the embodiment of the present invention can be obtained. Specifically, the following dyes 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 pyrenone-based dyes include dyes commercially available with color indexes such as Solvent Orange 60, Solvent Orange 78, Solvent Orange 90, Solvent Violet 29, Solvent Red 135, Solvent Red 162, and Solvent Red 179.

Examples of perylene 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 commercially available with color indexes such as Solvent Orange 80, Solvent Yellow 93, and Disperse Yellow 201. Examples of quinoline dyes include dyes commercially available with color indexes such as Solvent Yellow 33, Solvent Yellow 98, Solvent Yellow 157, Disperse Yellow 54, Disperse Yellow 201, and the like.

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 is preferably selected from the group consisting of phthalocyanine pigments, anthraquinone pigments and heterocyclic pigments. At least one of the pigments.

(B2) The coloring agent preferably contains a phthalocyanine-based pigment, and examples of such phthalocyanine-based pigments 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. Examples of such a heterocyclic dye include SDO-C8 commercially available from Yuhon Chemical Industry Co., Ltd. and the like.

(B2) The coloring agent preferably contains an anthraquinone-based pigment, and examples of the anthraquinone-based pigment include SDO-C33 commercially available from Arihon Chemical Industry Co., Ltd.

The resin composition according to the embodiment of the present invention preferably contains 0.01 to 2.0 parts by mass of a colorant (B) containing a pigment with a maximum absorption wavelength of less than 900 nm, based on 100 parts by mass of the aromatic polycarbonate resin (A). More preferably, it contains 0.012-1.5 parts by mass, and still more preferably, it contains 0.014-1.0 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 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 preferably one selected from the following general formula ( I) At least one of the group consisting of the phosphate 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 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, more preferably an alkyl group having 2 to 25 carbon atoms. Moreover, m is preferably 1 or 2. Examples of the phosphate ester compound of formula (I) include acid monostearyl phosphate or acid distearyl phosphate, and stearyl phosphate mixed esters (monostearyl phosphate about 50 mol%) are known. A mixture of about 50 mol% with distearyl phosphate, trade name "AX-71" manufactured by Adeka Co., Ltd.), etc.

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

In the resin composition according to 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 based on 100 parts by mass of the aromatic polycarbonate resin (A). The compound (C1) preferably contains 0.007 to 0.1 parts by mass, and further preferably contains 0.009 to 0.08 parts by mass. Or it is more preferable that it contains 0.0001-0.004 parts by mass of phosphoric acid (C2), it is more preferable that it contains 0.0001-0.001 parts by mass, it is more preferable that it contains 0.0003-0.0008 parts by mass, and it is further more preferable that it contains 0.0004-0.0006 parts by mass.

The aromatic polycarbonate resin composition according to 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 target aromatic polycarbonate resin composition can be obtained in the present invention. However, it is preferable to include a phosphite compound having the following phosphite structure. [Chemical 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) and the following formula (12) At least one compound among 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).

Formula (11): [Formula 2] (In the formula, R ¹ represents an alkyl group with 1 to 20 carbon atoms, and a represents an integer from 0 to 3)

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

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

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

Formula (12): [Formula 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 carbon atoms, a cycloalkyl group with 5 to 8 carbon atoms, and an alkyl ring with 6 to 12 carbon atoms. Alkyl group, aralkyl group with 7 to 12 carbon atoms or phenyl group; R ⁴ represents a hydrogen atom or an alkyl group with 1 to 8 carbon atoms; X represents a single bond, a sulfur atom or a group represented by the formula: -CHR ⁷ - ( Among them, 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 - group (where R ⁸ represents a single bond or an alkylene group with 1 to 8 carbon atoms, and * represents a bond on the oxygen side); either Y and Z represent a hydroxyl group, an alkoxy group with 1 to 8 carbon atoms, or Aralkyloxy group with 7 to 12 carbon atoms, the other represents a hydrogen atom or 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, or an alkyl group having 6 to 12 carbon atoms. Alkylcycloalkyl, aralkyl having 7 to 12 carbon atoms, or phenyl.

Here, examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, and third butyl. tripentyl, isooctyl, tertiary octyl, 2-ethylhexyl, etc. Examples of the cycloalkyl group having 5 to 8 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. 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 benzyl group, α-methylbenzyl group, 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. Particularly preferably, R ² and R ⁵ are each independently a third alkyl group such as a third butyl group, a third pentyl group, a third octyl group, a cyclohexyl group or a 1-methylcyclohexyl group. Particularly preferably, R ³ is an alkane having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, third pentyl, etc. group, more preferably R ³ is methyl, tert-butyl or tert-pentyl.

The above-mentioned 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, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-propyl group, or a hydrogen atom. Butyl, isobutyl, second butyl, third butyl, third pentyl and other alkyl groups with 1 to 5 carbon atoms.

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 R ² , R ³ , R ⁵ and R ⁶ above. 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 the formula (12), X represents a single bond, a sulfur atom or a group represented by the formula: -CHR ⁷ -. Among them, 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 illustrated in the description of R ² , R ³ , R ⁵ and R ⁶ , respectively. X is particularly preferably a single bond, methylene, or methylene substituted by methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc., and more preferably single key.

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, etc., preferably propylene group. Also, formula: ∗-COR ⁸ -where R 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 ethyl group. Also, the formula: ∗-COR ⁸ -where ∗ is the bond on the oxygen side, indicating the bond between the oxygen atom of the carbonyl group and the phosphite group.

In formula (12), either Y or 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 represents a hydrogen atom or a carbon number 1 to 8 The alkyl group. Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, propoxy group, tert-butoxy group, pentyloxy group, and the like. 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 R ² , R ³ , R ⁵ and R ⁶ above.

Examples of the compound represented by formula (12) include: 2,4,8,10-tetratert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butylbenzene) methyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphene, 6-[3-(3,5-di-tert-butyl-4-hydroxybenzene methyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphene, 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]dioxaphosphetacyclo, 6-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propyloxy]-4,8-di-tert-butyl -2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphetacyclo etc. Among them, especially when the obtained aromatic polycarbonate resin composition is used in a field requiring optical properties, 2,4,8,10-tetratertiarybutyl-6-[3- (3-Methyl-4-hydroxy-5-tert-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphene, e.g. commercially available 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).

Formula (13): [Formula 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 from 0 to 3)

Examples of the compound represented by formula (13) include bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, and the like. Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite is commercially available under the trade name "Adekastab PEP-24G" manufactured by ADEKA Co., Ltd. Adekastab PEP-36 ("Adekastab" is a registered trademark) manufactured by ADEKA Co., Ltd. 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 can be mutually exclusive. 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 each independently represent an integer from 0 to 5; X ¹ to X ⁴ each independently represents a single bond Or a carbon atom; when X ¹ to X ⁴ are single bonds, the functional groups connected to the single bonds in R ¹¹ to R ²² are excluding general formula (14)).

Specific examples of the compound represented by formula (14) include bis(2,4-dicumylphenyl)pentaerythritol diphosphite. 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)) manufactured by ADEKA Co., Ltd. propylphenylphenyl) pentaerythritol diphosphite).

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

Preferably, the above 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-tetratert-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) contains 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa- 3,9-diphosphospiro[5,5]undecane; and The phosphite compound represented by the above formula (14) contains bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

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

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

As the ultraviolet absorber, for example, benzotriazole-based compounds, trisulfonate-based compounds, benzophenone-based compounds, oxalate aniline-based compounds, and other ultraviolet absorbers that are usually blended in polycarbonate resins can be used. They can be used alone or Use a combination of 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 ylphenyl)-5-chloro-2H-benzotriazole, 2-(3,5-di-3-pentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2H-benzotriazole Triazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalyliminomethyl)phenol, 2-(2-hydroxy-4-octyloxy ylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tertiary 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] etc. Among them, 2-(2-hydroxy-5-tertiary octylphenyl)benzotriazole and the like are particularly preferred. For example, TINUVIN 329 (TINUVIN is a registered trademark) manufactured by BASF Co., Ltd. and SHIPRO KASEI Co., Ltd. are commercially available. ), Chemisorb 79 manufactured by CHEMIPRO KASEI Co., Ltd., etc.

Examples of the trisulfonate-based compound include: 2,4-diphenyl-6-(2-hydroxyphenyl-4-hexyloxyphenyl)1,3,5-trisaccharide, 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 and the like are commercially available as TINUVIN 1577 manufactured by BASF Corporation.

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

Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and the like.

The amount of the ultraviolet absorber is 0 to 1.0 parts by mass, preferably 0 to 0.5 parts by mass relative to 100 parts by mass of the aromatic polycarbonate resin (A). When the amount of the ultraviolet absorber exceeds 1.0 parts by mass, the initial hue of the obtained aromatic polycarbonate resin composition may be reduced. 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 exerted.

Furthermore, the aromatic polycarbonate resin composition of the embodiment may be suitably blended with a heat stabilizer, other antioxidants, and a release agent (for example, those manufactured by Riken Vitamin Co., Ltd.) within a range that does not impair the effects of the present invention. Rikemal S-100A, etc.), various additives such as softeners, antistatic agents and impact modifiers, polymers other than aromatic polycarbonate resin (A), etc.

The aromatic polycarbonate resin composition according to the embodiment of the present invention can be produced by mixing an aromatic polycarbonate resin (A), a colorant (B), and a phosphate compound or phosphoric acid (C), If necessary, the phosphorus-based antioxidant (D), the above-mentioned various additives, and polymers other than the aromatic polycarbonate resin (A) are mixed. As long as the target aromatic polycarbonate resin composition can be obtained by the present invention, the production method is not particularly limited, and the types and amounts of each component can be appropriately adjusted. The mixing method of the ingredients is not particularly limited, and examples thereof include mixing using a known mixer such as a drum mixer and a belt mixer, or melting and kneading using an extruder. 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, the shape of the particles may include elliptical columnar shape, cylindrical shape, etc. As for the size of the particles, the length is preferably about 2 to 8 mm. In the case of an elliptical cylinder, the major diameter of the cross-sectional ellipse is preferably about 2 to 8 mm and the minor diameter is about 1 to 4 mm. In the case of a cylinder, the particle size is preferably about 2 to 8 mm in length. In the case of a cross-section, the diameter of the cross-section circle is preferably about 1 to 6 mm. Furthermore, each particle obtained may be of this size, all the particles forming the particle aggregate may be of this size, or the average value of the particle aggregate may be of this size, and there is no particular requirement. 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, more preferably the Δ after the molded article is retained for 30 minutes is 200 nm or less, and still more preferably The Δ after the molded product is retained for 60 minutes is 200 nm or less. The thermal stability of the resin composition can be measured by the method described in the Examples.

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 product is 16,000 or more after the molded product is left to stand for 240 hours at 85°C and 95% RH, and more preferably, the molded product is left to stand at 120°C. After standing for 240 hours under these conditions, its molecular weight is over 16,000. The reliability of the resin composition can be measured using the method described in the Examples.

The molded article according to 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 target molded article can be obtained in the present invention. Examples thereof include methods of molding the aromatic polycarbonate resin composition by known injection molding methods, compression molding methods, and the like.

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

The embodiments have been described above as illustrations of the invention. However, the technology in the present invention is not limited to this, and can also be applied to embodiments with appropriate changes, replacements, additions, omissions, etc. [Example]

Hereinafter, the present invention will be described specifically and in detail through Examples and Comparative Examples. However, 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 as follows. (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 Co., Ltd. "SD POLYCA" is a registered trademark of Sumika Polycarbonate Co., Ltd.

(B) Pigments with a maximum absorption wavelength less than 900 nm (b1) Anthraquinone pigments (solvent blue 97) Macrolex Blue RR (trade name) manufactured by Bayer AG, maximum absorption wavelength: 630 nm [Chemical 6]

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

(b3) Anthraquinone-based pigment (SD-3, mixture) Manufactured by Kenei Kogyo Co., Ltd., maximum absorption wavelength: 630 nm (b4) Anthraquinone-based pigment (Solvent Green 3) Manufactured by Mitsui Fine Chemicals Co., Ltd. Mitsui PS Green B (trade name), maximum absorption wavelength: 640 nm [Chemical 8]

(b5) Methine 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 [Chemical 10]

(b7) Phthalocyanine pigments (FDN-002 trade name) Manufactured by Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 807 nm (b8) Phthalocyanine pigments (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 pigment (SDO-C33 trade name) Arihon Chemical Industry Co., Ltd., maximum absorption wavelength: 846 nm

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

(C) Phosphoric acid or phosphate compound (c1) Phosphate compound stearyl phosphate mixed ester (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 Phosphoric acid (H ₃ PO ₄ ) manufactured by Nacalai Tesque Co., Ltd.

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

(x1) Release agent Rikemal S-100A (trade name) manufactured by Riken Vitamin Co., Ltd.

These components were prepared at the mass ratios shown in Tables 1 to 3 to produce polycarbonate compositions of Examples 1 to 13 and Comparative Examples 1 to 4.

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. Then, it was allowed to stay in the cylinder (320°C) for 10, 30 or 60 minutes to obtain a molded product (1 mm). Regarding the optical spectrum of the molded product, the transmission spectrum was evaluated using UH4150 manufactured by Hitachi High-Tech Science Co., Ltd., and the change in optical properties was quantified in the following manner. 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 reduction start wavelength - the reduction end wavelength (Δ) is 200 nm or less is regarded as a good product. The case where Δ is 200 nm or more is considered defective. Furthermore, in a specific wavelength selective filter, the optical spectrum is expected to be steep. When the wavelength difference is large, that is, when the above Δ is 200 nm or more (a case where it is not steep), there may be cases where the filter produces abnormalities. Therefore it is 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. The polycarbonate resin composition was molded using J100 E2P manufactured by Nippon Steel at a cylinder temperature of 320°C and a mold temperature of 100°C. The molded product was evaluated under the conditions of 85°C, 95% RH and heat aging resistance of 120°C. Each was left to stand for 240 hours to obtain a sample (for evaluation). Determine its weight average molecular weight. A product with a weight average molecular weight of 16,000 or more is considered a good product, and a product with a weight average molecular weight of less than 16,000 is considered a defective product. The weight average molecular weight was measured using an Alliance HPLC system manufactured by Nihon Waters Co., Ltd. as a GPC device. As a column for GPC, PLgel 5 μm MiniMIX-C manufactured by Agilent Technologies was used. The sample was dissolved using methylene chloride as a solvent to prepare a solution. THF (Tetrahydrofuran, 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 the measured value. Use a sample with a known weight average molecular weight (monodisperse polystyrene) to prepare a calibration curve for gel permeation chromatography (GPC), and calibrate the measured values 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 Reduce the starting wavelength (after 60 minutes of residence) 828nm 848 nm 830nm 854nm 778 nm 778 nm 800nm 798 nm Thermal stability benchmark 114nm 114nm 110nm 112nm 100nm 100nm 110nm 110nm Stay for 10 minutes 108nm 112nm 110nm 120nm 100nm 100nm 108nm 110nm Stay for 30 minutes 110nm 126nm 114nm 136nm 104nm 104nm 110nm 112nm Stay for 60 minutes 108nm 134nm 122nm 148nm 102nm 108nm 110nm 118nm 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 Reduce the starting wavelength (after 60 minutes of residence) 898 nm 861 nm 900nm 846 nm 935nm Thermal stability benchmark 130nm 118nm 108nm 120nm 130nm Stay for 10 minutes 132nm 120nm 110nm 120nm 128nm Stay for 30 minutes 130nm 120nm 108nm 120nm 128nm Stay for 60 minutes 134nm 120nm 108nm 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 Reduce the starting wavelength (after 60 minutes of residence) 1040nm 984 nm 830nm 828nm Thermal stability benchmark 122nm 114nm 108nm 110nm Stay for 10 minutes 274 nm 282nm 110nm 110nm Stay for 30 minutes 366 nm 370nm 108nm 110nm Stay for 60 minutes 380nm 376 nm 108nm 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 include aromatic polycarbonate resin (A), a colorant (B) containing a pigment with a maximum absorption wavelength of less than 900 nm, and a phosphate compound or phosphoric acid (C) , containing 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 containing 0.005 to 0.3 parts by mass of the phosphate ester with respect to the phosphoric acid or phosphate ester compound (C) It is compound (C1) or contains 0.0001 to 0.04 parts by mass of phosphoric acid (C2). The polycarbonate resin compositions of Examples 1 to 13 have excellent thermal stability and reliability, and are suitable as wavelength-selective and transmissive polycarbonate resin compositions for filters.

In the molded products of Comparative Examples 1 and 2, the wavelength at which the transmittance decreases starts to shift to the longer wavelength side, and the wavelength width from the transmittance decrease start wavelength to the decrease end wavelength is large, so the near-infrared rays of 850-950 nm used in Lidar cannot be used. Appropriate penetration. Therefore, there is a risk that the detection capability of Lidar may be reduced. In contrast, in the cases of Examples 1 to 13 using the phosphate ester compound or phosphoric acid of the present invention, even if the residence time is 60 minutes, the transmittance decrease starting wavelength and wavelength width do not change significantly, and it is obvious that the It appropriately transmits near-infrared rays from 850 nm to 950 nm, making it excellent as a wavelength selective filter.

When an excessive amount of phosphate ester or phosphoric acid is prepared 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, there is a risk that the cover may be damaged due to collision with stones on the road, etc. On the other hand, it was found that when appropriate amounts of phosphate ester and phosphoric acid are added, significant decrease in molecular weight is not seen and the characteristics of the polycarbonate resin can be maintained. [Industrial availability]

The polycarbonate resin composition according to the embodiment of the present invention can be molded using ordinary equipment to produce a molded article, and the optical properties do not substantially change during the molding process. Therefore, the polycarbonate resin composition according to the embodiment of the present invention can provide a molded article that has appropriate wavelength selectivity and does not substantially change the optical characteristics. This molded article can be suitably 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 underlying applications are incorporated into this specification by reference.

Claims (14)

A wavelength-selective aromatic polycarbonate resin composition, characterized in that it contains aromatic polycarbonate resin (A), a colorant (B) containing a pigment with a maximum absorption wavelength of less than 900 nm, and a phosphorus-based antioxidant. (D) contains 0.01 to 2.0 parts by mass of the colorant (B) based on 100 parts by mass of the aromatic polycarbonate resin (A), and the phosphorus-based antioxidant (D) contains the following phosphite structure Phosphite compounds:

The wavelength-selective aromatic polycarbonate resin composition of claim 1, wherein the colorant (B) includes a colorant (B1) and/or a colorant (B2), and the colorant (B1) contains an absorption maximum wavelength Pigments with wavelengths less than 700 nm, the above-mentioned colorant (B2) contains pigments with maximum absorption wavelengths in the range of 700 nm or more and less than 900 nm. The wavelength-selective aromatic polycarbonate resin composition of claim 1 or 2, wherein the colorant (B) containing a pigment with a maximum absorption wavelength less than 900 nm is selected from the group consisting of anthraquinone pigments, pyrenone pigments, and perylene At least one type of pigments, methine pigments, azo pigments, quinoline pigments, phthalocyanine pigments and heterocyclic pigments. The wavelength-selective aromatic polycarbonate resin composition of claim 2, wherein the above The coloring agent (B1) containing a dye having a maximum absorption wavelength of less than 700 nm contains at least one selected from the group consisting of anthraquinone-based dyes, pyrenone-based dyes, perylene-based dyes, and methine-based dyes. The wavelength-selective aromatic polycarbonate resin composition of claim 2 or 4, wherein the colorant (B1) containing a pigment having a maximum absorption wavelength of less than 700 nm contains an anthraquinone-based pigment. The wavelength-selective aromatic polycarbonate resin composition of claim 5, wherein the anthraquinone pigment is selected from the group consisting of solvent yellow 163, dispersed violet 28, solvent blue 97, solvent green 28, solvent green 3, and dispersed blue 60 At least one of the groups formed. The wavelength-selective aromatic polycarbonate resin composition of claim 2 or 4, wherein the colorant (B2) containing a pigment having a maximum absorption wavelength in the range of 700 nm or more and less than 900 nm includes a phthalocyanine pigment selected from the group consisting of , at least one of anthraquinone pigments and heterocyclic pigments. The wavelength-selective aromatic polycarbonate resin composition of claim 1, 2, or 4, which contains 0.5 parts by mass or less of the above-mentioned phosphorus antioxidant () relative to 100 parts by mass of the aromatic polycarbonate resin (A). D). The wavelength-selective aromatic polycarbonate resin composition of claim 8, wherein the phosphorus-based antioxidant (D) includes a phosphite compound represented by the following formula (11), a phosphite compound represented by the following formula (12) At least one compound among the phosphite compound represented, the phosphite compound represented by the following formula (13), and the phosphite compound represented by the following formula (14):

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

(In the formula, R ² , R ³ , R ⁵ and R ⁶ respectively independently represent a hydrogen atom, an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 5 to 8 carbon atoms, and an alkyl ring with 6 to 12 carbon atoms. Alkyl group, aralkyl group with 7 to 12 carbon atoms or phenyl group; R ⁴ represents a hydrogen atom or an alkyl group with 1 to 8 carbon atoms; X represents a single bond, a sulfur atom or a group represented by the formula: -CHR ⁷ - ( Among them, 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 - group (where R ⁸ represents a single bond or an alkylene group with 1 to 8 carbon atoms, * represents a bond on the oxygen side); either Y and Z represent a hydroxyl group, an alkoxy group with 1 to 8 carbon atoms, or Aralkoxy group with 7 to 12 carbon atoms, the other represents a hydrogen atom or alkyl group with 1 to 8 carbon atoms)

(In the formula, R ⁹ and R ¹⁰ each independently represent an alkyl group with 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 from 0 to 3)

(In the formula, R ¹¹ ~ R ¹⁸ each independently represents an alkyl or alkenyl group with 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 exclusive. Bonded to form a ring; R ¹⁹ ~ R ²² each independently represents a hydrogen atom or an alkyl group with 1 to 20 carbon atoms; d ~ g each independently represents an integer from 0 to 5; X ¹ ~ X ⁴ each independently represents a single bond Or a carbon atom ^; when ^{X 1 ~} The wavelength-selective aromatic polycarbonate resin composition of claim 1, 2 or 4, which further contains a heat stabilizer, antioxidant, release agent, ultraviolet absorber, softener, antistatic agent and At least one of the group of impact modifiers. The wavelength-selective and transmissive aromatic polycarbonate resin composition of claim 1, 2 or 4 further contains a release agent. A wavelength-selective and transmissive aromatic polycarbonate resin molded article containing the wavelength-selective and transmissive aromatic polycarbonate resin composition according to any one of claims 1 to 11. The wavelength-selective and transmissive aromatic polycarbonate resin molded article of claim 12 is a lidar cover. A method for manufacturing a wavelength-selective and transparent aromatic polycarbonate resin molded article, which includes the step of molding the resin composition according to any one of claims 1 to 11.