CN114381109B - Polycarbonate compositions that are transparent to infrared light - Google Patents

Polycarbonate compositions that are transparent to infrared light Download PDF

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CN114381109B
CN114381109B CN202011132227.3A CN202011132227A CN114381109B CN 114381109 B CN114381109 B CN 114381109B CN 202011132227 A CN202011132227 A CN 202011132227A CN 114381109 B CN114381109 B CN 114381109B
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CN114381109A (en
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李思均
E·L·L·布罗卡特
S·哈巴
T·M·艾根汇森
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SABIC Global Technologies BV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/59—Transmissivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/30—Applications used for thermoforming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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Abstract

The present invention relates to a polycarbonate composition comprising a polycarbonate, an acid stabilizer and at least one anthraquinone-based colorant having at least one hydroxyl group, wherein the composition has a transmittance of at least 80% in the infrared wavelength range of 760-1120nm, wherein the transmittance is determined for an injection molded plate having a thickness of 2mm prepared by injection molding the composition at a maximum temperature of 320 ℃ and a residence time of 10 minutes. Preferably the composition has a transmittance of at most 10% in the visible wavelength range of 380-740 nm.

Description

Polycarbonate compositions that are transparent to infrared light
Technical Field
The present invention relates to a polycarbonate composition, in particular for a panel having a relatively low transmission in the visible wavelength range and a high transmission in the infrared wavelength range. The invention further relates to a panel comprising or consisting of the polycarbonate composition and to the use thereof.
Background
Polycarbonate panels having relatively low transmission in the visible wavelength range and high transmission in the infrared wavelength range are advantageously used in applications requiring the use of sensors that operate based on infrared radiation and in which the sensor itself is not observable by the human eye. For example, the sensor is located on one side of the panel facing the internal structure, while the other side of the panel is viewable in normal use. By way of example, such panels may be used as (part of) a front panel of a vehicle, wherein the sensor and accompanying electronics are placed such that they are not visible in normal use, thereby allowing for the manufacture of a vehicle having a desired aesthetic in combination with the prior art safety regulations provided by the sensor.
Polycarbonate compositions having low transmission in visible light are known per se and can be prepared, for example, by compounding polycarbonate with carbon black. Such compositions can be produced at low cost and provide sufficiently low visible light transmission. Carbon black also absorbs infrared light, making the use of such compositions less suitable for such applications.
Polycarbonate compositions having low transmission in visible light can also be made by using a combination of colorants that do not absorb infrared light or absorb infrared light to a lesser extent. However, some of these contain hydroxyl groups, and the inventors have found that at high molding temperatures the hydroxyl groups react with the polycarbonate, thereby causing undesirable changes in the light absorbing properties of the colorant and thus the polycarbonate composition.
WO2019/102349 discloses a panel for use on a vehicle comprising a first portion having a relatively high transmission in visible light and optionally a second portion having a relatively low visible light transmission and being at least partially transmissive to infrared light such that the infrared sensor can be hidden but such that the infrared light is transmitted through the second portion.
US2015/368434 discloses colored molding compounds based on polycarbonate, in particular this reference discloses polycarbonate compositions containing specific organic colorants which have a high color stability against weathering due to the use of specific stabilizers based on phosphate esters. US2015/368434 further discloses a polymer composition comprising at least one thermoplastic substance, at least one organic colorant, preferably a combination of at least two organic colorants having a specific structure, and at least one phosphate-based stabilizer.
US2014/128526 discloses a method of making a polycarbonate composition comprising: reacting an aromatic dihydroxy compound and a diaryl carbonate in the presence of a catalyst to form a polycarbonate; and adding a polydiorganosiloxane having a kinematic viscosity of less than or equal to 20mm 2/sec as determined according to ASTM D445 at 25 ℃ and optional additives to the polycarbonate to form a polycarbonate composition; wherein the polydiorganosiloxane has a phenyl content; and wherein a 3mm plaque of the polycarbonate composition has a haze of less than or equal to 1% as determined according to astm D1003-07, procedure a, illuminant CIE-D65.
US2013/116365 discloses a polycarbonate resin composition containing 100 parts by weight of a polycarbonate resin (a) containing at least a structural unit derived from a dihydroxy compound having a moiety represented by the following formula (1) as a part of its structure, and 0.1×10 -4 to 10.0×10 -4 parts by weight of a bluing agent, characterized in that a molded object (thickness 3 mm) formed from the polycarbonate resin composition has a Yellowness Index (YI) value of 12 or less after having been subjected to a metal halide lamp irradiation treatment with irradiance of 1.5kW/m 2 in a wavelength range of 300 to 400nm for 100 hours in an environment of 63 ℃ and relative humidity of 50% as determined by transmitted light inspection according to ASTM D1925-70.
-(CH2-O)- [ Chemical formula 1]
[ Excluding the case where the moiety represented by the general formula (1) constitutes-CH 2 -O-H. ]
KR20170036252 discloses a polycarbonate thermoplastic resin composition, and more particularly, a thermoplastic resin composition having excellent infrared transmittance and visible light shielding ratio. More specifically, this document discloses a polycarbonate resin composition comprising 90 to 99.89 wt.% of a polycarbonate resin, 0.1 to 5 wt.% of a metal salt of an aromatic sulfone sulfonic acid; (UL-94 test) is V-0, visible light (wavelength of 300nm or more and shorter than 700nm range) has a transmittance of 5% or less, and the thermoplastic resin composition has an infrared transmittance of 85% or more in the wavelength range of 700nm or more.
Disclosure of Invention
The inventors have found that the infrared absorption of certain colorants is affected by the conditions under which polycarbonate compositions containing such colorants are processed. In particular, it was found that certain conditions lead to an unfavorable shift in the absorption spectrum of such colorants, which in turn reduces the transmittance in the infrared wavelength range.
It is therefore an object of the present invention to provide a polycarbonate composition suitable for the manufacture of panels having a high transmittance in the infrared wavelength range.
It is another object of the present invention to provide a polycarbonate composition suitable for manufacturing a panel having a combination of low transmittance in the visible wavelength range and high transmittance in the infrared wavelength range.
More specifically, it is an object of the present invention to provide such polycarbonate compositions which can be processed in molding equipment under extreme conditions, such as high temperatures and/or high residence times, into molded articles, such as e.g. panels, wherein the influence of the processing on the optical properties in the visible and infrared wavelength range is minimized.
The inventors have unexpectedly found that when a polycarbonate composition containing an anthraquinone-based colorant having one or more hydroxyl groups further comprises an acid stabilizer, the change in transmission properties upon molding of the polycarbonate composition can be minimized.
The present invention therefore relates to a polycarbonate composition comprising a polycarbonate, an acid stabilizer and at least one anthraquinone-based colorant having at least one hydroxyl group, wherein the composition has a transmittance of at least 80% in the infrared wavelength range of 760 to 1120nm, wherein the transmittance is determined for an injection molded plate having a thickness of 2mm prepared by injection molding the composition at a maximum temperature of 320 ℃ and a residence time of 10 minutes.
More specifically, the present invention relates to a polycarbonate composition comprising an interfacial polycarbonate, an acid stabilizer, and at least one anthraquinone-based colorant having at least one hydroxyl group, wherein the composition has a transmittance of at least 80% in the infrared light wavelength range of 760-1120nm, wherein the transmittance is measured on an injection molded plate having a thickness of 2mm prepared by injection molding the composition at a maximum temperature of 320 ℃ and a residence time of 10 minutes, and wherein the acid stabilizer is a sulfonic acid or sulfonate, an organic phosphorous acid, or an ester thereof, or a combination comprising at least one of the foregoing.
The above object is at least partly achieved when applying the present invention.
Detailed Description
Polycarbonates
The term "polycarbonate composition" as used herein is understood to mean a composition comprising a polymer polycarbonate as the major component. The invention is disclosed herein as being based on polycarbonate being the only polymeric material in the composition. But other polymers may be present in lesser amounts. Thus, and for the avoidance of doubt, the amount of polycarbonate in the composition is at least 60 wt%, preferably at least 80 wt%, more preferably at least 90 wt%, more preferably at least 95 wt%, even more preferably at least 99 wt%, based on the total amount of polymeric material in the composition. Preferably, the polycarbonate composition consists essentially of polycarbonate as the polymeric material, and other polymeric materials are not present in the composition. It is therefore preferred that the polymeric material in the composition consists of polycarbonate, in particular interfacial polycarbonate. In embodiments where additional polymers are present in the composition, the additional polymers should be considered part of the polycarbonate.
Additional polymers that may be present as minor components may be polybutylene terephthalate, polyethylene terephthalate and/or Acrylonitrile Butadiene Styrene (ABS) copolymers.
The polycarbonate in the polycarbonate composition may be a mixture of at least two polycarbonates, each of which may be a homopolymer or a copolymer. Specific examples of mixtures consist of bisphenol a polycarbonate homopolymer and polycarbonate-polysiloxane copolymer. Preferably the polycarbonate is a polycarbonate homopolymer obtained by reacting a bisphenol, such as bisphenol a, with a carbonate source, such as phosgene or a diaryl carbonate, such as diphenyl carbonate. Thus, polycarbonates of the polycarbonate composition according to the invention may be prepared using the so-called interfacial process in which BPA is reacted with phosgene, or may be prepared by means of the so-called melt or direct transesterification process in which BPA is reacted with diphenyl carbonate. These two types of polycarbonates are known to those skilled in the art and may also be referred to herein as interfacial polycarbonates and melt polycarbonates. Those skilled in the art will appreciate that these two types of polycarbonates differ in the amount of Fries branching, which is present only in the melt polycarbonate, and in the terminal hydroxyl content of the interfacial polycarbonate, which is generally much lower.
Preferably the polycarbonate is obtained via an interfacial process, since said process generally provides a polycarbonate with a small number of hydroxyl chain ends compared to a melt process. The small amount of hydroxyl chain ends contributes to the thermal stability and color retention of the polycarbonate. Nevertheless, the use of polycarbonates obtained via the melt process, i.e. melt polycarbonates, in the present invention is not excluded. In one embodiment, the polycarbonate is a mixture of at least one polycarbonate obtained via an interfacial process and at least one polycarbonate obtained using a melt process. In such embodiments, the amount of melt polycarbonate may be from 30 to 70 weight percent and the amount of interfacial polycarbonate is from 70 to 30 weight percent, based on the combined weight of the melt polycarbonate and the interfacial polycarbonate.
Preferably the polycarbonate comprises or consists of an interfacial polycarbonate. More preferably, the polycarbonate is an interfacial polycarbonate prepared by reacting bisphenol A and phosgene. Thus, preferably the polycarbonate is bisphenol A polycarbonate or bisphenol A polycarbonate homopolymer.
The polycarbonate or the mixture of polycarbonates preferably has a Melt Volume Rate (MVR) of 3 to 35cm 3/10 min as determined according to ISO 1133 (300 ℃,1.2 kg). Preferably the MVR is from 6 to 25, more preferably from 14 to 21cm 3/10 min.
The polycarbonate composition preferably has a melt volume rate of 3 to 35cm 3/10 min as determined according to ISO 1133 (300 ℃,1.2 kg). Preferably the MVR is from 6 to 25, more preferably from 14 to 21cm 3/10 min.
Acid stabilizers
The acid stabilizer is preferably a sulfonic acid or sulfonate ester, an organic phosphorus acid (organophosphorous acid) or an ester thereof, or a combination comprising at least one of the foregoing, i.e., a combination comprising two or more of the foregoing. A preferred stabilizer is n-butyl tosylate (BuTos).
The sulfonate may comprise an organic sulfonic acid stabilizer having the formula:
Wherein each R 7 is independently C 1-30 alkyl, C 6-30 aryl, C 7-30 alkylarylene, C 7-30 arylalkylene, or a polymer unit derived from C 2-32 ethylenically unsaturated aromatic sulfonic acid or ester thereof; and R 8 is hydrogen, C 1-24 alkyl, or a group of formula-S (=o) 2-R7, wherein R 7 is C 6-12 aryl or C 7-24 alkylarylene. The sulfonic acid may comprise alkylbenzenesulfonic acid, polystyrene sulfonic acid, or p-toluenesulfonic anhydride. Preferably, the acid stabilizer is p-toluenesulfonic acid or butyl p-toluenesulfonate (i.e., n-butyl toluenesulfonate). The acid stabilizer is preferably applied to the polymer composition in an amount of 0.5ppm to 5ppm based on the total weight of the polymer composition.
The organic phosphorus acid or ester thereof may include a phosphorous acid, a phosphoric acid, a phosphite, a phosphine, a phosphonite compound, or a combination comprising at least one of the foregoing. Without wishing to be limited thereto, the inventors believe that the sulfonic acid or ester thereof, the organic phosphorus acid or ester thereof, or a combination comprising at least one of the foregoing helps to stabilize the anthraquinone-based colorant having at least one hydroxyl group. The inventors postulate that the reaction between the colorant and the polycarbonate results in a shift in the absorption spectrum of the colorant and, therefore, a change in the transmission properties of the polycarbonate composition.
For the avoidance of doubt, it is noted that in the context of the present invention the term "acid stabiliser" means an acid or an ester of such an acid. Other acid-derived compounds, such as, for example, salts, are not considered acid stabilizers and are therefore excluded from the term "acid stabilizers". More specifically, the acid stabilizer is not an alkali or alkaline earth metal salt, such as an alkali or alkaline earth metal salt of a sulfonic acid or an organic phosphorus acid.
Coloring agent
The compositions disclosed herein contain at least one anthraquinone-based colorant having at least one hydroxyl group. The term "anthraquinone-based" means that the molecules comprising the colorant contain one or more anthraquinone moieties. Such colorants can react with polycarbonate due to hydroxyl groups, particularly under more extreme, sometimes referred to as "harsh" processing conditions. Such conditions involve relatively high temperatures and relatively long residence times. The negative effect of this reaction may be a change in the absorption spectrum of the colorant, which in turn changes the overall absorption spectrum and hence the transmittance of the composition. As a result, absorption of light in the infrared wavelength range may increase, which in turn may cause malfunction or at least less reliable operation of infrared sensors that need to transmit and/or receive infrared light through panels made of the composition.
Preferred anthraquinone-based colorants are green colorants, more preferably solvent green 28, having CAS registry 28198-05-2, 71839-01-5, or 4851-50-7.
In order to obtain the desired low visible light transmission, a combination of colorants is used, wherein at least one such colorant, preferably a green colorant, is an anthraquinone-based colorant having at least one hydroxyl group. It is therefore preferred that the anthraquinone-based colorant in the polycarbonate composition is a green colorant and that the composition further comprises one or more of a red colorant, a blue colorant, a yellow colorant and an orange colorant, preferably a red colorant and a blue colorant. The combination of red, blue and green colorants allows for the manufacture of compositions, including products molded therefrom, having a black appearance and having low visible light transmission. Yellow or orange colorants may be added to fine tune the final hue of the product. For the avoidance of doubt, it is noted that the compositions of the present invention may contain a colourant which does not have an anthraquinone moiety.
The colorant is preferably an organic dye. The red dye is preferably one or more selected from the group consisting of solvent red 52, solvent red 111, solvent red 135, solvent red 169, solvent red 179, solvent red 207, disperse red 22, and vat red 41.
The blue dye is preferably one or more selected from the group consisting of disperse blue 73, solvent blue 97, solvent blue 101, solvent blue 104, solvent blue 122, and solvent blue 138. Optionally, solvent violet 13 may also be included in the compositions disclosed herein, solvent violet 13 should be considered a blue colorant for purposes of the present invention.
The yellow dye is preferably one or more selected from the group consisting of disperse yellow 201, solvent yellow 33, solvent yellow 114, solvent yellow 93, solvent yellow 98, solvent yellow 163, solvent yellow 160:1, solvent yellow 188.
The orange dye is preferably one or more selected from the group consisting of solvent orange 60, solvent orange 63, disperse orange 47.
The total amount of colorant is generally selected so as to obtain the desired color intensity. The total amount of colorant in the polymer composition may be from 0.1 to 1000ppm by weight.
The composition preferably does not contain inorganic pigments, as these may absorb excessive infrared radiation. Organic pigments may be used in the compositions disclosed herein provided that they do not significantly absorb light in the infrared wavelength range in the wavelength range 760-1120 nm.
Composition and method for producing the same
Preferably the composition is translucent or opaque as determined for injection molded plaques having a thickness of 2mm prepared by injection molding the composition at a maximum temperature of 320 ℃ and a residence time of 10 minutes. Thus, it is preferred that the composition has a transmittance of at most 50% in the visible wavelength range of 380-740 nm.
For opaque compositions, the composition has a transmittance of at most 10% in the visible wavelength range of 380-740 nm.
The composition may have a transmittance of 11 to 50%, such as 20-40%, in the visible wavelength range of 380-740 nm.
The composition may have a transmittance of 0 to 10%, such as 2-8%, in the visible wavelength range of 380-740 nm.
The transmittance in visible light can be adjusted by means of the concentration and type of colorants used as is well known. To achieve the transmittance requirement in the wavelength range of 380-740nm, a combination of green, red and blue colorants is typically used, optionally with some additional colorants to modify the final hue. An overall black hue is generally desired.
In embodiments of lower relevance or importance of the shading force of panels made from the compositions disclosed herein, the compositions can have a transmittance of 51 to 90%, such as 60-80%, in the visible wavelength range of 380-740 nm.
The composition preferably has a melt volume rate of 3 to 35cm 3/10 min as determined according to ISO 1133 (300 ℃,1.2 kg). Preferably the MVR is from 6 to 25, more preferably from 14 to 21cm 3/10 min.
Preferably, the polycarbonate compositions disclosed herein comprise a red colorant, a blue colorant, and a green colorant, wherein at least the green colorant is an anthraquinone-based colorant having at least one hydroxyl group, wherein the weight of the composition is based on the weight of the composition:
the amount of red colouring agent is at most 0.5% by weight, preferably 0.05 to 0.5% by weight
The amount of blue colorant is up to 0.5% by weight, preferably from 0.05 to 0.5% by weight
The amount of green colorant is up to 0.5% by weight, preferably from 0.05 to 0.5% by weight
The amount of acid stabilizer is up to 3ppm by weight, preferably 0.1 to 3ppm.
The polycarbonate compositions disclosed herein may comprise an anthraquinone-based green colorant having at least one hydroxyl group and optionally a red and/or blue colorant, wherein the weight of the composition is based on the weight of the composition:
the amount of red colorant, if present, is up to 0.5% by weight, preferably from 0.01% to 0.5% by weight
The amount of blue colorant, if present, is up to 0.5% by weight, preferably from 0.01% to 0.5% by weight
The amount of green colorant is up to 0.5% by weight, preferably from 0.01 to 0.5% by weight
The amount of acid stabilizer is up to 3ppm by weight, preferably 0.1 to 3ppm. Such compositions may be suitable for compositions that do not require low transmission in the visible wavelength range, or where only certain transmission in a specific wavelength range is required.
The compositions as disclosed herein may also contain additives common in the art, such as mold release agents, antioxidants, UV stabilizers, flame retardants, and fillers, provided that their amounts do not cause significant deterioration of infrared radiation in the wavelength range 760-1120 nm. Preferably, the composition of the present invention does not contain a flame retardant. More specifically, it is preferred that the composition does not contain an aromatic sulfonic acid metal salt. Even more specifically, it is preferred that the composition does not comprise sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, sodium 4,4' -dibromodiphenylsulfone-3-sulfonate, calcium 4-chloro-4 ' -nitrobenzenesulfone-3-sulfonate, disodium diphenylsulfone-sulfone-3, 3' -disulfonate, or a combination of two or more of the foregoing.
The present invention further relates to a method of making a composition as disclosed herein comprising combining a polycarbonate, an acid stabilizer, and an anthraquinone-based colorant having at least one hydroxyl group, and optionally one or more of a red colorant, a blue colorant, a yellow colorant, and an orange colorant, in a melt mixing device, followed by melt mixing the composition into a substantially homogeneous composition.
The invention further relates to a molded article, preferably an injection molded article, comprising or consisting of the polycarbonate composition of the invention. The molded article preferably has a portion having a thickness of 0.1 to 10mm, preferably 2 to 7mm, more preferably 4 to 6 mm. Such parts are parts that are preferably used for transmitting and/or receiving infrared radiation, such as those transmitted and/or received by sensors in the automotive industry.
The invention further relates to an extruded sheet comprising the composition disclosed herein and any thermoformed article made from such sheet.
The present invention also relates to a detection system comprising the injection molded article disclosed herein and a sensor, wherein the sensor detects infrared radiation traveling through the injection molded article. In other words, the present invention also relates to a detection system comprising the injection molded article disclosed herein and a sensor capable of detecting infrared radiation traveling through the injection molded article.
In use, such a detection system is preferably configured such that the sensor cannot be observed during normal use of the panel. For example, the sensor cannot be observed from outside the vehicle when incorporated into the vehicle. This can be achieved when the composition has a transmittance (for 2mm injection molded plaques) of at most 50%, preferably at most 10% in the visible wavelength range of 380-740 nm. Examples of sensors for use in vehicles that may use infrared radiation are proximity and/or automotive detection sensors. A schematic example of such a detection system is shown in fig. 1, wherein panel 1 is a panel (injection) molded from the composition disclosed herein. The sensor 2 is a sensor operating at a wavelength in the infrared wavelength range. The sensor 2 transmits and/or receives infrared radiation 3 travelling through the panel 1. Because the panel 1 has a relatively low visible light transmittance, the sensor cannot be observed from the side opposite to the side on which the sensor 2 is placed.
The invention further relates to an electric vehicle, preferably an electric vehicle, comprising the injection molded article or the detection system disclosed herein.
The present invention relates to the use of an acid stabilizer, preferably a sulfonic acid or sulfonate ester, in a polycarbonate composition comprising an anthraquinone colorant having at least one hydroxyl group for the manufacture of molded articles at a temperature of at least 300 ℃ to maintain a transmittance of at least 80% in the infrared wavelength range of 760 to 1120 nm.
The invention further relates to the use of an acid stabilizer, preferably a sulfonic acid or sulfonate ester, in a polycarbonate composition comprising an anthraquinone colorant having at least one hydroxyl group for stabilizing said colorant.
The invention will now be further elucidated on the basis of the following non-limiting examples.
Examples
TABLE 1
The sample material was dried at 120 ℃ for 2.5 hours, followed by injection molding. All compositions were compounded on a Werner & Pfleiderer co-rotating twin screw extruder (length to diameter (LID) ratio = 30/1, vacuum orifice located at near die face) unless otherwise indicated. Twin screw extruders have sufficient dispensing and dispersing mixing elements to produce good mixing between the polymer compositions. The composition was then molded on an Engel-75 injection molding machine according to ISO 294. The dimensions of the molded test pieces were 60X 2mm.
The following temperature profile was used for the extruder of the injection molding machine:
the residence time of the material in the screw is controlled by the cooling of the injection plate. In the following table "temperature" refers to the temperature of zone 3 of the extruder.
Optical properties were determined on injection molded plates having a thickness of 2mm and a width and length of 50mm, respectively, using a PERKIN ELMER labsphere 950 ultraviolet-visible-near infrared spectrophotometer, measured in transmission mode using an integrating sphere. Measurements were carried out at room temperature, i.e. 25 ℃. Transmittance is the ratio of the intensity of light received at the sensor to the intensity of light transmitted through the sample. Typically this is expressed as a percentage, i.e. T% = 100× (I Detector for detecting a target object /I0), where I Detector for detecting a target object is the light intensity detected by the detector and I 0 is the light intensity delivered into the sample. This is known per se to the skilled person. Therefore, using a spectrophotometer, the transmittance is measured in a transmittance mode using an integrating sphere. The transmittance reported herein is expressed as a percentage.
TABLE 2
CE0 CE1 CE2 CE3 CE4 CE5 CE6 CE7
PC1 [ Wt.%) 20 20 20 20 20 20 20 20.
PC2 [ Wt.%) 79.31 79.31 79.31 79.31 79.31 79.31 79.31 79.31
UV [ Wt.%) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Release agent [ Wt.%) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
Stabilizer 1 [ Wt.%) 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05
AO [ Wt.%) 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02
Stabilizer 2 [ Wt.%) - - - - - - - -
SRd135 [ Wt.%) 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03
SRd52 [ Wt.%) 0.023 0.023 0.023 0.023 0.023 0.023 0.023 0.023
SGr28 [ Wt.%) 0.067 0.067 0.067 0.067 0.067 0.067 0.067 0.067
Temperature (temperature) [℃] 280 300 300 300 320 320 320 340
Time of [min] 5 10 30 60 10 30 60 10
T_720 [％] 0.1 0.04 0.3 1.1 0.2 2.0 4.3 3.1
T_740 [％] 3.0 1.8 2.9 4.0 2.6 5.35 6.1 6.5
T_820 [％] 87.5 82.9 59.2 39.4 58.8 39.3 27.6 33.9
T_820-920 [％] 89.1 87.5 73.7 57.9 73.0 57.5 49.7 51.9
Time refers to the residence time of the composition in the extruder of the injection molding apparatus.
T_720, t_740, and t_820 refer to transmittance at 720nm, 740nm, and 820nm wavelengths, respectively.
T_820-920 refers to the numerical average of the transmittance of the test sample over the wavelength range of 820 to 920 nm.
From table 2 it can be observed that the transmittance of the test sample decreases significantly in the infrared wavelength range under more severe molding conditions, i.e. elevated temperature and/or increased residence time.
TABLE 3 Table 3
CE8 CE9 CE10 CE11
PC1 [ Wt.%) 20 20 20 20
PC2 [ Wt.%) 79.23 79.21 79.23 79.08
UV [ Wt.%) 0.15 0.15 0.15 0.15
Release agent [ Wt.%) 0.3 0.3 0.3 0.3
Stabilizer 1 [ Wt.%) 0.05 0.05 0.05 0.05
AO [ Wt.%) 0.02 0.02 0.02 0.02
Stabilizer 2 [ Wt.%) - - - -
SRd135 [ Wt.%) 0.12 0.12
PB15:4 [ Wt.%) 0.01 0.03
G5B [ Wt.%) 0.12 0.12 0.25 0.4
Temperature (temperature) [℃] 280 280 280 280
Time of [min] 5 5 5 5
T_720 [％] 0.2 0.2 2.1 1
T_740 [％] 0.4 0.1 47.8 30.6
T_820 [％] 81 72.9 89.7 88.6
T_820-920 [％] 88 86.6 89.4 88.9
TABLE 4 Table 4
CE12 CE13 CE14 CE15 CE16 CE17 CE18 CE19
PC1 [ Wt.%) 20 20 20 20 20 20 20 20
PC2 [ Wt.%) 76.48 76.48 76.48 76.48 76.48 76.48 76.48 76.48
UV [ Wt.%) 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15
Release agent [ Wt.%) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
Stabilizer 1 [ Wt.%) 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05
AO [ Wt.%) 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02
Stabilizer 2 [ Wt.%) - - - - - - - -
SGr3 [ Wt.%) 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0
Temperature (temperature) [℃] 280 300 300 300 320 320 320 340
Time of [min] 5 10 30 60 10 30 60 10
T_720 [％] 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T_740 [％] 0.1 0.1 0.1 0.0 0.1 0.0 0.0 0.0
T_820 [％] 67.2 72.2 54.4 30.0 42.4 18.3 10.3 15.9
T_820-920 [％] 73.5 77.6 68.2 53.8 62.2 42.6 27.1 41.9
TABLE 5
E1 E2 E3 E4 E5 CE20 CE21 CE22
PC1 [ Wt.%) 20 20 20 20 20 20 20 20
PC2 [ Wt.%) 79.3 79.3 79.3 79.3 79.3 79.3 79.3 79.3
UV [ Wt.%) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Release agent [ Wt.%) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
Stabilizer 1 [ Wt.%) 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05
AO [ Wt.%) 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02
Stabilizer 2 [ppm] 2 2 2 2 2 2 2 2
SRd135 [ Wt.%) 0.03 0.03 0.030 0.03 0.03 0.03 0.03 0.03
SRd52 [ Wt.%) 0.023 0.023 0.023 0.023 0.023 0.023 0.023 0.023
SGr28 [ Wt.%) 0.067 0.067 0.067 0.067 0.067 0.067 0.067 0.067
Temperature (temperature) [℃] 280 300 300 300 320 320 320 340
Time of [min] 5 10 30 60 10 30 60 10
T_720 [％] 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
T_740 [％] 0.1 0.1 0.1 0.0 0.1 0.0 0.0 0.0
T_820 [％] 87.2 86.8 86.0 84.9 84.8 77.2 51.8 53.7
T_820-920 [％] 89.2 89.0 88.7 88.1 89.4 84.4 68.0 69.9
Table 5 shows that the addition of butyl tosylate in combination with solvent green 28 allows relatively high transmission in the infrared wavelength range even under severe molding conditions.

Claims (22)

1. A polycarbonate composition comprising an interfacial polycarbonate, an acid stabilizer, and at least one anthraquinone-based colorant having at least one hydroxyl group, wherein the composition has a transmittance of at least 80% in the infrared wavelength range of 760 to 1120nm, wherein the transmittance is determined for an injection molded plate having a thickness of 2mm prepared by injection molding the composition at a maximum temperature of 320 ℃ and a residence time of 10 minutes,
Wherein the acid stabilizer is a sulfonic acid or sulfonate ester and optionally an organic phosphorus acid or ester thereof,
Wherein the anthraquinone-based colorant having at least one hydroxyl group is a green colorant, and
Wherein the amount of green colorant is up to 0.5 weight percent, and the amount of acid stabilizer is up to 3ppm by weight, based on the weight of the composition.
2. The polycarbonate composition of claim 1, wherein the transmittance in the visible light wavelength range of 380-740nm is at most 50%.
3. The polycarbonate composition of claim 1, wherein the transmittance in the visible light wavelength range of 380-740nm is at most 10%.
4. The polycarbonate composition of any of claims 1-3, wherein the anthraquinone-based colorant is a green colorant, and wherein the composition further comprises one or more of a red colorant, a blue colorant, a yellow colorant, and an orange colorant.
5. The polycarbonate composition of claim 4, wherein the composition further comprises a red colorant and a blue colorant.
6. The polycarbonate composition of any of claims 1-3, wherein the green colorant is solvent green 28 having CAS registry 28198-05-2, 71839-01-5, or 4851-50-7.
7. The polycarbonate composition of any of claims 1-3, wherein the acid stabilizer is a sulfonate ester.
8. The polycarbonate composition of any of claims 1-3, wherein the acid stabilizer is butyl p-toluenesulfonate.
9. The polycarbonate composition of any of claims 1-3, comprising a red colorant, a blue colorant, and a green colorant, wherein at least the green colorant is an anthraquinone-based colorant having at least one hydroxyl group, wherein based on the weight of the composition:
The amount of red colorant is at most 0.5% by weight,
The amount of blue colorant is at most 0.5% by weight,
The amount of green colorant is at most 0.5% by weight,
The amount of acid stabilizer is at most 3ppm by weight.
10. The polycarbonate composition of any of claims 1-3, comprising a red colorant, a blue colorant, and a green colorant, wherein at least the green colorant is an anthraquinone-based colorant having at least one hydroxyl group, wherein based on the weight of the composition:
the amount of red colorant is from 0.05 to 0.5% by weight,
The amount of blue colorant is from 0.05 to 0.5% by weight,
The amount of green colorant is from 0.05 to 0.5% by weight,
The amount of acid stabilizer is from 0.1 to 3ppm by weight.
11. A method of making the composition of any of claims 1-10, comprising combining the polycarbonate, the acid stabilizer, and the at least one anthraquinone-based colorant having at least one hydroxyl group, and optionally one or more of a red colorant, a blue colorant, a yellow colorant, and an orange colorant, in a melt mixing device, followed by melt mixing the composition into a substantially homogeneous composition.
12. The method of claim 11, wherein the acid stabilizer is included in the polycarbonate prior to combining the polycarbonate and the colorant in the melt mixing device.
13. Injection molded article comprising or consisting of the composition according to any one of claims 1-10.
14. The injection molded article of claim 13, wherein the article is a panel for use in or on a vehicle.
15. The injection molded article of claim 14, wherein the article is a panel for use in or on an electric vehicle.
16. The injection molded article of claim 14, wherein the article is a panel for use in or on an electric automobile.
17. The injection molded article of any of claims 14-16, wherein the article is an exterior front panel for an electric vehicle.
18. A method of making an article according to any one of claims 13-17 comprising injection molding the composition according to any one of claims 1-10.
19. A detection system comprising the injection molded article of any of claims 13-17 and a sensor, wherein the sensor is capable of detecting infrared radiation traveling through the injection molded article.
20. An electric vehicle comprising an injection molded article according to any one of claims 13-17 and/or a detection system according to claim 19.
21. The electric vehicle of claim 20, which is an electric vehicle.
22. Use of an acid stabilizer in a polycarbonate composition comprising an anthraquinone-based colorant having at least one hydroxyl group for the manufacture of a molded article at a temperature of at least 300 ℃ to maintain a transmittance of at least 80% in the infrared wavelength range of 760 to 1120nm, wherein the acid stabilizer is a sulfonic acid or sulfonate ester and optionally an organic phosphorous acid or ester thereof.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101473246A (en) * 2006-06-19 2009-07-01 沙伯基础创新塑料知识产权有限公司 Infrared transmissive thermoplastic composition, and articles formed therefrom
CN104837924A (en) * 2012-11-07 2015-08-12 沙特基础全球技术有限公司 Process for producing polycarbonate compositions
KR20170036252A (en) * 2015-09-24 2017-04-03 롯데케미칼 주식회사 Thermopolastic resin composition having excellent infrared transmittance and visible light shielding rate
CN110621733A (en) * 2017-06-16 2019-12-27 沙特基础工业全球技术有限公司 Use of sulfonic acids as stabilizers in polycarbonates

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5040827B2 (en) * 2008-06-20 2012-10-03 三菱エンジニアリングプラスチックス株式会社 Filter resin composition
KR101796441B1 (en) * 2010-06-25 2017-11-10 미쯔비시 케미컬 주식회사 Polycarbonate resin composition and molded article
WO2014095967A1 (en) * 2012-12-20 2014-06-26 Bayer Materialscience Ag Organic colorants and coloured polymer compositions with good processing properties
CN109328210A (en) * 2016-06-17 2019-02-12 沙特基础工业全球技术有限公司 Stable polycarbonate compositions
KR20200086361A (en) * 2017-11-24 2020-07-16 사빅 글로벌 테크놀러지스 비.브이. Panel, integral structure, and method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101473246A (en) * 2006-06-19 2009-07-01 沙伯基础创新塑料知识产权有限公司 Infrared transmissive thermoplastic composition, and articles formed therefrom
CN104837924A (en) * 2012-11-07 2015-08-12 沙特基础全球技术有限公司 Process for producing polycarbonate compositions
KR20170036252A (en) * 2015-09-24 2017-04-03 롯데케미칼 주식회사 Thermopolastic resin composition having excellent infrared transmittance and visible light shielding rate
CN110621733A (en) * 2017-06-16 2019-12-27 沙特基础工业全球技术有限公司 Use of sulfonic acids as stabilizers in polycarbonates

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