JP6584915B2 - Polycarbonate resin composition for solar radiation sensor cover - Google Patents

Description

  The present invention relates to a polycarbonate resin composition for a solar radiation sensor cover that has excellent visible light selective transparency, thermal stability, and weather resistance without impairing the original properties of the polycarbonate resin. More specifically, the present invention relates to a polycarbonate resin composition for a solar radiation sensor cover that selectively transmits wavelengths in the visible light region and shields wavelengths in the ultraviolet region and infrared region, and has excellent visible light selective transparency.

Polycarbonate resins have excellent transparency, heat resistance, mechanical strength, etc., and are therefore widely used in electrical, mechanical, automotive, medical applications and the like. For example, applications such as optical information recording media, optical lenses, and glazing materials for buildings and vehicles can be mentioned.

  In addition, a solar radiation sensor that detects the intensity of sunlight and outputs a signal corresponding to the intensity of the light in order to automatically control the interior light and the car air conditioner is known. In general, a solar radiation sensor receives sunlight in order to perform automatic control of a car air conditioner or the like as described in, for example, Patent Document 1 and Patent Document 2, and a voltage corresponding to the intensity of the light. Some have a light receiving element that outputs a signal. However, if sunlight is incident on the light receiving element as it is, the output signal will not easily have characteristics suitable for automatic control of car air conditioners, etc., so that the sunlight is attenuated on the front surface of the light receiving element to correct the output characteristics. A transparent or translucent resin cover is often attached.

  And as such resin cover for solar radiation sensors, the above-mentioned polycarbonate resin composition may be used, but as a characteristic required for recent solar sensor resin covers, the wavelength in the visible light region (380 nm) Visible light selective transmission (characteristic as a visible light selective transmission filter) that selectively transmits light in a wavelength range of ˜780 nm, particularly a wavelength band having a peak at 550 nm, and substantially blocks wavelengths in the ultraviolet and infrared regions. In addition, it is desired that the resin cover is excellent in thermal stability and weather resistance in consideration that the vehicle on which the solar radiation sensor is installed is exposed to a severe outdoor environment.

  Conventionally, a polycarbonate resin composition having excellent visible light selective permeability, heat stability, and weather resistance as described above has not been obtained.

JP-A-6-201459 JP-A-11-160147

  An object of the present invention is to provide a polycarbonate resin composition for a solar radiation sensor cover that is excellent in visible light selective transparency, thermal stability, and weather resistance, without impairing the original properties of the polycarbonate resin.

  As a result of diligent research in view of such problems, the present inventors have blended a polycarbonate resin containing an inorganic oxide with a specific antioxidant and, if necessary, a specific amount of an ultraviolet absorber, In order to complete the present invention, it is found that a polycarbonate resin composition having excellent visible light selective transparency and excellent thermal stability and also weather resistance can be obtained without impairing various excellent properties possessed by the polycarbonate resin. It came.

That is, the present invention is selected from 100 parts by weight of the polycarbonate resin (A), 0.023 to 0.23 parts by weight of the cesium tungsten oxide fine particles as the inorganic oxide (B), a phosphorus-based antioxidant, and a phenol-based antioxidant. A polycarbonate resin composition for solar sensor cover, comprising 0.05 to 1 part by weight of one or more antioxidants (C) and 0 to 2 parts by weight of an ultraviolet absorber (D) Is to provide.

  The polycarbonate resin composition for a solar radiation sensor cover of the present invention selectively selects wavelengths in the visible light region (380 nm to 780 nm, particularly a wavelength band having a peak at 550 nm) without impairing various excellent properties of the polycarbonate resin. In addition to being excellent in visible light selective transmission to be absorbed into the light, it is also excellent in thermal stability and weather resistance.For example, it selectively transmits wavelengths in the visible light range transmitted to the solar radiation sensor, and in the ultraviolet and infrared wavelengths. It can utilize suitably as a resin composition for covers which shields.

  Hereinafter, embodiments will be described in detail. However, more detailed explanation than necessary may be omitted. For example, detailed descriptions of already well-known matters and repeated descriptions for substantially the same configuration may be omitted. This is to avoid the following description from becoming unnecessarily redundant and to facilitate understanding by those skilled in the art.

  In addition, the inventors provide the following explanation for those skilled in the art to fully understand the present invention, and are not intended to limit the subject matter described in the claims.

  The polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted. A typical example of the polymer is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like.

  These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, and the like may be used in combination.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  Although there is no restriction | limiting in particular in the viscosity average molecular weight of polycarbonate resin (A), Usually, it is 10,000-100000, More preferably, it is 15000-30000, More preferably, it is the range of 17000-26000 from the surface of moldability and intensity | strength. Moreover, when manufacturing this polycarbonate resin, a molecular weight modifier, a catalyst, etc. can be used as needed.

The particle diameter of the inorganic oxide (B) used in the present invention is preferably 1 nm to 800 nm, more preferably 1 nm to 600 nm, and further preferably 1 nm to 300 nm. If the particle diameter is smaller than 1 nm, the coagulation effect is increased, so that dispersibility is likely to occur. If it is larger than 800 nm, defects such as an increase in the cloudiness of the solar sensor cover may occur. Examples of the inorganic oxide include tungsten inorganic oxide, lanthanum inorganic oxide, tin inorganic oxide, and antimony inorganic oxide. Among these, tungsten-based inorganic oxides are preferable from the viewpoint of selective visible light permeability and haze, and among them, composite tungsten oxide fine particles are particularly preferable. Examples of commercially available products include YMDS874 (manufactured by Sumitomo Metal Industries, Ltd., average particle size 5 nm, cesium tungsten fine particles Cs _0.33 WO ₃ (23 wt%) and dispersant).

The composite tungsten oxide fine particles can be obtained by heat-treating a tungsten compound as a starting material in an inert gas atmosphere or a reducing gas atmosphere. The composite tungsten oxide fine particles obtained through the heat treatment have sufficient visible light selective permeability.

The composite tungsten oxide fine particles are preferably coated with a dispersant. Dispersants include polycarbonate, polysulfone, polyacrylonitrile, polyarylate,
Examples include polyethylene, polyvinyl chloride, polyvinylidene chloride, fluororesin, polyvinyl butyral, polyvinyl alcohol, polystyrene, silicone resins, and derivatives thereof, which improves the dispersibility when added to the resin. In addition, there is an effect of preventing deterioration of mechanical properties. As a coating method using a dispersant, the composite tungsten oxide fine particles and the dispersant are dissolved in a solvent such as toluene and stirred to prepare a dispersion, and then the composite tungsten oxide fine particles are removed by removing the solvent by a treatment such as vacuum drying. Examples of the method include coating.

  Moreover, as a method of adding the inorganic oxide (B) to the polycarbonate resin, a method of directly adding the composite tungsten oxide fine particles or the coated composite tungsten oxide fine particles, or after diluting with 1 to 100 times the polycarbonate resin The method of adding is mentioned.

  Content of the inorganic oxide (B) used by this invention is 0.1-1 weight part with respect to 100 weight part of polycarbonate resin (A), 0.2-0.8 weight part is preferable, 0.3-0.6 weight part is more preferable. When the content of the inorganic oxide (B) is less than 0.1 parts by weight, the infrared shielding ability cannot be sufficiently exhibited, and the discoloration of the polycarbonate resin is visually caused by the color tone peculiar to the composite tungsten oxide fine particles. The reduction effect is reduced, and if it exceeds 1 part by weight, the visible light transmittance is very small.

  In the resin composition of the present invention, one or more antioxidants (C) selected from phosphorous antioxidants and phenolic antioxidants are used, and the blending amount thereof is 100% by weight of the polycarbonate resin (A). The amount is 0.05 to 1 part by weight per part. If the blending amount is less than 0.05 parts by weight, the thermal stability is poor, which is not preferable. On the other hand, when the amount exceeds 1 part by weight, the thermal stability becomes insufficient at the time of retention during the molding process, and it is not preferable because it turns yellow. More preferably, it is 0.05-0.8 weight part.

Examples of the phosphorus antioxidant used in the present invention include those composed of one or more compounds represented by the following general formulas 1, 2 and 3.
General formula 1:

（一般式１において、Ｒ１〜４は炭素数１〜２０のアルキル基、またはアルキル基で
置換されてもよいアリール基を示す。）
一般式２：

(In General Formula 1, R1-4 represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group.)
General formula 2:

（一般式２において、Ｒ５、Ｒ６は炭素数１〜２０のアルキル基、またはアルキル基で置換されてもよいアリール基を、ａ、ｂは整数０〜３を示す。）
一般式３：

(In General Formula 2, R5 and R6 represent an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group, and a and b represent integers 0 to 3.)
General formula 3:

（一般式３において、Ｒ７は炭素数１〜２０のアルキル基、またはアルキル基で置換されてもよいアリール基を、ｃは０〜３の整数を示す。）

(In General Formula 3, R7 represents an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group, and c represents an integer of 0 to 3)

  The compound of general formula 1 is Sandstub P-EPQ manufactured by Clariant Japan, the compound of general formula 2 is Adekastab PEP-36 manufactured by Adeka, and the compound of general formula 3 is Irgafos 168 manufactured by Ciba Japan. Are commercially available.

Moreover, as a phenolic antioxidant used by this invention, the compound of the following general formula 4 is mentioned.
General formula 4:

（一般式４において、Ｒ８は炭素数１〜２０のアルキル基、またはアルキル基で置換されてもよいアリール基を示す。）

(In General Formula 4, R8 represents an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted with an alkyl group.)

As a compound of the general formula 4, Adekastab AO-50 (n-octadecyl-3 (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate) manufactured by Asahi Denka Co., Ltd. is commercially available. .

  Examples of the ultraviolet absorber (D) used in the present invention include various ultraviolet absorbers that are benzotriazole-based, triazine-based, and benzophenone-based compounds. These may be used alone or in combination of two or more. Can be used. Among these, benzotriazole compounds can be preferably used.

  Examples of benzotriazole compounds include 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (3-tert-2-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2 -(3,5-di-tert-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2H-benzotriazole-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophenylmethyl) phenol, 2- (2-hydroxy-4-octylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5- ert-octylphenyl) -2H-benzotriazole, 2- [2′-hydroxy-3,5-di (1,1-dimethylbenzoyl) phenyl] -2H-benzotriazole, 2,2′-methylenbis [6- (2H-benolz] 2-yl) 4- (1,1,3,3-tetramethylbutyl) phenol]. Among them, 2,2′-methylenbis [6- (2H-benzotriazol-2-yl) 4- (1,1,3,3-tetramethylbutyl) phenol] is preferable because of its good transpiration during thermoforming. Used for.

  Examples of triazine compounds include 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2- (4,6 -Diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol and the like.

  Examples of the benzophenone compounds include 2,4-dihydroxybenzobenzone, 2-hydroxy-4-n-octoxybenzone, and the like.

  The compounding quantity of a ultraviolet absorber (D) exists to 2 weight part per 100 weight part of polycarbonate resin (A). Exceeding 2 parts by weight is not preferable because the heat stability is inferior, for example, the mold is contaminated due to generation of a large amount of gas during molding. The preferred amount is up to 1 part by weight, more preferably up to 0.6 part by weight.

  There are no particular limitations on the method of blending the various blending components (A), (B), (C), and (D) of the present invention, and these are mixed by an optional mixer such as a tumbler, ribbon blender, high-speed mixer, or the like. In addition, it can be easily melt-kneaded with an ordinary single screw or twin screw extruder. Moreover, there is no restriction | limiting in particular also about these compounding orders.

  In addition, other known additives such as mold release agents, ultraviolet absorbers, fillers, antistatic agents, antioxidants, phosphorous heat stabilizers, dyes and pigments, spreading agents (epoxies) may be used as necessary. Soybean oil, liquid paraffin, etc.) can be blended.

  Examples of the filler include glass fiber, glass bead, glass flake, carbon fiber, talc powder, clay powder, mica, potassium titanate whisker, aluminum borate whisker, wollastonite powder, silica powder and the like. Examples of mica include muscovite, biotite, phlogopite, and artificial phlogopite, and those having a flake shape are suitable.

  As described above, the embodiments have been described as examples of the technology disclosed in the present application. However, the technology in the present invention is not limited to this, and can also be applied to embodiments in which changes, replacements, additions, omissions, etc. are made as appropriate.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “parts” and “%” are based on weight.

The following were used as raw materials.
1. Polycarbonate resin (A):
Polycarbonate resin synthesized from bisphenol A and carbonyl chloride (trade name Caliber 200-20, manufactured by Sumika Stylon Polycarbonate Co., Ltd., “Caliver” is a registered trademark of Trinzeo Europ GmbH, viscosity average molecular weight: 19000, (hereinafter “ PC "abbreviated)

2. Inorganic oxide (B): Composite tungsten-based inorganic oxide YMDS874 (manufactured by Sumitomo Metal Industries, average particle size 5 nm)
Consists of cesium tungsten oxide fine particles, Cs _0.33 WO ₃ (23 wt%) and a dispersant. (Hereinafter abbreviated as “Compound B”)

3. Antioxidant (C):
3-1. Hostalox P-EPQ manufactured by Clariant Japan (hereinafter abbreviated as “AO1”)
3-2. Asahi Denka Co., Ltd. ADK STAB AO-50 (hereinafter abbreviated as “AO2”)

4). Ultraviolet absorber (D): Benzotriazole ultraviolet absorber 4-1. ADEKA ADEKA STAB LA-31 (hereinafter abbreviated as “UVA1”)
4-2. TINUVIN 329 manufactured by BASF (hereinafter abbreviated as “UVA2”)

  The above-mentioned various raw materials are collectively put into a tumbler at a blending ratio shown in Tables 1 to 3, and after dry mixing for 10 minutes, using a twin-screw extruder (KTX37 manufactured by Kobe Steel) to a melting temperature of 280 ° C. And kneaded to obtain pellets of the polycarbonate resin composition. Various test pieces were processed from the obtained pellets using an injection molding machine (J100E-E2P manufactured by Nippon Steel), and various data were collected by the following methods. Each evaluation result was shown to Tables 1-3.

(1) Visible light selective transparency (evaluation of the property of selectively transmitting wavelengths in the visible light region and shielding the wavelengths in the ultraviolet region and infrared region):
Each of the obtained pellets was dried at 120 ° C. for 4 hours, and then a flat plate test piece (length: 50 mm) using an injection molding machine (Japan Steel Works J100E2P) at a cylinder set temperature of 280 ° C. , The transmittance in the ultraviolet region 300 nm, visible light region 550 nm and near infrared region 900 nm was measured with a spectrophotometer (UH-4150 type spectrophotometer manufactured by Hitachi High-Tech Science Co., Ltd.). The transmittance at 300 nm and 900 nm is 5% or less, and the transmittance at 550 nm is 40% or more as good (◯).

(2) Thermal stability Each of the obtained pellets was dried at 120 ° C. for 4 hours, and then subjected to a cylinder setting temperature of 300 ° C. using an injection molding machine (J100E2P manufactured by Nippon Steel). Then, a flat plate test piece (length 50 mm, width 50 mm, thickness 1 mm) before and after retention for 15 minutes was prepared, and the change in YI (ΔYI) was measured with a spectrophotometer (CMS-35SP manufactured by Murakami Color Research Laboratory). ΔYI represents the difference in yellowness before and after the stay. The smaller ΔYI, the smaller the color change and the better the thermal stability. As a criterion for evaluation of ΔYI, a value of ΔYI of less than 5 was judged as good (◯), and a value of 5 or more was judged as bad (x).

(3) Weather resistance After drying the obtained various pellets under the conditions of 120 ° C. × 4 hours, for weather resistance evaluation at a cylinder set temperature of 280 ° C. using an injection molding machine (J100E2P manufactured by Nippon Steel) A test piece (length 50 mm, width 50 mm, thickness 1 mm) was prepared. The obtained test piece was attached to a xenon weather meter (Super Xenon Weather Meter SX75 manufactured by Suga Test Instruments Co., Ltd.), and the setting was made with an irradiance of 180 W / m ² , a humidity of 50% RH, and a black panel temperature of 63 ° C. for 1 hour. The irradiation test was performed for 600 hours in the 18-minute rainfall cycle following the minute irradiation, and the change in YI (ΔYI) was measured with a spectrophotometer (CMS-35SP manufactured by Murakami Color Research Laboratory). ΔYI represents the difference in yellowness before and after the irradiation test. The smaller the ΔYI, the smaller the color change and the better the weather resistance. As a criterion for evaluation of ΔYI, a case where the value of ΔYI was less than 10 was judged as good (◯), and a case where it was 10 or more was judged as bad (×).

  As shown in Tables 1 and 2, when the polycarbonate resin composition satisfied all the constituent requirements of the present invention (Examples 1 to 12), good results were shown over all the evaluation items.

On the other hand, as shown in Table 3, when the polycarbonate resin composition did not satisfy the constituent requirements of the present invention, each case had some drawbacks.
Comparative Example 1 was a case where the compounding amount of Compound B was less than the specified amount and was inferior in visible light selective permeability and weather resistance.
Comparative Example 2 was a case where the compounding amount of Compound B was larger than the specified amount, and was inferior in visible light selective permeability and thermal stability.
Comparative Example 3 was a case where the blending amount of AO1 was less than the specified amount and was inferior in thermal stability.
In Comparative Example 4, the amount of AO1 was greater than the specified amount, and the thermal stability was poor.
In Comparative Example 5, the blending amount of UVA1 was larger than the specified amount, and the heat stability was poor.

  As described above, the embodiments have been described as examples of the technology in the present invention. To that end, a detailed explanation was provided.

  Accordingly, the components described in the detailed description include not only components essential for solving the problem but also components not essential for solving the problem in order to illustrate the above technique. obtain. Therefore, it should not be immediately recognized that these non-essential components are essential as the non-essential components are described in the detailed description.

  Moreover, since the above-mentioned embodiment is for demonstrating the technique in this invention, a various change, replacement, addition, abbreviation, etc. can be performed in a claim or its equivalent range.

  The polycarbonate resin composition for the solar radiation sensor cover of the present invention is excellent in visible light selective transparency and thermal stability, and further in weather resistance without impairing various excellent performances possessed by the polycarbonate resin. It can be suitably used as a resin composition for a cover that selectively absorbs the wavelength in the visible light range transmitted to the solar radiation sensor and blocks the wavelengths in the ultraviolet region and the infrared region, and has extremely high industrial utility value.

Claims (4)

One or more selected from 100 parts by weight of polycarbonate resin (A), 0.023 to 0.23 parts by weight of cesium tungsten oxide fine particles as inorganic oxide (B), phosphorus antioxidant and phenolic antioxidant A polycarbonate resin composition for a solar sensor cover, comprising 0.05 to 1 part by weight of an antioxidant (C) and 0 to 2 parts by weight of an ultraviolet absorber (D). One or more antioxidants (C) selected from 100 parts by weight of polycarbonate resin (A), 0.1 to 1 part by weight of inorganic oxide (B), phosphorus antioxidant and phenolic antioxidant 0.05 to 1 part by weight, and 0 to 2 parts by weight of an ultraviolet absorber (D), the inorganic oxide (B) being cesium tungsten oxide fine particles Cs _0.33 WO ₃ A polycarbonate resin composition for a solar radiation sensor cover, comprising (23 wt%) and a dispersant. The polycarbonate resin composition for solar radiation sensor cover according to claim 1 or 2 , wherein the cesium tungsten oxide fine particles have a particle diameter of 1 nm to 800 nm. The polycarbonate resin for solar sensor cover according to claim 1 or 2 , wherein the ultraviolet absorber (D) is one or more ultraviolet absorbers selected from benzotriazole-based, triazine-based and benzophenone-based compounds. Composition.