JP2008214596A - Polycarbonate resin composition and heat ray shielding molded article using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition that has a low haze, an excellent transparency, a low solar transmittance, a sufficient heat-ray shielding property, an excellent mechanical strength, melt heat stability and is suitable for window glass of general architectural structure, window glass of automobile, etc., and a heat-ray shielding molded article thereof. <P>SOLUTION: The heat-ray shielding molded article having a low haze, an excellent transparency, a low solar transmittance and a sufficient heat-ray shielding property is obtained by mixing an aromatic polycarbonate resin having a specific viscosity-average molecular weight and a specific terminal hydroxy group concentration with a very small amount of tungsten oxide fine particle as an inorganic near infrared absorber. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention has a low solar transmittance and a sufficient heat ray shielding function, has a particularly low haze and excellent transparency, and also has excellent mechanical strength and fusion heat stability. The present invention relates to a polycarbonate resin composition suitable for automobile window glass and the like and a heat ray shielding molded article using the same.

  Near-infrared rays that penetrate through window glass of general buildings and window glass of automobiles and enter the room are a cause of excessively increasing the indoor temperature. In order to prevent this, there is a strong need to provide a heat ray shielding resin composition and a heat ray shielding molded article having a low solar transmittance and a sufficient heat ray shielding function, and particularly having low haze and excellent transparency. . In response to such demands, Patent Documents 1 and 2 disclose that polycarbonate resins (hereinafter sometimes abbreviated as PC resins), poly (meth) acrylic resins, polyethylene resins, polyester resins, polystyrene resins, or vinyl chloride resins. Although a heat ray shielding material containing a phthalocyanine compound is disclosed, a large amount of a phthalocyanine compound must be added to provide sufficient heat ray shielding properties, and if it is added in a large amount, haze increases and transparency decreases. In addition, the weather resistance was insufficient.

  Patent Documents 3 and 4 also disclose a heat ray shielding resin plate in which a heat ray reflective film on which a metal or a metal oxide is deposited is laminated on a transparent resin plate. However, the heat ray reflective film is expensive and cumbersome lamination. A process was necessary, and the utility was low.

Further, the present applicant selects in Patent Document 5 from polycarbonate resin, poly (meth) acrylate resin, saturated polyester resin, cyclic olefin resin, polyimide resin, polyether sulfone resin and fluorine resin. Has proposed a heat-shielding resin molded product in which hexaboride is blended with at least one thermoplastic resin, but it requires adjustment of haze and transparency. There was a problem for glass.
Patent Document 6 uses tungsten oxide obtained by hydrolyzing tungstic acid, and by adding an organic polymer having a specific structure called polyvinylpyrrolidone to the tungsten oxide, The ultraviolet rays inside are absorbed by tungsten oxide to generate excited electrons and holes, and the appearance amount of pentavalent tungsten is remarkably increased by a small amount of ultraviolet rays, and the coloring reaction is accelerated, and the coloring density is increased accordingly. together, by blocking the light, using a pentavalent tungsten very rapidly hexavalent is oxidized decoloring reaction faster on the characteristics, fast coloring and decoloring reactions to sunlight, the near-infrared region when the colored An absorption peak appears at a wavelength of 1250 nm, and it is proposed that a sunlight-modulable light insulating material capable of blocking the near-infrared ray of sunlight can be obtained. That.

  Further, the present applicant, in Patent Document 7, by dissolving tungsten hexachloride in alcohol and evaporating the solvent as it is, or evaporating the solvent after heating to reflux, and then heating at 100 ° C. to 500 ° C. Obtaining a powder composed of tungsten trioxide or a hydrate thereof, or a mixture of both, obtaining an electrochromic device using the tungsten oxide fine particles, and forming a multilayer stack and introducing protons into the film It has been proposed that the optical characteristics of the film can be changed.

Further, in Patent Document 8, a meta-type ammonium tungstate and various water-soluble metal salts are used as raw materials, and a dried product of the mixed aqueous solution is heated at a heating temperature of about 300 to 700 ° C., and inactive during the heating. By supplying hydrogen gas to which gas (addition amount: about 50 vol% or more) or water vapor (addition amount: about 15 vol% or less) is supplied, M _x WO ₃ (M: metal element such as alkali, alkaline earth, rare earth, etc.) , 0 <x <1), various methods for producing tungsten bronzes have been proposed. In addition, a method for producing various tungsten bronze-coated composites by performing the same operation on the support has been proposed, and it has been proposed to be used as an electrode catalyst material for fuel cells and the like.

Further, the present applicant has disclosed in Patent Document 9 an infrared shielding material fine particle dispersion in which infrared shielding material fine particles are dispersed in a medium, and the infrared shielding material fine particles have the general formula WyOz (where W is tungsten, O is oxygen, fine particles of tungsten oxide represented by 2.2 ≦ z / y ≦ 2.999, or / and general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal) , Rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, One or more types selected from Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I Elements, W is tungsten, O is acid , 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0), and the particle diameter of the infrared shielding material fine particles is 1 nm or more and 800 nm. It discloses the optical properties, conductivity, and manufacturing method of the infrared shielding material fine particle dispersion characterized by the following.
JP-A-6-240146 JP-A-6-264050 Japanese Patent Laid-Open No. 10-146919 Japanese Patent Laid-Open No. 2001-179887 JP 2004-162020 A JP-A-9-127559 JP 2003-121884 A JP-A-8-73223 International Publication WO2005 / 37932

  The present invention has been made in view of the above circumstances, using a new inorganic near-infrared absorber, having low haze, excellent transparency, low solar transmittance, and sufficient heat ray shielding (particularly for visible light). Polycarbonate resin composition that has transparency and a function of selectively shielding infrared rays), and is excellent in mechanical strength and melting heat stability, and is suitable for window glass of general buildings, window glass of automobiles, etc. An object and a heat ray shielding molded body using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that a minute amount of inorganic polycarbonate as a near-infrared absorber for an aromatic polycarbonate resin having a specific viscosity average molecular weight and a specific terminal hydroxyl group concentration. It has been found that the above-mentioned problems can be solved by blending the tungsten oxide fine particles, and the present invention has been achieved.

That is, the first invention of the present invention is 100 parts by weight of an aromatic polycarbonate resin (A) having a viscosity average molecular weight of 12,000 to 50,000 and a terminal hydroxyl group concentration in the range of 100 to 1800 ppm, A polycarbonate resin composition containing 0.001 to 5 parts by weight of an inorganic near-infrared absorber (B) that absorbs sunlight in a wavelength region of ˜2600 nm,
The inorganic near-infrared absorber (B) is a tungsten oxide represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), and / or Formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag , Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re , Be, Hf, Os, Bi, I, one or more elements selected from W, tungsten is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3. 0) Inorganic fine particles made of composite tungsten oxide Providing polycarbonate resin composition according to symptoms.

  According to a second aspect of the present invention, there is provided the polycarbonate resin composition according to the first aspect, wherein the aromatic polycarbonate resin is polymerized by an ester exchange reaction from an aromatic dihydroxy compound and a carbonic acid diester. provide.

  According to a third aspect of the present invention, there is provided the polycarbonate resin composition according to the first aspect or the second aspect, wherein the aromatic polycarbonate resin has a terminal hydroxyl group concentration of 300 to 1500 ppm.

  4th invention of this invention is a heat ray shielding molded object which shape | molds the polycarbonate resin composition in any one of 1st-3rd invention, Comprising: It has a plate-shaped part of thickness 0.2-10mm And the heat ray shielding molded object characterized by the haze in this plate-shaped part being less than 5%, and the solar radiation transmittance | permeability is 70% or less.

  A fifth invention of the present invention is characterized in that at least one coating layer selected from a hard coat layer and an antireflection layer is provided on one or both sides of the plate-like portion of the molded article. The heat ray shielding molded product according to the invention of 4 is provided.

According to a sixth aspect of the present invention, when the hue of the plate-like portion is evaluated in the L ^* a ^* b ^* color system, L ^* value = 93 to 35, a ^* value = 0 to −12, and b ^*. A heat ray shielding molded article according to the fourth or fifth invention is provided, which is in a range represented by a value = 3 to -7.

  A seventh invention of the present invention provides the heat ray shielding molded article according to any one of the fourth to sixth inventions, wherein the molded article is a window or window part for a general building or a vehicle. To do.

  The polycarbonate resin composition of the present invention and the heat ray-shielding molded article using the polycarbonate resin composition have a specific viscosity-average molecular weight and a trace amount as an inorganic near infrared absorber in an aromatic polycarbonate resin having a specific terminal hydroxyl group concentration. By blending tungsten oxide fine particles, the haze is low, the transparency is excellent, and the solar radiation transmittance is low enough to provide sufficient heat ray shielding (particularly the function of being transparent to visible light and selectively blocking infrared rays). In addition, because it has excellent mechanical strength and heat stability, it can be used for general building and automobile window glass, roofing materials such as arcades and carports, optical materials such as infrared cut filters, and agricultural films. It is usable and useful.

(A) Aromatic polycarbonate resin The aromatic polycarbonate resin used in the present invention has a viscosity average molecular weight of 12,000 to 50,000 and a terminal hydroxyl group concentration of 100 to 1800 ppm (by weight). It is. The terminal hydroxyl group concentration may be 100 to 1800 ppm (weight basis), preferably the terminal hydroxyl group concentration may be 300 to 1500 ppm, and particularly preferably an aromatic polycarbonate resin having a terminal hydroxyl group concentration of 400 to 1200 ppm. .

  The molecular weight of the aromatic polycarbonate resin used in the present invention is 12,000 to 50,000 in terms of a viscosity average molecular weight converted from a solution viscosity measured at 25 ° C. using methylene chloride as a solvent. Necessary, preferably 15,000 to 40,000, particularly preferably 17,000 to 32,000. If the viscosity average molecular weight is less than 12,000, the mechanical strength is low, and if it exceeds 50,000, the moldability tends to decrease.

  By using the aromatic polycarbonate resin in the present invention, a polycarbonate resin composition having particularly low haze and excellent transparency can be obtained.

  The aromatic polycarbonate resin production method includes an interfacial polymerization method, a pyridine method, and a transesterification method, but the production method of the aromatic polycarbonate resin used in the present invention is not particularly limited. Preferably it is manufactured. Specifically, the aromatic polycarbonate resin used in the present invention is preferably produced by subjecting an aromatic dihydroxy compound and a carbonic acid diester as raw materials to transesterification and polymerization in a molten state in the presence of a transesterification catalyst. It is.

  Hereinafter, the aromatic polycarbonate resin used in the present invention will be specifically described.

(A) Aromatic dihydroxy compound Typical examples of the aromatic dihydroxy compound which is one of the raw materials of the aromatic polycarbonate resin used in the present invention include, for example, bis (4-hydroxyphenyl) methane, 2,2- Bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1- Bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4 Examples include '-dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, and bis (4-hydroxyphenyl) ketone.

  These aromatic dihydroxy compounds can be used alone or in admixture of two or more. Furthermore, polyvalent phenols having three or more hydroxy groups in the molecule such as 1,1,1-tris (4-hydroxylphenyl) ethane (THPE), 1,3,5-tris (4-hydroxyphenyl) benzene Etc. can be used together in small amounts as a branching agent. Among these aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (hereinafter also referred to as “bisphenol A” and sometimes abbreviated as “BPA”) is preferable.

(B) Carbonic acid diester Carbonic acid diester which is one of the other raw materials for producing the aromatic polycarbonate resin used in the present invention is, for example, diaryl carbonate, dimethyl represented by diphenyl carbonate, ditolyl carbonate and the like. Examples thereof include dialkyl carbonates typified by carbonate, diethyl carbonate, di-tert-butyl carbonate and the like. These carbonic acid diesters can be used alone or in admixture of two or more. Among these, diphenyl carbonate (hereinafter sometimes abbreviated as “DPC”) and substituted diphenyl carbonate are preferable.

  The amount of the carbonic acid diester is preferably 50 mol% or less, more preferably 30 mol% or less, and may be substituted with dicarboxylic acid or dicarboxylic acid ester. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate, and the like. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

  The aromatic polycarbonate resin used in the present invention has a terminal hydroxyl group concentration of 100 to 1800 ppm (weight basis), preferably 300 to 1500 ppm, more preferably 400 to 1200 ppm.

  In order to obtain the aromatic polycarbonate resin, the carbonic acid diester (including the above-mentioned substituted dicarboxylic acid or dicarboxylic acid ester; the same shall apply hereinafter) is usually used in excess relative to the aromatic dihydroxy compound. That is, the carbonic acid diester is used in a molar ratio within the range of 1.001 to 1.3, preferably 1.01 to 1.2 with respect to the aromatic dihydroxy compound. When the molar ratio is less than 1.001, the terminal hydroxyl group of the produced polycarbonate increases, and particularly when it exceeds 1800 ppm, the thermal stability and hydrolysis resistance deteriorate. Moreover, when the molar ratio is larger than 1.3, the terminal hydroxyl group of the aromatic polycarbonate resin decreases, but the rate of the transesterification reaction decreases under the same conditions, making it difficult to produce polycarbonate polymers and oligomers having a desired molecular weight. Further, if the terminal hydroxyl group concentration is less than 100 ppm, the haze of the polycarbonate resin composition becomes high and the transparency is lowered, which is not preferable.

  The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the aromatic polycarbonate resin. The method for measuring the terminal hydroxyl group is not particularly limited, but the titanium tetrachloride / acetic acid method (the method described in Macromol. Chem. 88 215 (1965)) is common.

  The reason why the aromatic polycarbonate resin produced by the transesterification method has a good haze is not clear, but the heterogeneous skeleton structure produced by the transesterification reaction is a functional group such as an OH group or a COOH group in the structural unit. It is presumed that these functional groups have a group and have a function similar to that of the terminal OH group.

  The amount of the heterogeneous skeleton structure as a percentage (mol%) of the total number of moles of the different structural units represented by the following formulas (2) and (3) with respect to the normal number of moles of the structural unit represented by the following formula (1) (Hereinafter referred to as “heterogeneous structure amount”), in the present invention, the heterogeneous structure amount of the aromatic polycarbonate resin produced by the transesterification method is usually 0.01 to 1 mol%, Preferably, it is 0.1-0.5 mol%. If the amount of the heterogeneous structure is too small, the effect of improving haze is insufficient, and if it is too large, gel formation and hue deterioration due to a crosslinking reaction are unfavorable.

（式中、Ｘは、単結合、炭素数１〜８のアルキレン基、炭素数２〜８のアルキリデン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルキリデン基、または、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ−及び−ＳＯ₂ −からなる群から選ばれる２価の基である。）
上記異種骨格構造の分析は、芳香族ポリカーボネート樹脂を塩化メチレンに溶解し、ナトリウムメトキシドメタノール溶液と純水の混合液で、室温で加水分解を行い、液体クロマトグラフ法で、検出波長２８０ｎｍのＵＶ検出器によって行う。定量は、各成分の吸光係数より求める。簡便法としては、ビスフェノールＡのピーク面積に対する各成分のピーク面積の比率から算出することもできる。

(In the formula, X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, or It is a divalent group selected from the group consisting of —O—, —S—, —CO—, —SO— and —SO ₂ —.
The heterogeneous skeletal structure is analyzed by dissolving an aromatic polycarbonate resin in methylene chloride, hydrolyzing at room temperature with a mixed solution of sodium methoxide methanol and pure water, and using liquid chromatography to detect UV light having a detection wavelength of 280 nm. Do by detector. Quantification is determined from the extinction coefficient of each component. As a simple method, it can also be calculated from the ratio of the peak area of each component to the peak area of bisphenol A.

(C) Transesterification catalyst When an aromatic polycarbonate resin is produced by subjecting an aromatic dihydroxy compound and a carbonic acid diester to a transesterification reaction in a molten state, a transesterification catalyst is usually used. In the production of the aromatic polycarbonate resin used in the present invention, the type of transesterification catalyst to be used is not limited, but in general, alkali metal compounds, alkaline earth metal compounds, basic boron compounds, basic phosphorus compounds Basic compounds such as basic ammonium compounds and amine compounds are used. These may be used alone or in combination of two or more.

  The catalyst is used in an amount of 0.05 to 200 μmol, preferably 0.08 to 10 μmol, more preferably 0.1 to 2 μmol, per 1 mol of the aromatic dihydroxy compound. If the amount of the catalyst used is less than the above amount, the polymerization activity necessary for producing an aromatic polycarbonate resin having a desired molecular weight cannot be obtained, and if it is more than this amount, the polymer hue tends to deteriorate.

  The transesterification catalyst is usually preferably used in the form of a catalyst solution dissolved in a solvent. Examples of the solvent include water, acetone, alcohol, toluene, phenol, a solvent that dissolves the raw material aromatic dihydroxy compound, carbonic acid diester, and the like. Among these solvents, water is preferable, and when an alkali metal compound is used as a catalyst, an aqueous solution is preferable.

(D) Manufacturing method of aromatic polycarbonate resin The manufacturing method of the aromatic polycarbonate resin used by this invention will not be specifically limited if it is a transesterification method, A well-known various method is employ | adopted.
For example, after stirring both the raw materials uniformly in a raw material mixing tank or the like, a catalyst is added and polymerization is performed to produce an aromatic polycarbonate resin. The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.

  The polymerization reaction of an aromatic polycarbonate resin (sometimes referred to as transesterification reaction) is generally carried out continuously in two or more stages, usually 3 to 7 stages, using two or more polymerization tanks. It is preferable. Specific reaction conditions include a temperature of 150 to 320 ° C., a normal pressure to 2 Pa, and an average residence time of 5 to 150 minutes. In each polymerization tank, the discharge of by-produced phenol is more effective as the reaction proceeds. In order to achieve this, within the above reaction conditions, the temperature is set stepwise to higher temperature and higher vacuum. In addition, in order to prevent quality degradation such as hue of the obtained aromatic polycarbonate resin, it is preferable to set as low a temperature as possible and as short a residence time as possible, and it may be appropriately adjusted according to the desired quality of the aromatic polycarbonate resin. .

  The apparatus used in the transesterification reaction may be any of a vertical type, a horizontal type, a tube type, or a column type. Turbine blades, paddle blades, anchor blades, full-zone blades (manufactured by Shinko Pantech Co., Ltd.), Sun Meller blades (manufactured by Mitsubishi Heavy Industries, Ltd.), Max Blend blades (manufactured by Sumitomo Heavy Industries, Ltd.), helical ribbons Following one or more vertical polymerization tanks equipped with blades, torsion lattice blades (manufactured by Hitachi, Ltd.), etc., horizontal type uniaxial polymerization tanks such as disk type and cage type, HVR, SCR, N-SCR (Mitsubishi) Heavy Industries Co., Ltd.), Vivolak (Sumitomo Heavy Industries, Ltd.), Glasses Wings, Lattice Wings (Hitachi, Ltd.), or Glasses Wings and Polymer Feeding Functions, eg Twist and Twist Etc., and / or a horizontal biaxial type polymerization tank equipped with a combination of blades with inclination and / or a combination of blades with an inclination, and the like can be used.

  In the aromatic polycarbonate resin produced by the transesterification method, a low molecular weight compound such as an aromatic hydroxy compound by-produced by a raw material monomer, a catalyst and a transesterification reaction usually remains. Among these, the raw material monomer and the aromatic hydroxy compound have a large residual amount and adversely affect physical properties such as heat aging resistance and hydrolysis resistance, and therefore are preferably removed upon commercialization.

  Specifically, as the amount of residual monomer in the polycarbonate resin, the aromatic dihydroxy compound is 150 ppm by weight or less, preferably 100 ppm by weight or less, more preferably 50 ppm by weight or less, and the aromatic monohydroxy compound is 100 ppm by weight or less. It is. Further, the residual amount of carbonic acid diester is 300 ppm by weight or less, preferably 200 ppm by weight or less, more preferably 150 ppm by weight or less.

  The method for removing the aromatic monohydroxy compound and the carbonic acid diester is not particularly limited, and for example, the aromatic monohydroxy compound and the carbonic acid diester can be removed by continuous deaeration using a vent type extruder. At that time, an acidic compound or a precursor thereof is added to the polycarbonate resin in advance, and the basic transesterification catalyst remaining in the resin is deactivated, thereby suppressing side reactions during degassing and efficiently. Raw material monomers and aromatic hydroxy compounds can be removed.

  The acidic compound to be added or its precursor is not particularly limited as long as it has an effect of neutralizing the basic transesterification catalyst used in the polycondensation reaction. Specifically, hydrochloric acid, nitric acid, boric acid , Sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, adipic acid, ascorbic acid, aspartic acid, azelaic acid, adenosine phosphoric acid, benzoic acid, formic acid, valeric acid, citric acid, glycolic acid, Glutamic acid, glutaric acid, cinnamic acid, succinic acid, acetic acid, tartaric acid, oxalic acid, p-toluenesulfinic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, nicotinic acid, picric acid, picolinic acid, phthalic acid, terephthalic acid, Bronsted acids such as propionic acid, benzenesulfinic acid, benzenesulfonic acid, malonic acid, maleic acid and their esters. It is. These may be used alone or in combination of two or more. Of these acidic compounds or precursors thereof, sulfonic acid compounds or ester compounds thereof, such as p-toluenesulfonic acid, methyl p-toluenesulfonate, and butyl p-toluenesulfonate are particularly preferable.

  The addition amount of the acidic compound or the precursor thereof is in the range of 0.1 to 50 times mol, preferably 0.5 to 30 times mol, with respect to the neutralization amount of the basic transesterification catalyst used in the polycondensation reaction. Can be added. The timing of adding the acidic compound or its precursor may be any time after the polycondensation reaction, and the addition method is not particularly limited, depending on the properties of the acidic compound or its precursor and the desired conditions. Any method such as a method of directly adding, a method of adding by dissolving in an appropriate solvent, a method of using a pellet or a flaky masterbatch may be used.

The extruder used for deaeration may be uniaxial or biaxial. As the twin screw extruder, a meshing type twin screw extruder is preferable, and the rotational direction may be the same direction or different direction. For the purpose of deaeration, those having a vent part after the acidic compound addition part are preferred. The number of vents is not limited, but usually a multistage vent of 2 to 10 stages is used. Moreover, in the said extruder, additives, such as a stabilizer, a ultraviolet absorber, a mold release agent, and a coloring agent, may be added as needed and knead | mixed with resin.
(B) Tungsten oxide fine particles, composite tungsten oxide fine particles The inorganic near-infrared absorber (B) used in the present invention absorbs sunlight in the wavelength range of 900 to 2600 nm from the viewpoint of cutting heat rays derived from solar energy. It is necessary to.

  As an inorganic near infrared absorber satisfying this condition, fine particles of tungsten oxide represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), and / or Or general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, One or more elements selected from Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0) composed of composite tungsten oxide Machine fine particles are necessary.

  In addition, even if it absorbs sunlight in the wavelength range of 900 to 2600 nm, phthalocyanine compounds and other organometallic compounds are poor in stability, kneading into PC resin, molding, and harsh usage environment It is not preferable because the quality changes below and adversely affects quality.

In the present invention, a mixture containing an inorganic near-infrared absorber can also be used, and examples thereof include a mixture of 25% by mass of composite tungsten oxide (Cs _0.33 WO ₃ ) and an acrylic dispersant. A PC resin masterbatch containing a composite tungsten oxide can also be used, and examples thereof include a PC resin masterbatch containing 1.5% by mass of Cs _0.33 WO ₃ .

In general, because there is no valid free electrons in WO _3, WO ₃ is less absorption reflection characteristics in the near infrared region, is not effective as an infrared-shielding material. Here, it is known that free electrons are generated in WO ₃ by reducing the ratio of oxygen to tungsten in WO ₃ from ₃ , but the present inventors have proposed that the composition of tungsten and oxygen. It has been found that there is a particularly effective range as an infrared shielding material in a specific part of the range.

The composition range of tungsten and oxygen is such that the composition ratio of oxygen to tungsten is 3 or less, and 2.2 ≦ z / y ≦ 2.999 when the infrared shielding material is described as WyOz. Is preferred. If the value of z / y is 2.2 or more, it is possible to avoid the appearance of a crystal phase of WO ₂ that is not intended in the infrared shielding material, and to improve the chemical stability as a material. Therefore, it can be applied as an effective infrared shielding material. On the other hand, if the value of z / y is 2.999 or less, a required amount of free electrons is generated, and an efficient infrared shielding material is obtained.

  In addition, in the tungsten oxide fine particles represented by the general formula WyOz, a so-called “Magneli phase” having a composition ratio represented by 2.45 ≦ z / y ≦ 2.999 is chemically stable, and a near infrared ray. Since the region has good absorption characteristics, it is preferable as an infrared shielding material.

Furthermore, the element M (wherein the M element is one or more elements selected from Cs, Rb, K, Tl, Ba, In, Li, Sn, Ca, Sr, and Na) is added to the WO _3. By adding, free electrons are generated in the WO ₃ and free electron-derived absorption characteristics are expressed in the near-infrared region, which is effective as a near-infrared absorbing material near 1000 nm. Here, from the viewpoint of stability in the WO ₃ to which the element M is added, the M element is selected from Cs, Rb, K, Tl, Ba, In, Li, Sn, Ca, Sr, and Na. One or more elements are preferred.

  Here, a more efficient infrared shielding material can be obtained by combining the control of the oxygen amount described above and the addition of an element that generates free electrons with respect to the WyOz. When the general formula of the infrared shielding material that combines the control of the amount of oxygen and the addition of an element that generates free electrons is described as MxWyOz (where M is the M element, W is tungsten, and O is oxygen) Infrared shielding material satisfying the relationship of 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0 is desirable.

  First, the value of x / y indicating the amount of element M added will be described.

  If the value of x / y is larger than 0.001, a sufficient amount of free electrons is generated and the intended infrared shielding effect can be obtained. As the amount of the element M added increases, the supply amount of free electrons increases and the infrared shielding efficiency also increases. However, when the value of x / y is about 1, the effect is saturated. Moreover, it is preferable that the value of x / y is smaller than 1 because an impurity phase can be prevented from being generated in the infrared shielding material.

  The element M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be , Hf, Os, Bi, I are preferably at least one selected from the group consisting of

  Here, from the viewpoint of stability in the MxWyOz to which the element M is added, the element M is an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh. Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te More preferably, the element is one or more elements selected from Ti, Nb, V, Mo, Ta, and Re. From the viewpoint of improving optical properties and weather resistance as an infrared shielding material, it is more preferable that the element M belongs to an alkaline earth metal element, a transition metal element, a group 4B element, or a group 5B element.

  Next, the value of z / y indicating the control of the oxygen amount will be described. Regarding the value of z / y, the same mechanism as that of the above-described infrared shielding material represented by WyOz works also in the infrared shielding material represented by MxWyOz, and also at z / y = 3.0. Therefore, 2.2 ≦ z / y ≦ 3.0 is preferable, and 2.45 ≦ z / y ≦ 3.0 is more preferable.

Furthermore, when the composite tungsten oxide fine particles described above have a hexagonal crystal structure, transmission of the fine particles in the visible light region is improved, and absorption in the near infrared region is improved. This will be described with reference to FIG. 1, which is a schematic plan view of the hexagonal crystal structure. In FIG. 1, six octahedrons formed of WO ₆ units indicated by reference numeral 1 are assembled to form a hexagonal void, and an element M indicated by reference symbol 2 is arranged in the void. The unit is composed of a large number of one unit and a hexagonal crystal structure is formed.

In order to improve the transmittance in the visible light region and improve the absorption characteristics in the near infrared region in this embodiment, the unit structure (WO ₆₎ described in FIG. It is sufficient that six octahedrons formed as a unit are assembled to form a hexagonal void, and the element M is arranged in the void), and the composite tungsten oxide fine particles are crystalline. Or amorphous.

When the cation of the element M is added to the hexagonal void, the transmittance in the visible light region is improved, and the absorption characteristics in the near infrared region are improved. Here, generally, the hexagonal crystal is formed when the element M having a large ionic radius is added, and specifically, the hexagonal crystal is formed when Cs, K, Rb, Tl, In, Ba, Sn is added. It is preferable because it is easily formed. Of course, the above-mentioned elements other than these are not problematic because the additive element M can exist in the hexagonal void formed by the WO ₆ unit.

  When the composite tungsten oxide fine particles having a hexagonal crystal structure have a uniform crystal structure, the addition amount of the additive element M is preferably 0.2 or more and 0.5 or less, more preferably 0.33 in terms of x. It is. When the value of x is 0.33, it is considered that the additive element M is arranged in all of the hexagonal voids.

  Besides hexagonal crystals, tetragonal and cubic tungsten bronzes are also effective as infrared shielding materials. The absorption position in the near infrared region tends to change depending on the crystal structure, and the absorption position tends to move the tetragonal crystal to the longer wavelength side than the cubic crystal and the hexagonal crystal to move to the longer wavelength side than the tetragonal crystal. There is. Concomitantly, the absorption characteristic in the visible light region is the smallest in hexagonal crystals, followed by tetragonal crystals, and cubic crystals are the largest among them. Therefore, hexagonal tungsten bronze is preferably used for the purpose of transmitting light in the visible light region and shielding light in the infrared region. However, the tendency of the optical characteristics described here is merely a rough tendency, and changes depending on the kind of additive element, the amount of addition, and the amount of oxygen, and the present invention is not limited to this.

  In the present embodiment, the tungsten oxide fine particles and / or the composite tungsten oxide fine particles absorb a large amount of light in the near-infrared region, particularly in the vicinity of 1000 nm, so that the transmitted color tone is often from blue to green. .

  Moreover, the particle diameter of the particle | grains of the said infrared shielding material can each be selected according to the intended purpose. First, when using for the application which maintained transparency, it is preferable to have a particle diameter of 800 nm or less. This is because particles smaller than 800 nm do not completely block light due to scattering, and can maintain visibility in the visible light region and at the same time efficiently maintain transparency. In particular, when importance is attached to transparency in the visible light region, it is preferable to further consider scattering by particles.

  When importance is attached to the reduction of scattering by the particles, the particle diameter is 200 nm or less, preferably 100 nm or less. The reason is that if the particle size of the particles is small, the scattering of light in the visible light region of 400 nm to 780 nm due to geometric scattering or Mie scattering is reduced, and as a result, the infrared shielding film becomes like a frosted glass and is clear and transparent. This is because it is possible to avoid the loss of sex. That is, when the particle diameter is 200 nm or less, the geometric scattering or Mie scattering is reduced, and a Rayleigh scattering region is obtained. This is because in the Rayleigh scattering region, the scattered light is reduced in inverse proportion to the sixth power of the particle diameter, so that the scattering is reduced and the transparency is improved as the particle diameter is reduced. Further, when the particle diameter is 100 nm or less, the scattered light is preferably extremely small. From the viewpoint of avoiding light scattering, a smaller particle diameter is preferable. If the particle diameter is 1 nm or more, industrial production is easy.

  By selecting the particle size to be 800 nm or less, the haze value of the infrared shielding material fine particle dispersion in which the infrared shielding material fine particles are dispersed in the medium can be set to a visible light transmittance of 85% or less and a haze of 30% or less. . If the haze is greater than 30%, it becomes like frosted glass, and clear transparency cannot be obtained.

Since the above tungsten oxide and composite tungsten oxide have little absorption in the visible light region and large absorption in the near infrared region, they are effective as a visible light transmission type infrared shielding material for heat insulation of windows and the like.
(C) Method for producing tungsten oxide and composite tungsten oxide Fine particles of tungsten oxide represented by the above general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999) And / or general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd) , Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V , Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0) Composite tongue The ten oxide fine particles can be obtained by heat-treating a tungsten compound starting material in an inert gas atmosphere or a reducing gas atmosphere.

  As the tungsten compound starting material, tungsten trioxide powder, tungsten dioxide powder, or hydrated tungsten oxide, tungsten hexachloride powder, ammonium tungstate powder, or tungsten hexachloride was dissolved in alcohol. Tungsten oxide hydrate powder obtained by post-drying, or tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol and then adding water to precipitate it and drying it Or any one or more selected from a tungsten compound powder obtained by drying an ammonium tungstate aqueous solution and a metal tungsten powder.

  Here, in the case of producing tungsten oxide fine particles, from the viewpoint of ease of the production process, tungsten oxide hydrate powder, tungsten trioxide, or tungsten compound powder obtained by drying ammonium tungstate aqueous solution, More preferably, is used. Further, when producing composite tungsten oxide fine particles, it is more preferable to use an ammonium tungstate aqueous solution or a tungsten hexachloride solution from the viewpoint that each element whose starting material is a solution can be easily mixed uniformly. These raw materials are used and heat-treated in an inert gas atmosphere or a reducing gas atmosphere to obtain infrared shielding material fine particles containing tungsten oxide fine particles having the above-mentioned particle diameter and / or composite tungsten oxide fine particles. be able to.

Further, the infrared shielding material fine particles containing the composite tungsten oxide fine particles represented by the general formula MxWyOz containing the element M are the above-described tungsten of the infrared shielding material fine particles containing the tungsten oxide fine particles represented by the general formula WyOz. The starting material is a tungsten compound containing the element M in the form of a single element or a compound.
Here, in order to produce a starting material in which each component is uniformly mixed at the molecular level, it is preferable to mix each material with a solution, and the tungsten compound starting material containing the element M is dissolved in a solvent such as water or an organic solvent. Preferably it is possible. Examples thereof include tungstate, chloride, nitrate, sulfate, oxalate, oxide, and the like containing element M, but are not limited to these and are preferably in the form of a solution.

Here, the heat treatment condition in the inert atmosphere is preferably 650 ° C. or higher. The starting material heat-treated at 650 ° C. or higher has a sufficient near-infrared absorbing power and is efficient as infrared shielding fine particles. As the inert gas, an inert gas such as Ar or N ₂ is preferably used. As the heat treatment conditions in the reducing atmosphere, first, the starting material is heat-treated at 100 ° C. to 650 ° C. in the reducing gas atmosphere, and then heat-treated at a temperature of 650 ° C. to 1200 ° C. in an inert gas atmosphere. Good to do. The reducing gas at this time is not particularly limited, but H ₂ is preferable. When H ₂ is used as the reducing gas, the composition of the reducing atmosphere is preferably such that, for example, H ₂ is mixed with an inert gas such as Ar or N _{2 at a} volume ratio of 0.1% or more. Is preferably mixed at 0.2% or more. If H ₂ is 0.1% or more by volume, the reduction can proceed efficiently.

The raw material powder reduced with hydrogen contains a magnetic phase, exhibits good infrared shielding properties, and can be used as infrared shielding particles in this state. However, since hydrogen contained in tungsten oxide is unstable, application may be limited in terms of weather resistance. Therefore, a more stable infrared shielding fine particle can be obtained by heat-treating the tungsten oxide compound containing hydrogen at 650 ° C. or higher in an inert atmosphere. The atmosphere during the heat treatment at 650 ° C. or higher is not particularly limited, but N ₂ and Ar are preferable from an industrial viewpoint. By the heat treatment at 650 ° C. or higher, a Magneli phase is obtained in the infrared shielding fine particles, and the weather resistance is improved.

  In the present invention, a tungsten oxide represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999) which is a component of the inorganic near-infrared absorber (B) in the present invention. And / or general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni) , Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb , V, Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1,. 2 ≦ z / y ≦ 3.0) In addition to fine particles, 0.0001 to 0.1 parts by weight of at least one or more metal oxides selected from the group of Si, Zr, Ti and Al per 100 parts by weight of B component, metal nitriding It is preferable to contain a metal carbide (B ′ component).

  In the present invention, the tungsten oxide fine particles and / or the composite tungsten oxide fine particles may have a surface coated with a silane compound, a titanium compound, a zirconia compound, etc. By coating the surface of the fine particles with the compound, it becomes possible to improve the water resistance of the tungsten oxide fine particles and / or the composite tungsten oxide fine particles.

  Furthermore, in the present invention, the tungsten oxide fine particles and / or the composite tungsten oxide fine particles are preferably dispersed in a polymer-based dispersant in order to improve uniform dispersibility and workability. As such a polymeric dispersant, one having high transparency and high light transmittance in the visible light region can be used. Specific polymer dispersants include polyacrylate dispersants, polyurethane dispersants, polyether dispersants, polyester dispersants, polyester urethane dispersants, preferably polyacrylate dispersants, A polyether dispersant and a polyester dispersant. The blending ratio of the polymeric dispersant to the tungsten oxide fine particles and / or composite tungsten oxide fine particles is 0.3 weight with respect to 1 part by weight of the tungsten oxide fine particles and / or composite tungsten oxide fine particles. Part to 50 parts by weight, preferably 1 part to less than 15 parts by weight.

  The method of dispersing the tungsten oxide fine particles or / and the composite tungsten oxide fine particles in the polymer-based dispersant is, for example, the tungsten oxide fine particles or / and the composite tungsten oxide fine particles are an organic solvent and a polymer. An appropriate amount of a system dispersant is mixed, and bead mill mixing is performed for 5 hours using zirconia beads having a diameter of 0.3 mm, and tungsten oxide fine particles or / and composite tungsten oxide fine particle dispersion (tungsten oxide fine particles or / and Composite tungsten oxide fine particles: 15% by weight) are prepared. Furthermore, an appropriate amount of a polymeric dispersant is added to the dispersion, and the organic solvent is removed under reduced pressure at 60 ° C. while stirring to obtain tungsten oxide fine particles and / or composite tungsten oxide fine particle dispersion. Can do.

  The blending ratio of the aromatic polycarbonate resin and the tungsten oxide is preferably 0.001 to 5 parts by weight of tungsten oxide fine particles and / or composite tungsten oxide fine particles with respect to 100 parts by weight of the aromatic polycarbonate resin. Is 0.005 to 1 part by weight. If the blending ratio of the tungsten oxide fine particles and / or the composite tungsten oxide fine particles is less than 0.001 part by weight, the heat ray shielding effect is small, and if it exceeds 5 parts by weight, the haze is increased and the transparency is lowered and the cost is lowered. This is disadvantageous because it is disadvantageous.

Further, the polycarbonate resin composition of the present invention may be blended with the following weather resistance improver, heat stabilizer, antioxidant, release agent, and dye / pigment for use in molding or as a window or window part. Above, it is preferable because the hue stability is improved.
(D) Weatherability improver Examples of the weatherability improver include inorganic ultraviolet absorbers such as titanium oxide, cerium oxide, and zinc oxide, and organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds.

  In the present invention, among these, organic ultraviolet absorbers are preferred, and in particular, benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy]- Phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) ) Bis [4H-3,1-benzoxazin-4-one], [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester.

  Examples of the benzotriazole compound include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′- Hydroxy-5′-methacryloxyphenyl) -2H-benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- [2′- Droxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6) '' -Tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2'-methylene bis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2 -Yl) phenol], methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol and the like.

  Particularly preferred as weathering improvers are 2- (2′-hydroxy-5′-t-octylphenyl) -2H-benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4 , 6-Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2′-methylene bis [4- (1,1,3, 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol].

The compounding ratio of the weather resistance improving agent is 0.01 to 5 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin. When the amount exceeds 5 parts by weight, there is a problem such as mold deposit, and when the amount is less than 0.01 parts by weight, the effect of improving the weather resistance is insufficient. Although one type of weather resistance improver can be used, a plurality of types can also be used in combination.
(E) Heat stabilizer The heat stabilizer preferably used in the present invention is obtained by esterifying at least one ester in a molecule with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms. It is at least one selected from a phosphite compound, phosphorous acid and tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphonite.
Specific examples of the phosphite compound include trioctyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triisooctyl phosphite, tris (nonylphenyl) phosphite, tris (2,4 -Dinolylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, triphenylphosphite, tris (octylphenyl) phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, octyl Diphenyl phosphite, dilauryl phenyl phosphite, diisodecyl phenyl phosphite, bis (nonylphenyl) phenyl phosphite, diisooctylphenyl phosphite, diisodecyl pentaerythritol Diphosphite, dilauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, (phenyl) (1,3-propanediol) phosphite, (4-methylphenyl) (1,3-propanediol) phosphite, ( 2,6-dimethylphenyl) (1,3-propanediol) phosphite, (4-tert-butylphenyl) (1,3-propanediol) phosphite, (2,4-di-tert-butylphenyl) ( 1,3-propanediol) phosphite, (2,6-di-tert-butylphenyl) (1,3-propanediol) phosphite, (2,6-di-tert-butyl-4-methylphenyl) ( 1,3-propanediol) phosphite, (phenyl) (1,2-ethanedioe ) Phosphite, (4-methylphenyl) (1,2-ethanediol) phosphite, (2,6-dimethylphenyl) (1,2-ethanediol) phosphite, (4-tert-butylphenyl) (1 , 2-ethanediol) phosphite, (2,4-di-tert-butylphenyl) (1,2-ethanediol) phosphite, (2,6-di-tert-butylphenyl) (1,2-ethane Diol) phosphite, (2,6-di-tert-butyl-4-methylphenyl) (1,2-ethanediol) phosphite, (2,6-di-tert-butyl-4-methylphenyl) (1 , 4-butanediol) phosphite, diphenylpentaerythritol diphosphite, bis (2-methylphenyl) pentaerythritol diphosphat Bis (3-methylphenyl) pentaerythritol diphosphite, bis (4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dimethylphenyl) pentaerythritol diphosphite, bis (2,6-dimethyl) Phenyl) pentaerythritol diphosphite, bis (2,3,6-trimethylphenyl) pentaerythritol diphosphite, bis (2-tert-butylphenyl) pentaerythritol diphosphite, bis (3-tert-butylphenyl) penta Erythritol diphosphite, bis (4-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl) Ruphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol Examples thereof include diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (biphenyl) pentaerythritol diphosphite, and dinaphthyl pentaerythritol diphosphite.

The blending ratio of the heat stabilizer is 0.001 to 1 part by weight, preferably 0.001 to 0.4 part by weight, based on 100 parts by weight of the aromatic polycarbonate resin. When it exceeds 1 part by weight, there are problems such as deterioration of hydrolysis resistance.
(F) Antioxidant Antioxidants that are preferably used in the present invention include hindered phenolic antioxidants. Specific examples include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di -Tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxy Phenyl] methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene -2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy -M-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl) -4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) ) -1,3,5-triazin-2-ylamino) phenol, etc. Among them, in particular, pentaerythritol tetrakis [3- (3,5-di-tert-butyl- -Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, these two phenolic antioxidants are available from Ciba Specialty Chemicals. Commercially available under the names Knox 1010 and Irganox 1076.

The blending ratio of the phenolic antioxidant is preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the aromatic polycarbonate resin. If the blending amount of the phenolic antioxidant is less than 0.01 parts by weight, the effect as an antioxidant is insufficient, and even if it exceeds 1 part by weight, no further effect as an antioxidant can be obtained.
(G) Release Agent The release agent preferably used in the present invention includes aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000 and polysiloxanes. It is at least one compound selected from silicone oils.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, a preferable aliphatic carboxylic acid is a monovalent or divalent carboxylic acid having 6 to 36 carbon atoms, and an aliphatic saturated monovalent carboxylic acid having 6 to 36 carbon atoms is more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melissic acid, tetrariacontanoic acid, montanic acid , Adipic acid, azelaic acid and the like.

  As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, the same one as the aliphatic carboxylic acid can be used. Examples of the alcohol that reacts with the aliphatic carboxylic acid to form an ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, aliphatic includes alicyclic compounds. Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc. can be mentioned. These ester compounds of aliphatic carboxylic acid and alcohol may contain aliphatic carboxylic acid and / or alcohol as impurities, or may be a mixture of a plurality of compounds.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, as the aliphatic hydrocarbon, an alicyclic hydrocarbon is also included. Moreover, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, and partial oxides of polyethylene wax are preferable, and paraffin wax and polyethylene wax are more preferable. The number average molecular weight is 200 to 15,000, preferably 200 to 5,000. These aliphatic hydrocarbons may be a single substance, or a mixture of various constituent components and molecular weights, as long as the main component is within the above range.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. These may be used alone or in combination of two or more.

The compounding ratio of the release agent is 0.01 to 1 part by weight with respect to 100 parts by weight of the aromatic polycarbonate resin. When the compounding ratio of the release agent exceeds 1 part by weight, there are problems such as degradation of hydrolysis resistance and mold contamination during injection molding. One type of release agent can be used, but a plurality of release agents can be used in combination.
(H) Dye / pigment Examples of the dye / pigment used in the present invention include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow, silicate pigments such as ultramarine blue, titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, and zinc-iron. -Based brown, titanium-cobalt green, cobalt-green, cobalt-blue, oxide-based pigments such as copper-chromium black, copper-iron-based black, chromic pigments such as yellow lead, molybdate orange, ferrocyans such as bitumen And the like. Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green, azo dyes such as nickel azo yellow, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, Examples thereof include condensed polycyclic dyes such as quinophthalone, anthraquinone, heterocyclic, and methyl dyes. Of these, titanium oxide, carbon black, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability, and carbon black, anthraquinone-based compounds, and phthalocyanine-based compounds are more preferable. Specific examples thereof include MACROLEX Blue RR, MACROLEX Violet 3R, MACROLEX Violet B (manufactured by Bayer), Sumiplast Violet RR, Sumiplast Violet B, Sumiplast Blue OR, Sumitomo Chemical D, Sumitomo Chemical D Blue G, Diaresin Blue N (manufactured by Mitsubishi Chemical Corporation), and the like.

The blending ratio of the dye / pigment is 1 part by weight or less, preferably 0.3 part by weight or less, and more preferably 0.1 part by weight or less with respect to 100 parts by weight of the aromatic polycarbonate resin. The colorant can be used alone or in combination of two or more.
In the present invention, the dye / pigment is originally blended for the purpose of adjusting the visibility by transmitted light. That is, when the blending amount of the tungsten oxide fine particles and / or the composite tungsten oxide fine particles is increased, the hue of the molded body is changed and the visibility is lowered (specifically, the L ^* value is lowered, and a ^* The absolute value of the value and b ^* value) tends to increase), and the visibility by transmitted light is improved by selecting the type and / or blending ratio of the dye / pigment to be blended to an appropriate hue. Of course, depending on the use of the molded product, for example, in a sunroof or the like, a black pigment such as carbon black can be blended and the L value can be intentionally lowered within a range that does not impair the heat ray shielding property.
The polycarbonate resin composition of (I) an infrared absorbent present invention, in order to further improve the heat ray-shielding performance, if necessary, chosen more of antimony-doped tin oxide fine particles, an In, Ga, from the group consisting of Al and Sb Other organic and inorganic infrared absorbers such as zinc oxide fine particles, tin-doped indium oxide fine particles, phthalocyanine-based, naphthalocyanine-based, copper sulfide, and copper ions containing at least one kind of element can also be blended.
(J) Other Additives The polycarbonate resin composition of the present invention further includes other thermoplastic resins such as ABS, polystyrene, polyethylene, polypropylene, and polyester, phosphorus-based, metal, and the like within a range not impairing the object of the present invention. Salt-based, silicon-based flame retardants, impact modifiers, antistatic agents, slip agents, antiblocking agents, lubricants, antifogging agents, natural oils, synthetic oils, waxes, organic fillers, glass fibers, carbon Additives such as fibrous reinforcing materials such as fibers, plate-like reinforcing materials such as mica, talc, and glass flakes, or inorganic fillers such as whiskers such as potassium titanate, aluminum borate, and wollastonite can be blended. .
(K) Method for Producing Polycarbonate Resin Composition The method for producing the polycarbonate resin composition of the present invention is not particularly limited. For example, (1) during the polymerization reaction of aromatic polycarbonate resin or at the end of the polymerization reaction, tungsten oxide Method of mixing fine particles or / and composite tungsten oxide fine particles and other additives, (2) Tungsten oxide fine particles and / or composite tungsten oxidation in a state where the aromatic polycarbonate resin is melted, such as during kneading (3) Tungsten oxide fine particles and / or composite tungsten oxide fine particles and other additives are added to those in which the aromatic polycarbonate resin is in a solid state, such as pellets. A method of melting and kneading with an extruder or the like after mixing may be mentioned.
(L) Heat ray shielding molded article (a) Molding method and molded article The method of molding the heat ray shielding molded article from the polycarbonate resin composition of the present invention is not particularly limited, and is generally used for thermoplastic resins. Any molding method, for example, injection molding, injection blow molding, injection compression molding, blow molding, extrusion molding of film or sheet, profile extrusion molding, thermoforming, rotational molding, etc. can be applied. Furthermore, fluid-assisted molding such as gas or water, molding using supercritical or subcritical gas, insert molding of functionalized film or sheet such as various printing, two-color molding, in-mold molding, other resin or UV Coextrusion of the absorbent layer, lamination, etc. are also possible. Injection molding or injection compression molding is preferable because of the degree of freedom of the shape that can be molded. Furthermore, a hot runner can be used in injection molding or injection compression molding.

  The shape of the formed body can be formed into an arbitrary shape as necessary, but preferably has a planar or curved plate-like portion. Although there is no restriction | limiting in particular in the thickness of a plate-shaped part, The heat ray shielding molded object of this invention has a plate-shaped part 0.2 mm or more and 10 mm or less. The thickness of the plate-like portion is preferably 1 mm or more and 10 mm or less, and most preferably 3 mm or more and 8 mm or less. When the thickness of the plate-like portion is 0.2 mm or less, it is necessary to blend tungsten oxide fine particles and / or composite tungsten oxide fine particles at a high concentration in order to obtain sufficient heat ray shielding performance, and it is difficult to obtain transparency. Such a heat ray shielding molded body can be further subjected to an annealing treatment, if necessary, and bonded to other parts. The bonding method is not particularly limited, but known methods such as vibration welding and laser welding can be used in addition to bonding with a solvent.

Moreover, the heat ray shielding molded product of the present invention is an aromatic polycarbonate resin molded product having a plate-like portion having a thickness of 0.2 to 10 mm, and the haze in the plate-like portion in the heat ray shielding molded product is less than 5%. Preferably, it is less than 3%, more preferably 2.5% or less, and the solar transmittance is preferably 70% or less, preferably 60% or less, and the total light transmittance and the solar transmittance are The ratio (total light transmittance / solar radiation transmittance) is preferably 1.4 or more, more preferably 1.6 or more, and further 1.9 or more. A large ratio between the total light transmittance and the solar radiation transmittance indicates that the heat rays are selectively absorbed as compared with visible light, and this value is preferably large.
(B) Hard coat layer, antireflection layer In order to provide the heat ray-shielding molded product of the present invention with the performance required as a window or window part, from the hard coat layer and the antireflection layer on one side or both sides of the plate-like part. A heat ray shielding molded article having at least one selected coating layer is preferable.

  A method of laminating at least one coating layer selected from a hard coat layer and an antireflection layer on one or both sides of the heat ray shielding molded article having a plate-like portion having a thickness of 0.2 to 10 mm is particularly limited. Instead, various conventionally known methods are used.

The antireflection layer may be, for example, (A) various vacuum deposition methods such as electron beam heating method, resistance heating method, flash deposition method, etc .; (B) plasma deposition method; (C) bipolar sputtering method, direct current sputtering method, high frequency sputtering. Various sputtering methods such as sputtering, magnetron sputtering, ion beam sputtering, and bias sputtering; (D) DC method, RF method, multi-cathode method, activation reaction method, HCD method, field evaporation method, high-frequency ion plating method Various ion plating methods such as reactive ion plating method; (E) CVD method and the like. Furthermore, the antireflection layer is coated by dispersing a metal oxide sol having a high refractive index such as ZrO ₂ sol, TiO ₂ sol, Sb ₂ O ₅ sol, and WO ₃ sol in a silicon hard coat agent or primer. -It can also be formed by thermosetting.

  In order to form the hard coat layer, an undercoat layer is provided if desired, and a hard coat agent such as epoxy, acrylic, amino resin, polysiloxane, colloidal silica, or organic / inorganic hybrid is used as a dip. A method of applying by various coating methods such as a coating method, a spin coating method, a spray coating method, a flow coating method and the like and curing by means of heat or ultraviolet rays can be used.

One or more of these hard coat layers can be provided on the heat ray shielding molded article. For example, the hard coat agent can be applied directly on the heat ray shielding molded body, but may be applied on an undercoat layer previously formed on the substrate. Further, the surface of the hard coat layer can be subjected to an antifogging treatment, an antireflection film coating or the like in addition to an inorganic compound treatment such as SiO ₂ by plasma polymerization or the like. The hard coat layer is not only formed by applying a hard coat agent to the surface of the molded product, but a sheet or film having the hard coat layer is set in a mold, and a polycarbonate resin composition is injection-molded there. By doing so, it is also possible to create an integrally molded body having a hard coat layer.

  In these hard coat layers, various kinds of treatment agents, for example, UV absorbers such as triazole and triazine compounds, and metal / metal oxide fine particle heat ray shielding such as boride, ITO, ATO, ZnO, zinc antimonate, etc. Agent, copper compound, organic complex, phthalocyanine, naphthalocyanine, diimonium, anthraquinone, aminium, cyanine, azo compound, quinone, polymethine, diphenylmethane, etc. These various heat ray shielding agents can also be contained. These additives may be added to either the hard coat layer and / or the undercoat layer.

  The thickness of the antireflection layer or hard coat layer is 1 μm to 20 μm, preferably 2 μm to 10 μm. If the thickness is less than 1 μm, the durability of the antireflection layer or the hard coat layer is insufficient, and if it exceeds 20 μm, cracks are likely to occur in the antireflection layer or the hard coat layer. The surface coating layer of the heat ray shielding molded article of the present invention is preferably a hard coat layer from the viewpoint of a window or window part.

  The plate-shaped portion having a thickness of 0.2 to 10 mm which the heat ray shielding molded body according to the present invention has has a haze of less than 5%, preferably less than 3%, more preferably 2.5% or less, and solar radiation. The transmittance is preferably 70% or less, and particularly preferably 60% or less. If the haze is 5% or more, the transparency is lowered and it is not suitable as a window glass for general buildings or vehicles. Further, if the solar radiation transmittance exceeds 70%, the indoor temperature of a general building or vehicle may be excessively increased, and therefore excluded from the present invention.

The heat ray shielding molded article of the present invention can be subjected to arbitrary partial decoration on the coating layer or the polycarbonate resin, and can impart designability by blackout, various marks, characters, etc. The hue of the plate-like portion in the shielding molded body, which is not decorated, has an L ^* value of 93 to 35 and an a ^* value of when evaluated in the L ^* a ^* b ^* color system. It is preferably 0 to -12 and a b ^* value of 3 to -7. When the L value is less than 35, even if the a ^* value and the b ^* value are within the predetermined ranges of 0 to -12 and 3 to -7, respectively, blackening occurs and the transparency is lowered. Even if the L ^* value is 80 or more, if the a ^* value and the b ^* value are smaller than −12 and −7, respectively, green to bluish color is obtained. Unfavorably yellowish color. Furthermore, when the L ^* value, a ^* value, and b ^* value are out of the above ranges, the hue heat stability of the polycarbonate resin composition tends to be low.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In the following examples, details of the raw materials used are as follows.
〔raw materials〕
(1) Aromatic polycarbonate * PC-1: Polycarbonate resin produced by a transesterification method (viscosity average molecular weight = 21,000, terminal hydroxyl group concentration = 1000 ppm, heterogeneous structure amount = 0.30 mol%)
* PC-2: Polycarbonate resin produced by a transesterification method (viscosity average molecular weight = 21,000, terminal hydroxyl group concentration = 150 ppm, heterogeneous structure amount = 0.35 mol%)
* PC-3: Polycarbonate resin produced by the interfacial method (Mitsubishi Engineering Plastics Co., Ltd., trade name Iupilon S-3000, viscosity average molecular weight = 21,000, terminal hydroxyl group concentration = 150 ppm, heterogeneous structure amount = 0 mol) %)
* PC-4: Polycarbonate resin produced by an interfacial method (Mitsubishi Engineering Plastics, trade name: Novalex 7022pj, viscosity average molecular weight = 21,000, terminal hydroxyl group concentration = 50 ppm, heterogeneous structure content = 0 mol% )
(2) Composite tungsten oxide fine particles 1: Cs _0.33 WO ₃ fine particle dispersion, Cs _0.33 WO ₃ fine particle content 20% by weight
(3) Weather resistance improver: 2- (2′-hydroxy-5′-tert-octylphenyl) -2H-benzotriazole, manufactured by Cypro Kasei Co., Ltd., trade name Seasorb 709 (hereinafter “UV absorber 1”) Abbreviated)
(4) Thermal stabilizer: Tris (2,4-di-tert-butylphenyl) phosphite, manufactured by Asahi Denka Kogyo Co., Ltd., trade name ADK STAB AS2112 (hereinafter abbreviated as “phosphorous stabilizer 1”)
(5) Antioxidant: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals, trade name Irganox 1010 (hereinafter, “ Abbreviated as "phenolic stabilizer 1")
(6) Mold release agent 1: Pentaerythritol tetrastearate (Nippon Yushi Co., Ltd., trade name Unistar H476)

Moreover, in the following Examples, the evaluation method of the heat ray shielding molded object formed by shape | molding the obtained aromatic polycarbonate resin composition is as follows.
[Evaluation method]
(1) Haze / total light transmittance: According to JIS K-7136, a 3 mm-thick flat plate was used as a test piece, and measurement was performed with a HM-150W type haze meter manufactured by Murakami Color Research Laboratory.
(2) Solar radiation transmittance: From the value of the transmittance of light in the wavelength range 200-2600 nm measured using a U-4000 type spectrophotometer manufactured by Hitachi, Ltd., using a 3 mm thick flat plate as a test piece. The solar transmittance was calculated according to JIS R-3106.
(3) L ^* value, a ^* value, b ^* value: Using a 3 mm thick flat plate as a test piece, color tone (L ^* , a ^* , b ^* color) using a U-4000 type spectrophotometer manufactured by Hitachi, Ltd. System) was calculated.

(Examples 1-6, Comparative Examples 1-2)
After mixing the raw materials and additives described in Table 1, the mixture was supplied to a 40 mm single screw extruder and kneaded and pelletized at 280 ° C.

  The obtained pellets were dried at 120 ° C. for 5 hours and then 3 mm thick under the conditions of a cylinder temperature of 290 ° C., a mold temperature of 80 ° C. and a molding cycle of 40 seconds using an M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho A flat plate was formed. On this flat plate surface, an acrylic undercoat and a silicon hard coat were respectively applied and UV cured to form a 10 μm thick undercoat layer and a 5 μm thick hard coat layer. It was set as the test piece for 1)-(3). The evaluation results are shown in Table 1.

「評価」
上記表１において、実施例１〜３と比較例１、実施例４と比較例２の間では、複合タングステン酸化物の配合量が同一で比較するとき、末端水酸基濃度が所定の範囲から小さく外れているポリカーボネート樹脂を使用した場合は、ヘイズが高くなり、透明性が低下し、所定の範囲のポリカーボネート樹脂を使用した場合は、ヘイズが低く透明性に優れていることが明らかである。
また、実施例１〜３により、使用したポリカーボネート樹脂の末端水酸基濃度によって、ヘイズの低下効果に差があることが明らかである。
また、本発明の実施例の成形体は、ヘイズも低く、熱線遮蔽機能も十分優れており、色相も安定していることがわかる。

"Evaluation"
In Table 1 above, when Examples 1 to 3 and Comparative Example 1 and Example 4 and Comparative Example 2 are compared with the same compounding amount of the composite tungsten oxide, the terminal hydroxyl group concentration deviates slightly from the predetermined range. When a polycarbonate resin is used, the haze is increased and the transparency is lowered. When a polycarbonate resin in a predetermined range is used, it is clear that the haze is low and the transparency is excellent.
Moreover, it is clear from Examples 1-3 that there is a difference in the haze reduction effect depending on the terminal hydroxyl group concentration of the polycarbonate resin used.
Moreover, it turns out that the molded object of the Example of this invention has a low haze, the heat ray shielding function is sufficiently excellent, and the hue is also stable.

It is a schematic diagram which shows the crystal structure of the composite tungsten oxide fine particle which has a hexagonal crystal in this embodiment.

Explanation of symbols

1 WO ₆ unit 2 M element

Claims (7)

100 parts by weight of the aromatic polycarbonate resin (A) having a viscosity average molecular weight of 12,000 to 50,000 and a terminal hydroxyl group concentration in the range of 100 to 1800 ppm, and absorbs sunlight in the wavelength range of 900 to 2600 nm. A polycarbonate resin composition comprising 0.001 to 5 parts by weight of an inorganic near-infrared absorber (B),
The inorganic near-infrared absorber (B) is a tungsten oxide represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), and / or Formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag , Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re , Be, Hf, Os, Bi, I, one or more elements selected from W, tungsten is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3. 0) Inorganic fine particles made of composite tungsten oxide Polycarbonate resin composition according to symptoms.   2. The polycarbonate resin composition according to claim 1, wherein the aromatic polycarbonate resin is polymerized by an ester exchange reaction from an aromatic dihydroxy compound and a carbonic acid diester.   The polycarbonate resin composition according to claim 1, wherein the terminal hydroxyl group concentration of the aromatic polycarbonate resin is 300 to 1500 ppm.   A heat ray shielding molded article obtained by molding the polycarbonate resin composition according to any one of claims 1 to 3, having a plate-like portion having a thickness of 0.2 to 10 mm, and in the plate-like portion, A heat ray shielding molded article having a haze of less than 5% and a solar radiation transmittance of 70% or less.   5. The heat ray shielding molded article according to claim 4, wherein at least one coating layer selected from a hard coat layer and an antireflection layer is provided on one or both sides of the plate-like portion of the molded article. . When the hue of the plate-like portion is evaluated in the L ^* a ^* b ^* color system, L ^* value = 93 to 35, a ^* value = 0 to −12, and b ^* value = 3 to −7. The heat ray shielding molded article according to claim 4 or 5, wherein the heat ray shielding molded article is within a range.   The heat ray shielding molded body according to any one of claims 4 to 6, wherein the molded body is a window or a window part for a general building or a vehicle.

Images