JP2007169503A - Polycarbonate resin composition and molded article with heat radiation-shielding ability - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition which exhibits low transmission of solar radiation and sufficient heat radiation-shielding ability, especially has excellent heat stability and little variation in yellowness after being exposed to thermal stress for a long time, further is excellent in hydrolysis resistance under a wet heat atmosphere, and is suitable for a window glass for a general building, a window glass for a car, etc. and to provide a molded article using the same with sufficient heat radiation-shielding ability. <P>SOLUTION: The polycarbonate resin composition comprises (a) 0.0001-0.5 pt.wt. of boride fine particles of at least one metal selected from the group consisting of La, Ce, Pr, Nd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca, and (b) 0.005-1 pt.wt. of phosphine compound based on 100 pts.wt. of aromatic polycarbonate resin. The molded article having the heat radiation-shielding ability is obtained by molding the composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention has a low solar transmittance and a sufficient heat ray shielding function, is particularly excellent in heat-and-moisture stability, has a small change in yellowness even after being exposed to thermal stress for a long time, The present invention relates to a polycarbonate resin composition excellent in hydrolysis resistance below and suitable for a window glass of a general building, a window glass of an automobile, and the like, and a molded article having a heat ray shielding ability 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, provision of a heat ray shielding resin composition having a low solar transmittance and a sufficient heat ray shielding function and a molded body having a heat ray shielding ability is strongly demanded. In response to such demands, Patent Documents 1 and 2 disclose heat ray shielding materials in which a phthalocyanine compound is blended with a polycarbonate resin, a poly (meth) acrylic resin, a polyethylene resin, a polyester resin, a polystyrene resin, or a vinyl chloride resin. However, in order to provide sufficient heat ray shielding properties, a large amount of phthalocyanine compound has to be blended. When a large amount is blended, heat resistance is insufficient, coloring problems occur, and weather resistance is insufficient.
Patent Document 3 discloses a transparent thermoplastic resin containing an organic infrared absorber and a phosphine compound . However, the organic infrared absorber has insufficient heat resistance, and is an inorganic infrared absorber having excellent heat resistance. Although the combined use of metal oxides is disclosed, the heat resistance at the time of molding was insufficient due to the use of the organic infrared absorber. Furthermore, the hydrolysis resistance of the molded product is not mentioned at all.
Patent Document 4 discloses that a stable hard coat layer can be formed by adding a heat-resistant UV absorber and a phosphine compound to a polycarbonate resin, but it is exposed to heat ray shielding performance and thermal stress for a long time. No mention is made of the effects of the treatments and the hydrolysis resistance of the molded product.
Patent Document 5 discloses a molded body having a hard coat layer on the surface of a molded article obtained by injection molding of a metal boride and a polycarbonate containing a phosphite and / or phosphonite compound, but is exposed to thermal stress for a long time. No mention is made of the effects of this.
Further, Patent Document 6 discloses at least one selected from polycarbonate resins, poly (meth) acrylic ester resins, saturated polyester resins, cyclic olefin resins, polyimide resins, polyether sulfone resins, and fluorine resins. A heat ray shielding resin molded body in which hexaboride is blended with a kind of thermoplastic resin is disclosed. Although this technique achieves improved dispersion of the heat ray shielding component, the heat resistance in the molded product is insufficient. There was a large change in yellowness after prolonged exposure to thermal stress, and it was not satisfactory as a window glass for general buildings or window glass for automobiles.
Japanese Patent Laid-Open No. 06-240146 Japanese Patent Application Laid-Open No. 06-264050 JP 2003-12947 A JP 2004-167946 A JP 2005-179504 A JP 2004-162020 A

  The object of the present invention is particularly excellent in thermal stability, small change in yellowness even after long-term exposure to thermal stress, low solar radiation transmittance and sufficient heat ray shielding properties (particularly visible light transmission) And a polycarbonate resin composition suitable for window glass for general buildings, window glass for automobiles, etc., and having excellent resistance to hydrolysis in a humid heat atmosphere. It is providing the molded object provided with the heat ray shielding ability using this.

  As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by adding a specific compound when a trace amount of boride is added to an aromatic polycarbonate resin. That is, for 100 parts by weight of the aromatic polycarbonate resin, (a) from the group consisting of La, Ce, Pr, Nd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca Only when it contains 0.0001 to 0.5 part by weight of at least one selected metal boride fine particle and (b) phosphine compound 0.005 to 1 part by weight, it is particularly excellent in thermal stability and has a thermal stress. After a long exposure, the change in yellowness is small, the solar radiation transmittance is low, and there is sufficient heat ray shielding (particularly the function of being transparent to visible light and selectively blocking infrared rays) A polycarbonate resin composition that is also excellent in hydrolysis resistance in a humid heat atmosphere, that is inhibited from hydrolysis even when exposed to steam, and that has no decrease in transparency (an increase in haze). Becomes it found that molded bodies having a heat ray shielding ability is obtained, thereby completing the present invention.

  The polycarbonate resin composition of the present invention and a molded article having a heat ray shielding ability using the same are particularly excellent in thermal stability, have a small change in yellowness even after being exposed to thermal stress for a long time, and have a solar transmittance. And has sufficient heat ray shielding properties (especially the function of being transparent to visible light and selectively blocking infrared rays), and also has excellent hydrolysis resistance under humid heat atmosphere, and when exposed to steam In addition, there is no decrease in transparency (increase in haze) of polycarbonate, so it can be used as general building and automobile window glass, roofing materials such as arcades and carports, optical materials such as infrared cut filters, agricultural films, etc. .

Hereinafter, the present invention will be specifically described.
Aromatic polycarbonate resin The polycarbonate resin in the present invention is an aromatic polycarbonate polymer obtained by reacting an aromatic hydroxy compound with a phosgene or carbonic acid diester. The method for producing the aromatic polycarbonate resin is not particularly limited, and may be a conventional method such as a phosgene method (interfacial polymerization method) or a melting method (transesterification method).

  Typical examples of the aromatic dihydroxy compound that is one of the raw materials of the aromatic polycarbonate resin used in the present invention include, for example, bis (4-hydroxyphenyl) methane and 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′-dihydroxybiphenyl, bis 4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, 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.

  In the polymerization by the transesterification method, a carbonic acid diester is used as a monomer instead of phosgene. Representative examples of the carbonic acid diester include diaryl carbonates typified by diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates typified by dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. 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.

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

  When an aromatic polycarbonate is produced by a transesterification method, a catalyst is usually used. Although there is no limitation on the catalyst species, generally basic compounds such as alkali metal compounds, alkaline earth metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds are used. Of these, alkali metal compounds and / or alkaline earth metal compounds are particularly preferred. These may be used alone or in combination of two or more. In the transesterification method, the polymerization catalyst is generally deactivated with p-toluenesulfonic acid ester or the like.

  Preferred aromatic polycarbonates are those derived from 2,2-bis (4-hydroxyphenyl) propane or from 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy compounds. A polycarbonate copolymer is mentioned. Further, for the purpose of imparting flame retardancy and the like, a polymer or oligomer having a siloxane structure can be copolymerized. The aromatic polycarbonate may be a mixture of two or more kinds of polymers and / or copolymers having different raw materials, and may have a branched structure up to 0.5 mol%. The terminal OH group content of the aromatic polycarbonate is usually 30 to 2000 ppm, preferably 100 to 1500 ppm, more preferably 200 to 1000 ppm, and pt-butylphenol, phenol, cumylphenol, p-length as the sealing end. What was sealed with a chain alkyl-substituted phenol or the like can be used. As the amount of residual monomer in the polycarbonate resin, the aromatic dihydroxy compound is 150 ppm or less, preferably 100 ppm or less, and more preferably 50 ppm or less. When synthesized by the transesterification method, the residual amount of carbonic acid diester is 300 ppm or less, preferably 200 ppm or less, more preferably 150 ppm or less.

  Although there is no restriction | limiting in particular in the molecular weight of an aromatic polycarbonate, It is a thing of the range of 10,000-50,000 by the viscosity average molecular weight converted from the solution viscosity measured at the temperature of 20 degreeC using a methylene chloride as a solvent, It is preferably 11,000 to 40,000, particularly preferably in the range of 12,000 to 30,000.

Boride fine particles The boride used in the present invention was selected from the group consisting of La, Ce, Pr, Nd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca. At least one metal boride must be in the form of fine particles. The boride fine particles are preferably those whose surfaces are not oxidized, but even if they are somewhat oxidized, the effectiveness of the heat ray shielding effect can be used without change. These boride fine particles are colored powders such as gray black, brown black, green black, etc., but can be obtained if the particle size is sufficiently small compared to the visible light wavelength and dispersed in the resin molding. Visible light permeability is generated in the resin molded body having the heat ray shielding ability, and the infrared light shielding ability can be kept sufficiently strong. The boride fine particles have a particle size of 1000 nm or less, preferably 200 nm or less. A resin molded article having fine particles having a particle diameter larger than 1000 nm or coarse particles formed by agglomeration of fine particles is not preferred because haze increases and transparency decreases.

  In the present invention, boride fine particles whose surface is coated with a silane compound, titanium compound, zirconia compound or the like can be used, and boride fine particles can be obtained by coating the fine particle surface with these compounds. This makes it possible to improve the water resistance.

In the present invention, the boride fine particles are preferably dispersed in a polymer dispersant and / or an inorganic 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, and preferably polyacrylate dispersants. , Polyether dispersants and polyester dispersants. Examples of the inorganic dispersant include alkoxides of metals such as silicon, zirconium, titanium, and aluminum, or partial hydrolysis polymers of these metals. The blending ratio of the dispersant to the boride fine particles is 0.3 parts by weight or more and less than 50 parts by weight, preferably 1 part by weight or more and less than 15 parts by weight with respect to 1 part by weight of the boride fine particles.
A method of dispersing boride fine particles in a polymer-based dispersant is, for example, mixing an appropriate amount of boride fine particles, an organic solvent, and a dispersant, mixing the beads with a zirconia bead having a diameter of 0.3 mm for 5 hours, and boride. A fine particle dispersion (boride fine particle concentration: 6.5% by weight) is prepared. Furthermore, a boric fine particle dispersion can be obtained by adding an appropriate amount of a dispersant to the above dispersion and removing the organic solvent under reduced pressure at 60 ° C. while stirring.

  The blending ratio of the aromatic polycarbonate resin and boride is 0.0001 to 0.5 parts by weight of boride, more preferably 0.0005 to 0.1 parts by weight, with respect to 100 parts by weight of aromatic polycarbonate resin. More preferably, it is 0.001-0.05 weight part. If the blending ratio of boride is less than 0.0001 parts by weight, the heat ray shielding effect is small, and if it exceeds 0.5 parts by weight, the haze is increased and the transparency is lowered, which is disadvantageous in terms of cost.

Phosphine compound The phosphine compound used in the present invention is not particularly limited, and includes various organophosphines and salts thereof. Examples thereof include phosphine oxides, phosphonium salts with halogens, and derivatives such as diphosphines. It is done. In particular, an aliphatic or aromatic phosphine compound can be preferably used. Any of primary, secondary, and tertiary phosphine compounds can be used, and tertiary phosphine compounds are particularly preferable, and tertiary aromatic phosphine compounds or derivatives thereof are more preferable.
The tertiary aromatic phosphine compound is represented by the general formula R ₃ P (wherein R is an aromatic hydrocarbon group which may have a substituent and may be different from each other). R is preferably a phenyl group. As the substituent, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, n-hexyl group, isohexyl group , An alkyl group such as a cyclopentyl group and a cyclohexyl group, and an alkoxy group such as a methoxy group and an ethoxy group.
Specific examples of the tertiary aromatic phosphine compound or derivative thereof include triphenylphosphine, tri-m-tolylphosphine, tri-o-tolylphosphine, tri-p-tolylphosphine, tris-p-methoxyphenylphosphine, triphenylphosphine oxide, And tetraphenylphosphonium bromide, benzyltriphosphonium chloride, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, and more specifically, triphenylphosphine or triphenylphosphine Derivatives are preferably used, but other phosphine compounds may be used in combination. In addition, other heat stabilizers can be added at the same time as long as the effects of the present invention are not hindered.

  Content of a phosphine compound is 0.005-1 weight part with respect to 100 weight part of aromatic polycarbonate resin, Preferably it is 0.4 weight part or less. Exceeding 1 part by weight is not preferable because of problems such as deterioration of hydrolysis resistance.

Further, the polycarbonate resin composition of the present invention may be blended with a weather resistance improver, a heat stabilizer, an antioxidant, a mold release agent, and a dye / pigment when used as a window or window part. , Because hue stability is improved.
Weather resistance improvers Examples of weather resistance improvers 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) It is preferably at least one selected from bis [4H-3,1-benzoxazin-4-one], [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester.

  As the benzotriazole compound, a condensate with methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol is preferable. Specific examples of other benzotriazole compounds include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) -2H-benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- [2 -Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methylene bis [4- (1,1 3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxy Phenyl] propionate-polyethylene glycol] condensate.

  Among these, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole and 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl are particularly preferable. ] -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- (2N-benzotriazol-2-yl) phenol].

  The compounding ratio of the ultraviolet absorber 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. One type of ultraviolet absorber can be used, but a plurality of types can also be used in combination.

Antioxidant Antioxidants that are preferably used in the present invention include hindered phenol 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-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di -T-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-t-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri- p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-t-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-t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine-2 -Ylamino) phenol, etc. Among them, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- 3,5-di-t-butyl-4-hydroxyphenyl) propionate, these two phenolic antioxidants are commercially available from Ciba Specialty Chemicals under the names Irganox 1010 and Irganox 1076. Yes.

  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.

Release Agents As release agents preferably used in the present invention, aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, and polysiloxane silicone oils are used. It is at least one compound selected.

  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, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are 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. These ester compounds of aliphatic carboxylic acids and alcohols may contain aliphatic carboxylic acids and / or alcohols 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.

Dye / Pigment Examples of the dye / pigment used in the present invention include inorganic pigments, organic pigments, and organic dyes. Inorganic pigments include, for example, 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-based green, cobalt green, cobalt blue, copper-chromium black, oxide-based pigments such as copper-iron black, chromic pigments such as yellow lead and molybdate orange, ferrocyans such as bitumen Etc. 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 compounding amount of the metal boride fine particles is increased, the hue of the molded body is changed and the visibility is lowered (specifically, the L value is lowered and the absolute values of the a value and the b value are increased). Therefore, the visibility by the transmitted light is improved by selecting the type and / or blending ratio of the dye / pigment to be blended to obtain 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.

Infrared absorbing agent The polycarbonate resin composition of the present invention, if necessary, at least selected from the group consisting of antimony-doped tin oxide fine particles, In, Ga, Al and Sb, for the purpose of further improving the heat ray shielding performance. Other organic and inorganic infrared absorbers such as zinc oxide fine particles containing one kind of element, tin-doped indium oxide fine particles, phthalocyanine-based, naphthalocyanine-based, copper sulfide, and copper ions can also be blended.

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 salt-based, silicon and the like within a range not to impair the object of the present invention. Flame retardants, impact modifiers, antistatic agents, slip agents, antiblocking agents, lubricants, mold release agents, 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. .

Production method of polycarbonate resin composition The production method of 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, boride and other additions (2) A method of mixing borides and other additives while the aromatic polycarbonate resin is melted, such as during kneading, (3) Aromatic polycarbonate resin, such as pellets, is in a solid state Examples thereof include a method in which a boride and other additives are mixed and then melted and kneaded with an extruder or the like.

Molded body having heat ray shielding ability The method for molding a shaped body having heat ray shielding ability from the polycarbonate resin composition of the present invention is not particularly limited, and is a molding generally used for thermoplastic resins. Any of the methods such as injection molding, injection blow molding, injection compression molding, blow molding, extrusion molding of films and sheets, profile extrusion molding, thermoforming, rotational molding, and the like 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 ultraviolet rays Coextrusion of the absorbent layer, lamination, etc. are also possible. From the degree of freedom of the shape that can be molded, injection molding or injection compression molding is preferable. Furthermore, a hot runner can be used in injection molding or injection compression molding.
The shape of the molded body can be molded into an arbitrary shape as necessary, but it is preferable to have a flat or curved plate-like portion for use as a window or window part for general construction or vehicles. . Although there is no restriction | limiting in particular in the thickness of a plate-shaped part, The molded object provided with the heat ray shielding ability of this invention has a plate-shaped part of 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 boride at a high concentration in order to obtain sufficient heat ray shielding performance, and it is difficult to obtain transparency. The molded body having such a heat ray shielding ability 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 molded object provided with the heat ray shielding ability of the present invention is an aromatic polycarbonate resin molded article having a plate-like part having a thickness of 0.2 to 10 mm, and the plate-like part of the molded article provided with the heat ray shielding ability. (When postscript decoration is given, the solar radiation transmittance in the plate-like part before decorating) is 70% or less, preferably 60% or less. If the solar radiation transmittance exceeds 70%, the indoor temperature of general buildings and vehicles may increase excessively, which is not preferable.
Furthermore, the ratio of the total light transmittance and the solar radiation transmittance in the plate-like portion of the molded body having the heat ray shielding ability (the plate-like portion before being decorated). (Total light transmittance / solar radiation transmittance) is preferably 1.1 or more, more preferably 1.2 or more, and particularly preferably 1.3 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.

The molded body having the heat ray shielding ability of the present invention is also selected from a hard coat layer and an antireflection layer on one side or both sides of the plate-like portion in order to impart performance required as a window or window part. It is preferable to have at least one functionalized layer.
The method for forming at least one functionalized layer selected from a hard coat layer and an antireflection layer on one or both sides of a molded body 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 hard coat layers can be provided on the polycarbonate substrate. For example, it is possible to apply a hard coating agent directly onto a polycarbonate substrate, but it may be applied onto an undercoat layer previously formed on the substrate. Further, the surface of the formed hard coat layer can be subjected to an antifogging treatment, an antireflection film coating, etc. 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 composition is injection-molded there. Thus, it is also possible to create an integrally molded body having a hard coat layer.
In these hard coat layers, various additives such as ultraviolet absorbers such as triazole and triazine compounds, metal borides, ITO, ATO, ZnO, zinc antimonate and other metal / metal oxide fine particle heat rays Shielding agents, copper compounds, organic complexes, phthalocyanines, naphthalocyanines, diimonium, anthraquinones, aminium, cyanine, azo compounds, quinones, polymethines, diphenylmethane, etc. Various heat ray shielding agents such as these 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 formed by the above method 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 functionalized layer of the molded article having the heat ray shielding ability of the present invention is preferably a hard coat layer from the viewpoint of a window or window part.

The molded body having the heat ray shielding ability of the present invention can be subjected to arbitrary partial decoration on the functionalized layer surface or the polycarbonate resin surface, and imparts designability by blackout, various marks, characters, etc. be able to.
As for the molded object provided with the heat ray shielding ability of this invention, the hue of the plate-shaped part (plate-shaped part before decorating is given when the said decoration is given) is L value 92-35, The a value is preferably within the range of 5 to -15 and the b value within the range of 20 to -5. When the L value is less than 35, even if the a value and the b value are within the predetermined ranges of 5 to -15 and 20 to -5, respectively, blackening and transparency are lowered. Moreover, even if the L value is 80 or more, if the a value and the b value are smaller than −15 and −5, respectively, a strong green to bluish color is obtained. If the L value is larger than 5 and 20, the red to yellowish color is obtained. Strong color is not preferable. Furthermore, when the L value, the a value, and the b value are all out of the above ranges, the hue heat stability of the polycarbonate resin composition tends to be low. In general, the greater the L value, the better the visible light transmission, and the closer the a and b values are to zero, the less the coloring.

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: manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name NOVAREX 7022PJ, viscosity average molecular weight 21,000 (hereinafter abbreviated as “7022”).
(2) Boride: Lanthanum hexaboride fine particle dispersion (manufactured by Sumitomo Metal Mining Co., Ltd., trade name KHDS-02), lanthanum hexaboride fine particle content 10.5% by weight, zirconium oxide content 10.6% by weight, Polymeric dispersant content 78.9% by weight, particle size 20-100 nm (hereinafter abbreviated as “boride 1”).
(3) Phosphine compound: Triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) (hereinafter abbreviated as “phosphine compound 1”).
(4) Weather resistance improver: 2- (2′-hydroxy-5′-t-octylphenyl) -2H-benzotriazole, manufactured by Cypro Kasei Co., Ltd., trade name Seasorb 709 (hereinafter “UV absorber 1”) Abbreviated).
(5) Thermal stabilizer: Triphenyl phosphite (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) (hereinafter abbreviated as “phosphite compound 1”), bis (2,4-di-t-butyl-4-methyl) Phenyl) pentaerythritol phosphite, manufactured by Asahi Denka Kogyo Co., Ltd., trade name PEP-36 (hereinafter abbreviated as “phosphite compound 2”).
(6) Antioxidant: Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals, Inc., trade name Irganox 1010 (hereinafter referred to as “Irganox 1010”) Abbreviated as “phenolic stabilizer 1”).
(7) Release agent: glycerin monostearate, manufactured by Riken Vitamin Co., Ltd., trade name S-100A (hereinafter abbreviated as “release agent 1”).
(8) Dye 1: Macrolex Blue RR (manufactured by Bayer).
(9) Dye 2: Dialresin Red HS (manufactured by Mitsubishi Chemical Corporation).
(10) Carbon black: Carbon black # 1000 manufactured by Mitsubishi Chemical Corporation.

[Examples 1 and 2 and Comparative Examples 1 and 2]
Various additives listed in Table 1 were mixed with 100 parts by weight of aromatic polycarbonate (7022), then 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 M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho was used. The cylinder temperature was 290 ° C., the mold temperature was 80 ° C., and the molding cycle was 40 seconds. The three-stage plate (1 mm thickness, 2 mm thickness, and 3 mm thickness portions each having a size of 50 mm × 30 mm) was molded. On this flat plate surface, an acrylic undercoat and a silicon hardcoat were respectively applied and UV-cured to form a 10 μm-thick undercoat layer and a 5 μm-thick hardcoat layer to obtain a plate-like molded body.
This plate-like molded body was used as a test piece for the following evaluation methods (1) to (5), and measurement was performed using a 3 mm thick portion. The evaluation results are also shown in Table-1.

[Evaluation method]
(1) Haze / total light transmittance: According to JIS K-7105, a 3 mm-thick flat plate was used as a test piece, and measurement was performed with an NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd.
(2) Solar transmittance: From a value of light transmittance in a wavelength range of 300 to 2500 nm measured using a U-3100PC spectrophotometer manufactured by Shimadzu Corporation with a 3 mm thick flat plate as a test piece. The solar transmittance was calculated according to R-3106.
(3) L value, a value, b value, YI value: According to JIS K-7105, a 3 mm-thick flat plate was used as a test piece, and a transmission method using a SE2000 type spectral colorimeter manufactured by Nippon Denshoku Industries Co., Ltd. It was measured by.
(4) Heat aging test: The test piece was heat-stored in an air atmosphere at 130 ° C. for 500 hours, and the amount of change in the YI value before and after this heat storage was calculated as ΔYI, which was used as a heat resistance index.
(5) Humidity and heat resistance test: Using a pressure cooker tester (manufactured by Hirayama Seisakusho, HAESTEST, MODEL PC-SIII), the test piece is 120 ° C., a pressure of 1 kg / cm ² and a humidity of 100% in a steam atmosphere for 50 hours. The amount of change in haze value before and after this treatment was calculated as Δhaze, and used as an index of hydrolysis resistance.

  In Table 1 above, Examples 1 and 2 have a smaller ΔYI value after the heat aging test and a change rate of 10% or less as compared with Comparative Examples 1 and 2, and after the pressure cooker test. Since the Δhaze value of the sample is small and the rate of change is 100% or less, the addition of the phosphine compound indicates that the heat aging resistance and the moist heat resistance can be improved. Further, the plate-like molded bodies obtained in Examples 1 and 2 have sufficient heat ray shielding ability, and are useful as window parts for windows or sunroofs, roof panels, display panels, etc. for general buildings or vehicles. .

Claims (5)

  (A) selected from the group consisting of La, Ce, Pr, Nd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca with respect to 100 parts by weight of the aromatic polycarbonate resin A polycarbonate resin composition comprising 0.0001 to 0.5 part by weight of at least one metal boride fine particle and 0.005 to 1 part by weight of (b) a phosphine compound.   2. The polycarbonate resin composition according to claim 1, wherein the phosphine compound is triphenylphosphine or a triphenylphosphine derivative.   It is a molded object provided with the heat ray shielding ability which shape | molds the polycarbonate resin composition of Claim 1, 2, Comprising: It has a plate-shaped part of thickness 0.2-10mm, and in this plate-shaped part A molded article having a heat ray shielding ability, wherein the solar radiation transmittance is 70% or less.   4. The heat ray shielding ability according to claim 3, wherein the plate-like portion has at least one functionalized layer selected from a hard coat layer and an antireflection layer on one side or both sides thereof. Molded body provided. The said molded object is a window or window components for general buildings or vehicles, The molded object provided with the heat ray shielding ability of Claims 3 and 4 characterized by the above-mentioned.