JP2005344006A - Polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition solving problems caused by color unevenness of pellets of the polycarbonate resin composition containing a trace amount of inorganic fine particles represented by a heat ray screening agent and having good production efficiency of large-sized injection molded products and thermal stability and to provide the pellets composed of the resin composition. <P>SOLUTION: The resin composition is composed of 100 pts.wt. of the polycarbonate resin (component A), 0.01-0.5 pt.wt. of a fatty acid ester (component B) consisting essentially of a full ester composed of a higher fatty acid and a polyhydric alcohol and 0.1×10<SP>-4</SP>to 1,000×10<SP>-4</SP>pt.wt. of the inorganic fine particles (component C) having 2-500 nm average particle diameter. Thereby, the composition having excellent thermal stability and mold release properties and suitable for the large-sized molded products such as a window material is obtained. The pellets thereof are obtained. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polycarbonate resin composition containing a very small amount of inorganic fine particles represented by a heat ray shielding agent. In detail, it is related with the resin composition containing the fatty acid ester which satisfies specific conditions in this resin composition. The resin composition reduces the adverse effects caused by the uneven color of the pellets, is excellent in thermal stability and releasability, and provides a resin composition suitable for large molded articles such as window materials.

  Polycarbonate resins have excellent transparency, heat resistance, mechanical strength, and the like, and thus are widely used in electrical, mechanical, automotive, and medical applications. For example, applications such as optical information recording media, optical lenses, and glazing materials for buildings and vehicles (hereinafter sometimes simply referred to as “window materials”) can be specifically exemplified.

  In order to improve the production efficiency of the window material and to improve the design and productivity with a higher degree of freedom, examination by injection molding has been actively conducted. Therefore, resin compositions used for window materials have been required to have sufficient thermal stability.

  On the other hand, since the window material does not raise the temperature inside the window material, it may be required to have a property that it is difficult to transmit heat rays such as infrared rays and near infrared rays to the inside. There are cases where such a requirement is dealt with by using a heat ray shielding agent. In addition, metal oxide fine particles such as titanium oxide and carbon black also have a considerable effect of shielding heat rays, although the efficiency of transparency in the visible light region is inferior. A heat ray shielding agent made of a specific metal boride such as lanthanum boride, a coating liquid containing the shielding agent, and a resin film coated with the coating liquid are known. Furthermore, the shielding agent is superior in reflection / absorption effect in the near infrared region close to visible light compared to ATO and ITO having a relatively long wavelength in the near infrared region, and can form a film having low conductivity. It is well known in that respect (see Patent Document 1). However, since the shielding agent absorbs visible light to some extent, the resin composition containing the shielding agent (usually in the form of pellets) is colored. It is unavoidable that color irregularities that vary with time are generated. The pellets are often blended after their manufacture in order to dilute the effect of uneven color on the molded product. However, fine powder called so-called cut waste is generated in the blend. If the amount of the cut waste is too large, a filter attached to the pellet drying apparatus or the transportation pipe may be clogged or the efficiency of compressed air transportation may be reduced, which is not preferable in terms of production efficiency. Further, such cut waste affects the thermal stability during molding of the resin material, and in some cases, molding defects such as silver streak or yellowing may occur in large injection molded products with a high heat load.

  Transparency comprising a heat ray shielding inorganic compound comprising a polycarbonate resin, a metal oxide such as ATO and ITO, and a dispersant such as stearic acid monoglyceride, and the content of the inorganic compound and the dispersant satisfies a specific formula Resin compositions having are known. Further, a molded article formed by filling the resin composition in a mold in which a film in which a silicone hard coat is coated on the surface of a polycarbonate resin film not containing the inorganic compound and the dispersant is known. Yes (see Patent Document 1). However, the resin composition does not have sufficient thermal stability in a large-sized injection molded product, and a good molded product is often not obtained.

Japanese Patent Laid-Open No. 2000-072484 JP 2000-234066 A

  As described above, a polycarbonate resin composition containing a very small amount of inorganic fine particles generally tends to cause color unevenness. Further, when pellets are blended to reduce the influence of the color unevenness, the production efficiency at the time of molding the resin composition is improved. In particular, in large injection-molded products, a decrease in thermal stability may become apparent, and a good polycarbonate resin is required for any of the properties.

  An object of the present invention is to solve a problem caused by uneven color of pellets produced in large quantities in a polycarbonate resin composition containing a very small amount of inorganic fine particles typified by a heat ray shielding agent, and to form a large injection molded product An object of the present invention is to provide a polycarbonate resin composition suitable for applications such as window materials, which has good production efficiency and thermal stability, and pellets made of the resin composition. As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that in a polycarbonate resin composition containing a very small amount of inorganic fine particles, it is possible to solve such problems when a fatty acid ester satisfying specific conditions is further blended, The present invention has been completed.

According to the present invention, (1) 100 parts by weight of a polycarbonate resin (component A), a fatty acid ester (component B) containing as a main component a full ester composed of a higher fatty acid and a polyhydric alcohol. A resin composition comprising 01 to 0.5 parts by weight and inorganic fine particles (component C) having an average particle diameter of 2 to 500 nm of 0.1 × 10 ⁻⁴ to 1,000 × 10 ⁻⁴ parts by weight, Provided is a polycarbonate resin composition characterized in that the component satisfies the following condition-I. This resin composition is manufactured by mix | blending B component and C component with said A component. Particularly preferably, it is produced by blending the B component and the C component with the A component, and melt-kneading the mixture thereof.

  Condition-I: Molded product surface concentration of a resin composition (composition-S) obtained by blending 0.1 part by weight of B component with 99.9 parts by weight of bisphenol A type polycarbonate resin having a viscosity average molecular weight of 22,500 It is in the range of 4 to 11% by weight. Here, the molded product uses a disk-shaped mold cavity having a surface arithmetic mean roughness (Ra) of 0.01 μm, a diameter of 115 mm, a thickness of 3 mm, and a direct gate at the center. , A disk-shaped molded product obtained by injection molding the composition-S under conditions of a cylinder temperature of 300 ° C., a mold temperature of 80 ° C. and an injection time of 1.4 seconds, and the surface concentration is X Calculated by measuring with linear photoelectron spectroscopy.

Such surface concentration is calculated by the following method. That is, the ratio between the number of oxygen atoms and the number of carbon atoms (O _1S / C _1S ) in a disk-shaped molded product obtained by molding in the same manner as described above from a polycarbonate resin alone (ie, fatty acid ester concentration: 0% by weight). ) Is calculated by the ESCA method. The average value of 5 samples is taken as the value of the sample. On the other hand, O _1S / C _1S of fatty acid ester alone (ie, fatty acid ester concentration: 100% by weight) is calculated by the ESCA method. These O _1S / C _1S are connected by a straight line, and the proportional relationship between the fatty acid ester concentration and O _1S / C _1S is calculated. Furthermore, the surface concentration can be calculated from O _1S / C _1S of the target composition-S by the above method.

The O _1S / C _1S is one of the indices for the surface migration of the fatty acid ester in the polycarbonate resin. Good surface migration to some extent, such as prevention of unnecessary stagnation in the extruder, reduction of cutting resistance by the pelletizer blade, and reduction of frictional force between pellets are exhibited, making it difficult for cut waste to be generated. Inferred.

  According to the present invention, based on such an indicator, a polycarbonate resin composition containing a very small amount of inorganic fine particles and suitable for producing a good large-sized molded product can be obtained. The condition of the surface concentration depends on the content of the fatty acid ester and its surface transferability, and is thus achieved by adjusting the content of each fatty acid ester. However, in order to obtain both thermal stability and surface migration property of the fatty acid ester itself, the fatty acid ester of the B component is mainly composed of a full ester component composed of a higher fatty acid having a relatively high molecular weight and a polyhydric alcohol. In addition, it is preferable to contain a small amount of a component having a relatively low molecular weight. Appropriateness can be determined by a simple test along such a basic configuration. Preferred examples of such alkyl group-containing components include higher fatty acids and monoesters of higher fatty acids and monohydric alcohols, with higher fatty acids being particularly preferred. Carbon number of an alkyl group containing component becomes like this. Preferably it is 10-60, More preferably, it is 10-32.

  Further, the ratio of the alkyl group-containing component is such that the fatty acid ester (B component) mainly composed of a full ester composed of a higher fatty acid and a polyhydric alcohol is an ester composed of a higher fatty acid and a polyhydric alcohol (B-1 component), and It contains at least one selected from higher fatty acids and monoesters of higher fatty acids and monohydric alcohols (component B-2), and the molar ratio of components B-1 and B-2 (B-1 / B -2) is preferably in the range of 96/4 to 65/35, more preferably in the range of 90/10 to 70/30.

That is, according to another aspect of the present invention, (2) 100 parts by weight of a polycarbonate resin (component A), fatty acid ester (component B) having a full ester composed of a higher fatty acid and a polyhydric alcohol as a main component, 0.01 to A resin composition comprising 0.5 parts by weight and inorganic fine particles (component C) having an average particle diameter of 2 to 500 nm of 0.1 × 10 ⁻⁴ to 1,000 × 10 ⁻⁴ parts by weight, wherein the component B is And at least one selected from esters of higher fatty acids and polyhydric alcohols (B-1 component), and higher fatty acids and monoesters of higher fatty acids and monohydric alcohols, B A polycarbonate resin composition is provided wherein the molar ratio (B-1 / B-2) of the -1 component to the B-2 component is in the range of 96/4 to 65/35.

  In the present invention, the fatty acid ester mainly composed of a full ester composed of a higher fatty acid and a polyhydric alcohol can be determined based on the hydroxyl value of the fatty acid ester. The hydroxyl value in this invention is 30 or less, Preferably it is the range of 0.1-30, More preferably, it is the range of 1-30, More preferably, it is the range of 2-20. Here, the hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated, and can be determined by the method defined in JIS K 0070. .

  One of the suitable aspects of the present invention is (3) the polycarbonate resin composition of the above constitutions (1) to (2), wherein the component B is a full ester of a higher fatty acid and pentaerythritol. According to the configuration (3), a polycarbonate resin composition having good thermal stability and more suitable for a large molded product is provided.

  One of the preferred embodiments of the present invention is that (4) the C component is selected from the group consisting of La, Pr, Nd, Ce, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W. It is a polycarbonate resin composition of said structure (1)-(3) which is the inorganic fine particle which consists of 1 or more types of metal boride. According to this configuration (4), a polycarbonate resin composition having a good heat ray shielding effect, pellets thereof, and a molded article such as a window material formed from the resin composition are provided.

  One of the preferred embodiments of the present invention is (5) pellets composed of the polycarbonate resin composition of (1) to (4) above. According to the present invention, there is provided a molded article (especially a window material) having reduced thermal unevenness, which has solved the above problems, and good thermal stability, in particular, a heat ray shielding effect.

One of the preferable aspects of the present invention is (6) a polycarbonate resin molded body having a maximum projected area of 500 to 50,000 cm ² produced by injection molding of the pellet having the structure (5).
Details of the present invention will be described below.

<Component A: Polycarbonate resin>
The polycarbonate resin used as the component A in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly called bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropyl Pyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5 -Dibromo-4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) ) Fluorene and the like. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of impact resistance. That is, a particularly preferred component A of the present invention is a bisphenol A type polycarbonate resin.

  As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing a polycarbonate resin by interfacial polymerization of the above dihydric phenol and carbonate precursor, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, etc., as necessary. May be used. The polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. A copolymer polycarbonate resin copolymerized with a bifunctional alcohol (including an alicyclic group), and a polyester carbonate resin copolymerized with the bifunctional carboxylic acid and the bifunctional alcohol together. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

  Examples of trifunctional or higher polyfunctional aromatic compounds include 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane. Can be used.

When a polyfunctional compound that produces a branched polycarbonate is included, the amount is 0.001-1 mol%, preferably 0.005-0.9 mol%, particularly preferably 0.01-0, in the total amount of aromatic polycarbonate. 0.8 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0.005% in the total amount of the aromatic polycarbonate. Those having 9 mol%, particularly preferably 0.01 to 0.8 mol% are preferred. Such a ratio can be calculated by ¹ H-NMR measurement.

  The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and other straight-chain saturated aliphatic dicarboxylic acids, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.

  Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

  The reaction by the interfacial polymerization method is usually a reaction between a dihydric phenol and phosgene, and is reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, pyridine and the like are used.

  As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.

  In addition, catalysts such as tertiary amines and quaternary ammonium salts can be used for promoting the reaction, and monofunctional phenols such as phenol, p-tert-butylphenol, p-cumylphenol, etc. as molecular weight regulators. Are preferably used. Furthermore, examples of monofunctional phenols include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol. These monofunctional phenols having a relatively long chain alkyl group are effective when improvement in fluidity and hydrolysis resistance is required.

  The reaction temperature is usually 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is usually preferably maintained at 10 or higher.

  The reaction by the melting method is usually a transesterification reaction between a dihydric phenol and a carbonic acid diester, and the dihydric phenol and the carbonic acid diester are mixed in the presence of an inert gas and reacted at 120 to 350 ° C. under reduced pressure. The degree of vacuum is changed stepwise, and finally the phenols produced at 133 Pa or less are removed from the system. The reaction time is usually about 1 to 4 hours.

  Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among them, diphenyl carbonate is preferable.

A polymerization catalyst can be used to accelerate the polymerization rate. Examples of the polymerization catalyst include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide, boron and aluminum hydroxides, Alkali metal salt, alkaline earth metal salt, quaternary ammonium salt, alkoxide of alkali metal or alkaline earth metal, organic acid salt of alkali metal or alkaline earth metal, zinc compound, boron compound, silicon compound, germanium compound, Examples thereof include catalysts usually used for esterification and transesterification of organic tin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like. A catalyst may be used independently and may be used in combination of 2 or more types. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁵ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ equivalents, per 1 mol of the raw material dihydric phenol. Selected by range.

  In the polymerization reaction, in order to reduce phenolic end groups, for example, 2-chlorophenyl phenyl carbonate, 2-methoxycarbonylphenyl phenyl carbonate, 2-ethoxycarbonylphenyl phenyl carbonate, etc. Compounds can be added.

  Further, in the melt transesterification method, it is preferable to use a deactivator that neutralizes the activity of the catalyst. The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst. Further, it is used in a proportion of 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, and particularly preferably 0.01 to 100 ppm with respect to the aromatic polycarbonate after polymerization. Preferred examples of the deactivator include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.

  The details of reaction formats other than those described above are also well known in various documents and patent publications.

  The viscosity average molecular weight of the polycarbonate resin is 14,000 to 100,000, preferably 20,000 to 30,000, more preferably 22,000 to 28,000, and still more preferably 23,000 to 26,000. When the molecular weight is too low beyond the above range, the strength as a window material tends to be insufficient, and when the molecular weight is too high beyond the above range, injection molding tends to be difficult. In the above preferred range, for example, when hard coating is performed, the resistance to the hard coating agent is sufficient, and the disturbance of the resin flow occurring in the molded article can be reduced. Furthermore, in a more preferable range, both the impact resistance and the moldability are excellent. The polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range.

The viscosity average molecular weight (M) of the polycarbonate resin is obtained by inserting the specific viscosity (η _sp ) obtained at 20 ° C. from a solution of 0.7 g of the polycarbonate resin in 100 ml of methylene chloride into the following equation.
η _sp /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  Examples of the polycarbonate resin according to the present invention include the following. That is, it consists of an aromatic polycarbonate (PC-i) having a viscosity average molecular weight of 70,000 to 300,000 and an aromatic polycarbonate (PC-ii) having a viscosity average molecular weight of 10,000 to 30,000. Aromatic polycarbonate having a molecular weight of 15,000 to 40,000, preferably 20,000 to 30,000 (hereinafter sometimes referred to as “high molecular weight component-containing aromatic polycarbonate”) can also be used.

  Such an aromatic polycarbonate containing a high molecular weight component increases the entropy elasticity of the polymer due to the presence of PC-i, and becomes more advantageous at the time of injection press molding suitable in the present invention. For example, appearance defects such as hesitation marks can be further reduced, and the condition range of injection press molding can be expanded accordingly. On the other hand, the low molecular weight component of the PC-ii component lowers the overall melt viscosity, promotes relaxation of the resin, and enables molding with lower strain. The same effect is also observed in a polycarbonate resin containing a branched component.

<B component: fatty acid full ester>
The B component of the present invention is a full ester composed of a higher fatty acid and a polyhydric alcohol (hereinafter sometimes simply referred to as “fatty acid full ester”), and satisfies the above-mentioned condition-I. The surface concentration of the component B under such condition-I is preferably 4.5 to 10% by weight, more preferably 5 to 8% by weight. When satisfy | filling this specific surface concentration, generation | occurrence | production of the cut waste at the time of blend is suppressed for the pellet which consists of a resin composition. Due to such characteristics and the thermal stability of the B component itself, the pellet made of the resin composition of the present invention can provide a good large injection molded product with reduced molding defects such as silver streak.

  As described above, the B component fatty acid ester does not need to be composed of the fatty acid full ester component, and may contain a small amount of other components. In particular, it is preferable to contain a small amount of an alkyl group-containing component. Thereby, the fatty acid ester of B component can have the surface migration property which satisfies the said conditions, maintaining its own heat resistance.

  The polyhydric alcohol used as the constituent unit of the fatty acid ester of component B is an aliphatic polyhydric alcohol having 4 to 8 valences (hydroxyl groups) and 5 to 30 carbon atoms. Is preferred. The valence (number of hydroxyl groups) of the aliphatic polyhydric alcohol is preferably 4-6, and the number of carbon atoms is preferably 5-12, more preferably 5-10. The aliphatic polyvalent alcohol may contain an ether bond in the carbon chain. Specific examples of the aliphatic polyhydric alcohol include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. And dipentaerythritol are preferable, and pentaerythritol is particularly preferable.

  The higher fatty acid used as the constituent unit of the fatty acid ester of component B is one having 10 or more carbon atoms, preferably an aliphatic carboxylic acid having 10 to 32 carbon atoms, more preferably 10 to 22 carbon atoms. is there. Examples of such higher fatty acids include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, docosanoic acid. And saturated aliphatic carboxylic acids such as montanic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and setoleic acid. Among these, higher fatty acids having 14 to 20 carbon atoms are particularly preferable. Of these, saturated fatty acids are preferred. In particular, stearic acid and palmitic acid are preferred as the constituent unit of the fatty acid ester of the B component.

  Higher fatty acids such as stearic acid and palmitic acid are usually produced from natural fats such as animal fats (such as beef tallow and pork fat) and vegetable fats (such as palm oil). Accordingly, higher fatty acids such as stearic acid are usually mixtures containing other carboxylic acid components having different numbers of carbon atoms. In the production of the component B of the present invention, stearic acid and palmitic acid which are produced from such natural oils and fats and are in the form of a mixture containing other carboxylic acid components are preferably used. The preferable aspect of the composition ratio of each component in this mixture is as follows.

  The higher fatty acid constituting the B component includes a palmitic acid component and a stearic acid component, and the peak area in the pyrolysis methylated GC / MS (gas chromatography-mass spectrometry) method shows the area (Sp) of the palmitic acid component and stearin. The total of the acid component area (Ss) is preferably 80% or more of the total aliphatic carboxylic acid, and the area ratio (Ss / Sp) of both is 1.3 to 30.

  Here, pyrolysis methylation GC / MS method means that a fatty acid full ester as a sample and a reaction reagent methyl ammonium hydroxide are reacted on a pyrofil to decompose the fatty acid full ester and produce a methyl ester derivative of the fatty acid. This is a method of performing GC / MS measurement on such a derivative. Details of the method for measuring Ss / Sp are described in WO 03/095557 pamphlet.

  The total of Sp and Ss is preferably 85% or more of all fatty acid components, more preferably 90% or more, and further preferably 91% or more. On the other hand, the total of Sp and Ss can be set to 100%, but is preferably 98% or less and more preferably 96% or less from the viewpoint of manufacturing cost. Moreover, said area ratio (Ss / Sp) has the preferable range of 1.3-30. The upper limit of this range is preferably 10, more preferably 4, and still more preferably 3. These mixing ratios do not need to be satisfied with a single fatty acid, and may be satisfied by mixing two or more fatty acids.

  In addition, as fats and oils that are raw materials of fatty acids that satisfy the above mixing ratio, for example, animal fats such as beef tallow and lard, and linseed oil, safflower oil, sunflower oil, soybean oil, corn oil, peanut oil, cottonseed oil, There may be mentioned vegetable oils such as sesame oil and olive oil. Among these, animal fats and oils are preferable in view of containing more stearic acid, and beef tallow is more preferable. Furthermore, among the beef tallow, oleostearin containing a lot of saturated components such as stearic acid and palmitic acid is preferable.

  The fatty acid ester of component B does not necessarily need to have an esterification rate of 100% as a whole, but may be 80% or more, preferably 85% or more. As above-mentioned, the hydroxyl value is 30 or less, and the range of 0.1-30 is preferable. Such esters are excellent in their own thermal stability and have little thermal decomposition action on polycarbonate resins. As a result, a good heat-stable polycarbonate resin composition is provided. Further, the full ester component has an effect of reducing the frictional force between the resins inside the resin, realizing a smoother resin flow, and as a result, reducing distortion due to the disturbance of the resin flow inside the molded product.

  The method for producing the fatty acid ester of component B is not particularly limited, and various conventionally known methods can be used for alcohol and higher fatty acid. In order to satisfy the specific conditions of the present invention, in particular, in the production of full esters, the reaction is performed at a relatively early stage when the esterification reaction is apparently completed, rather than taking a sufficient time to complete the reaction. Is preferably terminated. Examples of the reaction catalyst include organic tin compounds such as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, calcium oxide, barium oxide, magnesium oxide, zinc oxide, sodium carbonate, potassium carbonate, and 2-ethylhexyltin. Is mentioned.

  As described above, the component of the present invention is at least one selected from esters (B-1 component) composed of higher fatty acids and polyhydric alcohols, and monoesters of higher fatty acids and higher fatty acids and monohydric alcohols (B- 2 component), and the molar ratio (B-1 / B-2) of the B-1 component to the B-2 component is preferably in the range of 96/4 to 65/35, more preferably 90/10 to 10/10. The range is 70/30.

  Usually, fatty acid esters contain free fatty acids. The molar ratio of the ester component (net ester compound) and free fatty acid contained in the fatty acid ester is calculated by the following method. That is, in calculating the molar ratio, the amount of hydroxyl groups that do not form an ester bond is taken into consideration. However, in order to calculate the amount of the hydroxyl group from the hydroxyl value, it is necessary to determine the total molecular weight. This will be specifically described below.

(I) Calculation of average chain length of fatty acid component Normally, the fatty acid as the raw material of the fatty acid ester is a mixture of fatty acids having different chain lengths, that is, alkyl groups having different carbon numbers. Therefore, it is necessary to reflect the influence of the distribution of the alkyl group on the molecular weight of the fatty acid ester. Therefore, the average chain length of the fatty acid is calculated. Such calculation is performed by ¹ H-NMR measurement using an NMR measuring apparatus having a measurement frequency of 400 MHz or more. More specifically, from the ratio between the peak area of the hydrogen atom in the methyl group (—CH ₃ group) at the terminal of the alkyl group and the peak area of the hydrogen atom in the methylene bond (—CH ₂ —bond) in the alkyl group, Calculate the average chain length. It is assumed that the average chain length is the same for both the ester component and the free fatty acid in the fatty acid ester. Such assumptions are reasonably reasonable considering manufacturing methods.

(Ii) Calculation of the number of moles (P) of the ester component in the fatty acid ester and the number of moles (Q) of the free fatty acid Since the fatty acid ester contains not a few free fatty acids, the fatty acid ester component in the fatty acid ester It is necessary to reflect the influence of the ratio with the free fatty acid on the molecular weight of the fatty acid ester.

(Ii-1) Calculation of ratio of free fatty acid to fatty acid component bonded to ester bond (Ff / Fe) For the calculation of P and Q, the ratio of fatty acid component bonded to ester bond and free fatty acid It is necessary to calculate to 1. Such calculation is performed by ¹ H-NMR measurement using a fatty acid ester with an NMR measuring apparatus having a measurement frequency of 400 MHz or more. Specifically, the peak area of hydrogen atoms of a hydrocarbon bond (for example, a methylene bond) bonded to a carboxyl group of a fatty acid (including any carboxyl group of a fatty acid component bonded to a free acid and an ester bond) is calculated. Such peak area is proportional to the amount of total fatty acid components. On the other hand, the peak area of the hydrogen atom of the hydrocarbon bond bonded to the ester bond in the alcohol component of the fatty acid ester is calculated. Such peak area is proportional to the amount of total ester bonds. Therefore, Ff / Fe (= y) can be calculated from these peak areas.

More specifically, for example, when the fatty acid ester is an ester of pentaerythritol, it is calculated as follows. The signal of the hydrogen atom of the methylene group bonded to the carboxyl group of the fatty acid appears at about 2.3 ppm. The peak area of this region is Sc. On the other hand, the hydrogen atom signal of the methylene group in the pentaerythritol component bonded to the ester bond appears at about 4.1 ppm. Let the peak area of such a region be Se. From these,
Ff / Fe = y = (Sc / 2-Se / 2) / (Se / 2)
From the relationship, Ff / Fe (= y) is calculated.

(Ii-2) Calculation of the number of moles of ester component (P) and the number of moles of free acid (Q) The number of moles of the fatty acid component bonded to the ester bond contained in 1 mole of fatty acid ester is α. Let x be the number of moles of hydroxyl groups (—OH groups) contained in one mole of fatty acid ester. Let the valence of the alcohol component of the fatty acid ester be v. At this time, the number of moles of the ester component which is a net ester compound contained in 1 mole of fatty acid ester is represented by (α−x) / v. When the sum of P and Q (P + Q) is 1, P represents the number of moles of the ester component contained in 1 mole of fatty acid ester. Therefore, P = (α + x) / v. On the other hand, Q = y × α = 1−P. Therefore, P and Q can be obtained by determining α and x.

(Iii) Calculation of molecular weight of fatty acid ester (iii-1) Calculation of α α, which is the number of moles of a fatty acid component bonded to an ester bond contained in 1 mol of fatty acid ester, is derived from the relationship between P and Q described above. , Α = (v−x) / (1 + v × y) is satisfied. Therefore, α can be obtained by determining x.

(Iii-2) Calculation of contribution amount Me of ester component to molecular weight of fatty acid ester 1 mol of fatty acid ester includes α mol of fatty acid component bonded to ester bond, P (= (α + x) / v) mol of fatty acid ester And the hydrogen atom of x mol of OH group are combined to form an ester component. Therefore, the contribution Me of the ester component to the molecular weight of the fatty acid ester is Me = (α × ms) + (P × mt) + (x × 1). Here, ms is the molecular weight of the fatty acid component, and mt is the molecular weight of the alcohol component in the fatty acid ester. ms can be calculated from the average chain length of the fatty acid component. It is necessary to determine x also in the calculation of Me.

(Iii-3) Calculation of contribution Mf of free fatty acid to molecular weight of fatty acid ester When Mf is the molecular weight of free fatty acid, Mf is Mf = mu × Q. mu can be calculated from the average chain length of the fatty acid component.

(Iii-4) Calculation of molecular weight (M) of fatty acid ester From the above, the molecular weight of fatty acid ester is calculated from M = Me + Mf. However, in order to calculate Me and Mf as described above, it is necessary to determine x. The number of moles x of hydroxyl groups (—OH groups) contained in 1 mol of the fatty acid ester can be calculated from the hydroxyl value of the fatty acid ester. However, in order to calculate x from the hydroxyl value, a numerical value of molecular weight M is required, and x is a function of M. It is possible to calculate M by introducing such x into the equation M = Me + Mf. More simply, M is calculated as follows. In other words, a temporary molecular weight (M ′) is calculated assuming x. Next, a temporary x, x ′, is calculated from the molecular weight M ′ and the hydroxyl value. A numerical value where x and x ′ coincide with each other is true x, and M is a molecular weight calculated from the true x.

  Since x is calculated in this way, the above P and Q can be obtained from x. That is, B-1 / B-2 = P / Q is calculated.

  When the B-2 component is a higher fatty acid, for example, a fatty acid ester having an acid value in the range of 4 to 20 is exemplified as a suitable B component. By blending a fatty acid ester that satisfies such a range, a free fatty acid component is appropriately mixed, and the above conditions are easily satisfied. The acid value is more preferably in the range of 4-18, and still more preferably in the range of 5-15. If the acid value exceeds 20, thermal stability may be insufficient. Here, the acid value is the number of mg of potassium hydroxide required to neutralize free fatty acids contained in 1 g of the sample, and can be determined by the method defined in JIS K 0070. Since the free fatty acid corresponds to the raw fatty acid of the full ester, the preferred embodiment is the same as the above higher fatty acid.

  Furthermore, a fatty acid which satisfies the above conditions can be obtained by adding a fatty acid separately to the full ester having a low acid value as described above. Similarly, it is possible to prepare a fatty acid ester satisfying the conditions of the present invention by mixing two or more fatty acid esters having different acid values.

  Moreover, as a suitable higher fatty acid in the fatty acid monoester component in the B-2 component, for example, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, Examples include stearic acid, isostearic acid, oleic acid, elaidic acid, petrothelic acid, linoleic acid, linolenic acid, eleosteararacinic acid, cadreic acid, behenic acid, and erucic acid. Of these, saturated fatty acids are more preferred.

  Examples of the monohydric alcohol include alcohol having 6 to 22 carbon atoms or Gerve alcohol derived from alcohol having 6 to 12 carbon atoms. Gerve alcohol is typically an oily agent obtained by base-catalyzed condensation of fatty alcohols. Examples of monohydric alcohols include capron alcohol, capryl alcohol, caprin alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, and lauryl alcohol. Examples of Gerve alcohol include Gerber alcohol derived from capron alcohol, capryl alcohol, caprin alcohol, or lauryl alcohol, and mixtures thereof. The esterification degree of the fatty acid monoester of the B-2 component may be 100%, but may be 70% or more.

  In the B component of the present invention, the iodine value is preferably low from the viewpoint of thermal stability. The iodine value of component C is preferably 10 or less, and more preferably 1 or less. The iodine value is an amount obtained by converting the amount of halogen to be bonded to the number of g of iodine when halogen is reacted with 100 g of a sample, and can be obtained by a method defined in JIS K0070.

<Molding conditions for measurement sample>
The molding conditions of the measurement sample manufactured for the determination of the condition-I regarding the component B of the present invention will be described. The molding machine is not particularly limited as long as it is a molding machine capable of molding the disk-shaped molded product. For example, a molding machine having a clamping force of 2548 kN is used. A cylinder having a maximum capacity of about 201 cm ³ is used. Cavity pellets for measurement consisting of Composition-S dried with hot air at 120 ° C. for 5 hours from a hopper of a molding machine, and then plasticized and melted at a cylinder temperature of 300 ° C. and set at a mold temperature of 80 ° C. It is injected and filled at an injection time of 1.4 seconds and an injection pressure (filling peak pressure) of 134 MPa. The amount of cushion during molding is set to 13.5 mm. The mold clamping adjustment is performed so that there is no movement of the movable mold during injection filling.

  Thereafter, a holding pressure of 90 MPa is held for 7 seconds in the pressure holding step, and 35 seconds is spent in the cooling and solidifying step. After the cooling step, mold opening is performed at an initial speed of 110 mm / second, and then the ejector pin is advanced by 17.5 mm at an ejection speed of 25 mm / second, thereby releasing the molded product. This molding is repeated several tens of shots, and a sample for measurement is taken when the molding is stable. The sample is immediately stored in a sealed container so as not to contaminate its surface.

<About the manufacturing method of Composition-S>
The pellet made of the composition-S used for the above sampling is manufactured by the following method. A bisphenol A type polycarbonate resin powder having a viscosity average molecular weight of 22,5000 is prepared. Such a polycarbonate resin is produced by an interfacial polymerization method using p-tert-butylphenol as a terminal stopper. Examples of the polycarbonate resin include “Panlite L-1225WP” (trade name) manufactured by Teijin Chemicals Ltd., and are easily available. The resin powder is dried with hot air at 120 ° C. for 5 hours, and then the fatty acid full ester (component B) is blended and dry blended. These ratios are 100 parts by weight in total of 99.9 parts by weight of bisphenol A type polycarbonate resin and 0.1 parts by weight of B component. The dry blended mixture is supplied to a vented twin screw extruder and melt extruded under the conditions of 260 ° C. and a vent vacuum of 3 kPa, and the resulting strand is cut by a pelletizer to produce pellets. A suitable shape of the pellet is 2.0 to 3.3 mm in diameter and 2.5 to 3.5 mm in length.

<C component: inorganic fine particles>
The C component of the present invention has an average particle size of 2 to 500 nm, preferably 5 to 200 nm, and more preferably 10 to 100 nm. The average particle diameter is obtained by calculating the area of each primary fine particle by image analysis of an image obtained by observation with an electron microscope, obtaining the diameter of a circle having the area, and weight-averaging the diameter. It is calculated. This calculation is performed by obtaining the converted diameter for 500 or more fine particles. According to the present invention, it is possible to provide a pellet having good heat resistance capable of obtaining a good molded product even when the color unevenness of the pellet over time due to the deterioration of dispersion of such ultrafine particles. The converted diameter of each inorganic fine particle is preferably 500 or less, more preferably 380 nm or less, and further preferably 150 nm or less. Furthermore, the converted diameter of each boride fine particle is preferably in the range of 50% of the average particle diameter before and after the average diameter, and more preferably in the range of 30% of the average particle diameter before and after.

  The inorganic fine particles of the present invention are oxidized of various metals (for example, La, Pr, Nd, Ce, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Si, Al, and Mg). Preferred examples include oxides, borides, nitrides and fluorides. Among them, a boride of one or more metals selected from the group consisting of La, Pr, Nd, Ce, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W is preferable. . Furthermore, the inorganic fine particles of the present invention contain a carbon compound such as carbon black.

Such boride fine particles include lanthanum boride (LaB ₆ ), praseodymium boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), titanium boride. (TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), molybdenum boride Typical examples thereof include fine particles such as (MoB ₂ , Mo ₂ B ₅ , MoB) and tungsten boride (W ₂ B ₅ ). In particular, lanthanum boride (LaB ₆ ) is preferred as the C component.

  Further, the boride fine particles used in the present invention are preferably not oxidized on the surface, but usually obtained products are often slightly oxidized, and surface oxidation occurs in the fine particle dispersion step. That is unavoidable to some extent. However, even in that case, the effectiveness of developing the heat ray shielding effect remains unchanged.

  The boride fine particles have a higher heat ray shielding effect as the crystal completeness is higher, but even if the crystallinity is low and an extremely broad diffraction peak is generated by X-ray diffraction, the basic inside of the fine particles can be obtained. If the bond is composed of a bond of metal and boron, a heat ray shielding effect is exhibited.

  The component C of the present invention can be blended in the polycarbonate resin of the component A by itself, but in order to improve the dispersibility in the resin, it is surface-treated with various surface treatment agents and surfactants. You may mix | blend in polycarbonate resin in the state of a mixture with an agent. More preferably, the component C is a mixture of metal boride fine particles and at least one or two or more metal oxides selected from the group of Si, Zr, Ti, and Al. In particular, the mixture is obtained by mixing metal boride fine particles with a metal alkoxide of Si, Zr, Ti or Al or a partial hydrolysis condensate of the metal alkoxide, and hydrolyzing and condensing the metal alkoxides in the mixture. Those produced are preferred. The mixing is preferably performed in water or an organic solvent, particularly in alcohol. An acid or alkali for adjusting pH, a surfactant, a coupling agent, and the like may be added to the mixed solution. In such mixing, various mills such as a bead mill, a ball mill, and a sand mill, an ultrasonic mixer, and the like can be used.

  Examples of the metal alkoxide include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and decaethoxytetraloxane as the metal alkoxide of Si, and examples of the metal alkoxide of Zr include tetramethoxyzirconium, tetrapropoxyzirconium, and tetrabutoxy. Zirconium, tetrapropoxyzirconium isopropanol complex and the like are exemplified, and titanium isopropoxide, titanium butoxide and the like are exemplified as the metal alkoxide of Ti. In particular, Zr metal alkoxides having good hue are preferred.

  The inorganic fine particles of the present invention may be bound by a resin binder. When the resin binder is a thermoplastic resin, it can be mixed with inorganic fine particles while the thermoplastic resin is melted or in solution. When the resin binder is a thermosetting resin, mixing with inorganic fine particles under a liquid compound constituting the thermosetting resin by reaction or under a solution of the compound constituting the thermosetting resin by reaction Can do. Such mixing is preferably carried out under a solution of a resin binder, a liquid compound that forms a resin binder by reaction, or a solution of a compound that forms a resin binder by reaction. After such mixing, a mixture is obtained by removing the solvent or curing the liquid compound, or simultaneously or after the hydrolytic condensation reaction of the metal alkoxide, or by removing the solvent or curing the liquid compound. Can do.

  The resin binder is preferably a thermosetting resin, and particularly preferably an epoxy resin. This is because the epoxy resin is excellent in compatibility with the polycarbonate resin, has little adverse effect on transparency, and has little attack on the polycarbonate resin.

<Composition ratio of each component>
Content of B component of this invention is 0.01-0.5 weight part on the basis of 100 weight part A component, Preferably it is 0.02-0.5 weight part, More preferably, it is 0.03-0. 3 parts by weight. The content of the component C of the present invention is 0.1 × 10 ⁻⁴ to 1,000 × 10 ⁻⁴ parts by weight, preferably 0.5 × 10 ⁻⁴ to 200 × based on 100 parts by weight of the component A. 10 ⁻⁴ parts by weight, more preferably 1 × 10 ⁻⁴ to 50 × 10 ⁻⁴ parts by weight.

<Other additives>
The polycarbonate resin composition of the present invention can contain various known additives as long as the object of the present invention is not impaired, in addition to the above components A to C.

<Additional ingredients that can be blended if necessary>
The polycarbonate resin composition of the present invention comprises a resin composition containing as essential components an A component aromatic polycarbonate, a B component specific fatty acid ester, and a C component inorganic fine particles. However, if desired, various additives may be added as additional components.

(I) Polymer other than Component A A polymer other than Component A can be blended with the resin composition of the present invention within a range where the object of the present invention is not impaired.

  Examples of such other polymers include polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides, polyimides, polyetherimides, polyurethanes, polyphenylene ethers, polyphenylene sulfides, polysulfones, polyolefins such as polyethylene and polypropylene, polystyrene, acrylonitrile / styrene copolymers. Examples thereof include polymers (so-called AS copolymers), acrylonitrile / butadiene / styrene copolymers (so-called ABS copolymers), acrylic resins such as polyacrylates and polymethacrylates, phenol resins, and epoxy resins.

  Such a polymer may be an elastomer. Examples of the elastomer include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and MBS (methyl methacrylate / sterene / butadiene) rubber that is a core-shell type elastomer. Examples include MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

  Of these, styrene polymers and aromatic polyesters can be particularly exemplified.

  Such styrenic polymers include polystyrene (PS) (including syndiotactic polystyrene), AS copolymer, ABS copolymer, acrylonitrile / acrylic rubber / styrene copolymer (so-called ASA copolymer), acrylonitrile / ethylene. Α-olefin copolymer rubber / styrene copolymer (so-called AES copolymer), and copolymers containing these acrylonitrile / styrene copolymer components are further copolymerized with an acrylic monomer component such as methyl methacrylate. Polymerized copolymers (represented by so-called MABS copolymers), copolymers obtained by replacing acrylonitrile of these copolymers containing acrylonitrile / styrene copolymer components with methyl methacrylate (so-called MBS copolymers) ), As well as styrene-none Maleic acid copolymer (so-called SMA copolymer) are exemplified. Among these, a copolymer containing an acrylonitrile / styrene copolymer component is preferable because of excellent compatibility with an aromatic polycarbonate. Such copolymers include so-called transparent ABS resins. The styrenic polymer may be modified with various functional groups typified by epoxy groups and acid anhydride groups. These styrenic polymers can be used in combination of two or more.

  As aromatic polyesters, polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene-2,6-naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1, In addition to 2-bis (phenoxy) ethane-4,4′-dicarboxylate, polyethylene terephthalate copolymerized with 1,4-cyclohexanedimethanol (so-called PET-G), polyethylene isophthalate / terephthalate, polybutylene terephthalate / Copolyesters such as isophthalate can also be used. Of these, polyethylene terephthalate and polyethylene-2,6-naphthalate are preferable. When a balance between moldability and mechanical properties is required, polybutylene terephthalate and polybutylene naphthalate are preferable, and blends and copolymers having a polybutylene terephthalate / polyethylene terephthalate ratio of 2 to 10 by weight are preferable. . Although there is no restriction | limiting in particular about the molecular weight of aromatic polyester, The intrinsic viscosity measured at 35 degreeC by using o-chlorophenol as a solvent is 0.4-1.2, Preferably it is 0.6-1.15.

  Furthermore, in the range which does not impair the objective or effect of this invention, in addition to the said styrenic polymer and aromatic polyester, other amorphous thermoplastic polymers and crystalline thermoplastic polymers can be included.

(Ii) Phosphorus stabilizer The aromatic polycarbonate resin composition forming the vehicle exterior molded article of the present invention preferably contains a phosphorus heat stabilizer. Examples of such phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Such phosphorus stabilizers can be used alone or in combination of two or more.

  Specifically, as the phosphite compound, for example, a trialkyl phosphite such as tridecyl phosphite, a dialkyl monoaryl phosphite such as didecyl monophenyl phosphite, a monoalkyl diaryl phosphite such as monobutyl diphenyl phosphite, Triaryl phosphites such as triphenyl phosphite and tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol Such as diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Intererythritol phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite and 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4- Examples include cyclic phosphites such as (di-tert-butylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, and diisopropyl phosphate. Triphenyl phosphate and trimethyl phosphate.

  Preferred examples of the phosphonite compound include tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite. Tetrakis (2,4-di-tert More preferred are -butylphenyl) -biphenylene diphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. An example of the tertiary phosphine is triphenylphosphine.

  The amount of the phosphorus heat stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and still more preferably 0.01 to 100 parts by weight based on 100 parts by weight of the component A. 0.3 parts by weight. Addition of such a phosphorus-based heat stabilizer can further improve the heat stability and obtain good molding characteristics.

(Iii) Hindered phenol stabilizer The hindered phenol stabilizer is effective in suppressing discoloration due to heat aging of an exterior molded article for vehicles. When such discoloration is important, it is preferable to add the stabilizer. Hindered phenol stabilizers include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6- (3′-tert-butyl-5′- Methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl- 4-hydroxy-5-methylphenyl) propionate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, N, N'-hexamethylenebis- (3,5- -Tert-butyl-4-hydroxyhydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and tetrakis [methylene -3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. Of these, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is preferably used. The hindered phenol stabilizers can be used alone or in combination of two or more. The amount of these stabilizers is preferably 0.0001 to 0.5 parts by weight, more preferably 0.005 to 0.3 parts by weight, based on 100 parts by weight of component A.

(Iv) Light Diffusing Agent The polycarbonate resin composition of the present invention can contain a light diffusing agent such as polymer fine particles. Such a light diffusing agent is useful, for example, in that it can be blindfolded or alleviated from incident sunlight without impairing the brightness of the room when used in a window material. Examples of such polymer fine particles include organic crosslinked particles obtained by polymerizing a non-crosslinkable monomer and a crosslinkable monomer. Examples of non-crosslinkable monomers include non-crosslinkable vinyl monomers such as acrylic monomers, styrene monomers, and acrylonitrile monomers, and olefin monomers. These can be used alone or in admixture of two or more. Furthermore, other copolymerizable monomers other than such monomers can also be used. Examples of the other organic crosslinked particles include silicone-based crosslinked particles. On the other hand, amorphous heat-resistant polymer particles such as polyethersulfone particles can also be cited as the polymer fine particles of the present invention. In the case of such polymer particles, the form of the fine particles is not impaired even when heated and melt-kneaded with the component A, so that a crosslinkable monomer is not necessarily required. Furthermore, as the polymer fine particles of the present invention, various epoxy resin particles, urethane resin particles, melamine resin particles, benzoguanamine resin particles, phenol resin particles, and the like can be used. Among light diffusing agents composed of polymer fine particles, organic crosslinked particles can be suitably used from the viewpoint of heat resistance. Further preferable polymer fine particles are silicone-based crosslinked particles typified by polymethylsilsesquioxane from the viewpoint of hue.

  The average particle size of the polymer fine particles is preferably 0.01 to 50 μm, more preferably 0.1 to 10 μm, and still more preferably 0.1 to 8 μm. The average particle size is represented by a 50% value (D50) of the cumulative distribution of particle sizes obtained by the laser diffraction / scattering method. Also, the particle size distribution is preferably narrow, and more preferably has a distribution in which the particles present in the range of the average particle size of −2 μm to the average particle size of +2 μm are in the range of 70% by weight or more.

  The refractive index of the polymer fine particles is preferably 1.33 to 1.7, more preferably 1.35 to 1.67. In order to obtain a good hue, the refractive index is preferably lower than that of the A component aromatic polycarbonate. Therefore, a more preferable refractive index is 1.35 to 1.55, more preferably 1.35 to 1.45. The shape of the polymer fine particles is preferably close to a sphere from the viewpoint of light diffusibility, and more preferably a shape close to a true sphere. Such a sphere includes an elliptical sphere.

(V) Hydrolysis Stabilizer The polycarbonate resin composition of the present invention impairs the object of the present invention with a compound conventionally known as a hydrolysis improver for aromatic polycarbonate for the purpose of further improving its hydrolysis resistance. It can also be blended in a range not included. Examples of such compounds include epoxy compounds, oxetane compounds, silane compounds, and phosphonic acid compounds, with epoxy compounds and oxetane compounds being particularly preferred. Examples of the epoxy compound include an alicyclic epoxy compound represented by 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, and a silicon atom-containing epoxy represented by 3-glycidylpropoxy-triethoxysilane. The compound is preferably exemplified. The hydrolysis improver is preferably 1 part by weight or less per 100 parts by weight of component A.

(Vi) Ultraviolet Absorber The polycarbonate resin composition of the present invention can contain an ultraviolet absorber in order to maintain its hue for a long time. Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, hydroxyphenyltriazine compounds, cyclic imino ester compounds, and cyanoacrylate compounds known as ultraviolet absorbers. More specifically, for example, benzotriazole compounds include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4- (1,1 , 3,3-tetramethylbutyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- [5-chloro (2H) -Benzotriazol-2-yl] -4-methyl-6-tert-butylphenol and 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3) -Tetramethylbutyl) phenol] and the like are preferably exemplified, and as the hydroxyphenyltriazine-based compound, 2- (4,6-diphenyl-1,3,5-triazine-2 -Yl) -5-[(hexyl) oxy] phenol is preferably exemplified, and 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) is preferred as the cyclic imino ester compound. Illustrative examples of cyanoacrylate compounds include 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl). A preferred example is oxy] methyl] propane.

  Furthermore, the ultraviolet absorber is a polymer type copolymer obtained by copolymerizing such an ultraviolet absorbing monomer and a monomer such as alkyl (meth) acrylate by taking the structure of a monomer compound capable of radical polymerization. An ultraviolet absorber may be sufficient. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylate. The

  Among these, from the viewpoint of having good thermal stability, a cyclic imino ester compound can be mentioned as a more preferable ultraviolet absorber. Other compounds having a relatively high molecular weight can provide better heat resistance. For example, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3 , 3-tetramethylbutyl) phenol], 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, and 1,3-bis [( 2-Cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] propane is preferably exemplified. The content of the ultraviolet absorber is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, still more preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the component A. It is.

  The polycarbonate resin composition of the present invention can also contain a hindered amine light stabilizer represented by bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate. The combined use of the hindered amine light stabilizer and the UV absorber effectively improves the weather resistance. In such a combination, the weight ratio (light stabilizer / ultraviolet absorber) of both is preferably in the range of 95/5 to 5/95, more preferably in the range of 80/20 to 20/80. You may use a photostabilizer individually or in mixture of 2 or more types. The content of the light stabilizer is preferably 0.0005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, still more preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of component A. It is.

(Vii) Blueing agent The polycarbonate resin composition of the present invention preferably further comprises 0.05 to 3.0 ppm (weight ratio) of a blueing agent in the resin composition. In the resin composition of the present invention, the use of a bluing agent is very effective for further reducing the yellowness and imparting a natural transparency to the molded product. Here, the bluing agent refers to a colorant that exhibits a blue or purple color by absorbing light of orange or yellow color, and a dye is particularly preferable. The resin composition of the present invention obtains a better hue by blending the bluing agent. If the amount of the bluing agent is less than 0.05 ppm, the effect of improving the hue may be insufficient. On the other hand, if it exceeds 3.0 ppm, the coloring becomes excessive and is not suitable. A more preferable amount of bluing agent is in the range of 0.2 to 2.0 ppm in the resin composition. Representative examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR manufactured by Bayer, and Polysynthrene Blue RLS manufactured by Clariant.

(Viii) Dye / pigment Various dyes / pigments can be used in the polycarbonate resin composition of the present invention as long as the object of the present invention is not impaired. Examples of such dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes Examples thereof include dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, fluorescent whitening agents such as bisbenzoxazolyl-stilbene derivatives, bisbenzoxazolyl-naphthalene derivatives, bisbenzoxazolyl-thiophene derivatives, and coumarin derivatives can also be used. Other metallic pigments can be blended to obtain a better metallic color, and appropriate heat ray reflection can be performed to keep the room temperature more appropriate. The content of the other dyes / pigments is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.8 part by weight, based on 100 parts by weight of the component A.

(Ix) Antistatic agent The polycarbonate resin composition of the present invention may require antistatic performance, and in such a case, it is preferable to include an antistatic agent. Examples of such antistatic agents include (1) organic sulfonic acid phosphonium salts such as (1) aryl sulfonic acid phosphonium salts represented by dodecylbenzene sulfonic acid phosphonium salts, and alkyl sulfonic acid phosphonium salts, and tetrafluoroboric acid phosphonium salts. Examples thereof include phosphonium borate salts. The content of the phosphonium salt is suitably 5 parts by weight or less based on 100 parts by weight of the component A, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, still more preferably. The range is 1.5 to 3 parts by weight.

  Antistatic agents include, for example: (2) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate And organic sulfonate alkali (earth) metal salts. Specifically, for example, metal salts of dodecylbenzenesulfonic acid, metal salts of perfluoroalkanesulfonic acid, and the like are exemplified. The content of the organic sulfonate alkali (earth) metal salt is suitably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, more preferably based on 100 parts by weight of the component A. 0.005 to 0.2 part by weight. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

  Examples of the antistatic agent include (3) organic sulfonic acid ammonium salts such as alkylsulfonic acid ammonium salt and arylsulfonic acid ammonium salt. The ammonium salt is suitably 0.05 parts by weight or less based on 100 parts by weight of component A. Examples of the antistatic agent include (iv) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less based on 100 parts by weight of component A.

(X) Organic compound having heat ray absorbing ability In the polycarbonate resin composition of the present invention, an organic compound having heat ray absorbing ability in an amount that does not impair the object of the present invention can be used. Preferred examples of the compound include phthalocyanine-based near infrared absorbers. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. The phthalocyanine-based near infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and still more preferably 0.001 to 0 parts, based on 100 parts by weight of the component A. .07 parts by weight.

(Xi) Others In the polycarbonate resin composition of the present invention, an amount of flame retardant that does not impair the object of the present invention can be used. Examples of the flame retardant include brominated epoxy resin, brominated polystyrene, brominated polycarbonate, brominated polyacrylate, monophosphate compound, phosphate oligomer compound, phosphonate oligomer compound, phosphonitrile oligomer compound, phosphonic acid amide compound, sulfonate salt Organic acid metal salts other than these, silicone flame retardants, and the like can be used, and one or more of them can be used. Each of these flame retardants can be blended in a known amount relative to the polycarbonate resin.

  Furthermore, the polycarbonate resin composition of the present invention can contain a flow modifier, an antibacterial agent, a photocatalytic antifouling agent, a photochromic agent, and the like.

<About the manufacturing method of a resin composition>
In producing the polycarbonate resin composition of the present invention, the production method is not particularly limited. However, in order to improve the dispersion of the inorganic fine particles, it is preferable to melt and knead the components A to C and an optional component with a twin screw extruder.

  A typical example of the twin screw extruder is ZSK (trade name, manufactured by Werner & Pfleiderer). Specific examples of similar types include TEX (trade name, manufactured by Nippon Steel Works, Ltd.), TEM (trade name, manufactured by Toshiba Machine Co., Ltd.), KTX (product name, manufactured by Kobe Steel, Ltd.), and the like. Can be mentioned. In addition, melt kneaders such as FCM (manufactured by Farrel, trade name), Ko-Kneader (manufactured by Buss, trade name), and DSM (manufactured by Krauss-Maffei, trade name) can be given as specific examples. Among the above, the type represented by ZSK is more preferable. In such a ZSK type twin screw extruder, the screw is a fully meshed type, and the screw includes various screw segments having different lengths and pitches, and various kneading disks having different widths (and corresponding kneading segments). It consists of

  A more preferable embodiment in the twin screw extruder is as follows. As the screw shape, one, two, and three screw screws can be used, and in particular, a two-thread screw having a wide range of application in both the ability to convey the molten resin and the shear kneading ability can be preferably used. The ratio (L / D) of the screw length (L) to the diameter (D) in the twin-screw extruder is preferably 20 to 45, more preferably 28 to 42. When L / D is large, uniform dispersion is likely to be achieved, whereas when it is too large, decomposition of the resin is likely to occur due to thermal degradation. The screw needs to have one or more kneading zones composed of kneading disk segments (or kneading segments corresponding thereto) for improving kneadability, and preferably 1 to 3 kneading zones.

  Furthermore, as an extruder, what has a vent which can deaerate the water | moisture content in a raw material and the volatile gas which generate | occur | produces from melt-kneading resin can be used preferably. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.

  Furthermore, the method for supplying the component B, component C and other additives (simply referred to as “additive” in the following examples) to the extruder is not particularly limited, but the following methods are typically exemplified. (I) A method of supplying the additive into the extruder independently of the polycarbonate resin. (Ii) A method in which the additive and the polycarbonate resin powder are premixed using a mixer such as a super mixer and then supplied to the extruder. (Iii) A method of melt-kneading an additive and a polycarbonate resin in advance to form a master pellet.

  One of the methods (ii) is a method in which all necessary raw materials are premixed and supplied to the extruder. Another method is a method in which a master agent containing a high concentration of additives is prepared, and the master agent is separately or further premixed with the remaining polycarbonate resin or the like and then supplied to the extruder. The master agent can be selected from either a powder form or a form obtained by compressing and granulating the powder. Examples of other premixing means include, for example, a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. A high-speed stirring type mixer such as a super mixer is preferable. . Yet another premixing method is, for example, a method in which a polycarbonate resin and an additive are uniformly dispersed in a solvent and then the solvent is removed.

  The resin extruded from the twin-screw extruder is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. Furthermore, when it is necessary to reduce the influence of external dust or the like, it is preferable to clean the atmosphere around the extruder. Further, in the production of such pellets, various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, further reduce miscuts, and generate fine powder during transportation or transportation. Further reduction of air bubbles and reduction of bubbles (vacuum bubbles) generated in the strands and pellets can be appropriately performed. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder (including an elliptical column) more preferably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. In the elliptic cylinder, the ratio of the minor axis to the major axis is preferably 60% or more, more preferably 65% or more. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

<About a molded product comprising the resin composition of the present invention>
The polycarbonate resin composition of the present invention obtained as described above can be usually produced by injection molding the pellets produced as described above to produce various products. Furthermore, the resin melt-kneaded by a twin screw extruder can be directly made into a sheet, a film, a profile extrusion molded product, a direct blow molded product, and an injection molded product without going through pellets.

  In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.

  In addition, the resin composition of the present invention can also be used in these shapes by producing various shaped extruded products, sheets, films and the like by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

The resin composition of the present invention, more specifically, a pellet made of the resin composition, has good thermal stability capable of producing a large molded article such as a window material by injection molding. Accordingly, such large molded products are mass-produced by the injection molding method, and as a result, such large molded products having excellent cost performance are provided. That is, according to the present invention, from 100 parts by weight of the A component, 0.01 to 0.5 parts by weight of the B component, and 0.1 × 10 ⁻⁴ to 1,000 × 10 ⁻⁴ parts by weight of the C component. A large-sized molded product obtained by injection molding the polycarbonate resin composition is provided.

<About injection press molding>
The polycarbonate resin composition of the present invention is suitable for producing a large molded article such as a window material by an injection molding method. In order to injection mold such a large molded article, an injection press molding method is preferably used. Such an injection press molding method is already widely known.

  In injection press molding, the need to fill the resin at high pressure is reduced, so that distortion in the molded product is reduced. Such distortion reduction is important in the uniformity of transmitted light. Furthermore, the reduction of the distortion enables the application of a hard coat agent with higher adhesion.

  From the viewpoint of reducing distortion on the surface of the molded product, it is also preferable to combine heat insulating mold forming and rapid heating / cooling mold forming (halogen lamp irradiation, induction heating, high-speed switching of heat medium, ultrasonic mold, etc.) It is.

  In addition, as is generally known, injection press molding enables molding at an extremely low pressure, so that the level of clamping pressure of the injection molding machine can be greatly reduced. In particular, this is a large molded product having a long flow length, so that the quality of the product can be improved and the cost of the equipment can be reduced. In another aspect, injection press molding is a molding method capable of reducing the molding temperature. However, there is a limit to reducing the heat load due to its large size. Examples of the heat load due to the large size include an extremely long flow path and a long injection time.

  In the above-described injection press molding, particularly injection press molding of a large molded product, it is important to maintain the parallelism between the molds in the intermediate clamping state and the intermediate clamping state to the final clamping state. Injection press molding is often performed by providing a molding machine having a small clamping force as described above with a high-weight mold close to the upper limit. Therefore, it is difficult to maintain parallelism in the mold clamping mechanism of the molding machine due to the weight of the mold. Also, an offset load is generated by the pressure at the time of resin filling, and it is difficult to maintain the parallelism of the mold. Misalignment of parallelism causes mold galling and makes mass production difficult. Furthermore, maintaining parallelism between molds achieves a more uniform pressure load on the resin within the mold. As a result, the pressure applied to the resin achieves a low pressure as a whole, and it is possible to provide a molded product with less distortion. When the parallelism between the molds is not sufficient, a difference occurs in the pressure applied due to the difference in the location of the resin molded product, which may cause one distortion.

  As a method for maintaining the parallelism between the molds, (i) the mold mounting plates are arranged between molds while adjusting the parallelism between the molds by using a mold clamping mechanism at a plurality of positions, preferably at four corners. Method of maintaining parallelism, and (ii) Adjusting the parallelism between molds by applying correction force to multiple locations, preferably 4 corners, on the mold mounting plate (mold mounting surface) A method for maintaining the parallelism between the molds is preferably exemplified. The method (i) is a method for maintaining parallelism by a mold clamping mechanism, and the method (ii) is a method for maintaining parallelism by a correction force applying mechanism provided separately. As a molding machine that realizes the method (i), for example, the MDIP series manufactured by Meiki Seisakusho Co., Ltd., which is a large molding machine capable of injection press molding provided with a platen four-axis parallel control mechanism can be exemplified. As the mold clamping mechanism and the correction force applying mechanism, a normal hydraulic cylinder is preferably used, but other combinations such as a pneumatic cylinder, a combination of a ball screw and a screw, and a combination of a rack gear and a pinion gear are exemplified.

  Furthermore, the molding conditions in the injection press molding will be briefly described. The magnification ratio of the mold capacity in the intermediate clamping state of injection press molding is preferably in the range of 1.2 to 5 times the target molded article capacity of the target molded article volume, and in the range of 1.3 to 4 times. Is more preferable, the range of 1.5 to 3.5 times is more preferable, and the range of 1.7 to 3 times is particularly preferable. However, this range is based on the premise that the following compression stroke amount is in an appropriate range. In such a range, even in a large injection molded product, there is little distortion of the molded product, and an injection molded product excellent in crack resistance can be obtained.

  Further, the magnification ratio of the mold capacity at the completion of the resin supply is preferably in the range of 1.05 to 4.5 times the target molded article capacity, more preferably in the range of 1.1 to 3.5 times. The range of 2 to 3 times is more preferable, and the range of 1.4 to 2.7 times is particularly preferable.

  The final clamping state of the injection press molding is preferably a state where the parting surfaces of the movable side mold and the fixed side mold do not contact each other. By adopting such a state, it is possible to uniformly transmit the pressure to the resin, and an injection molded product excellent in crack resistance can be obtained with less distortion of the molded product. The molding in such a state is stably performed while maintaining the parallelism between the molds. Therefore, the maintenance of the parallelism between the molds is important in injection press molding from this point. The distance between the parting surfaces of the movable mold and the fixed mold in the final mold clamping state is preferably in the range of 0.05 to 3 mm, and more preferably 1 to 2 mm.

  The amount of movement of the mold from the intermediate clamping state to the final clamping state of injection press molding (hereinafter sometimes referred to as a compression stroke) is preferably in the range of 1 to 10 mm, more preferably in the range of 1 to 6 mm. A range of 2 to 4 mm is more preferable. A retreat amount in such a range achieves both a low clamping force, which is an advantage of the injection press molding method, and good molding efficiency and appearance of the molded product. The thickness of the molded product is not particularly limited, but is preferably in the range of 0.5 to 10 mm, more preferably in the range of 1 to 7 mm.

  Furthermore, the moving speed when the mold is moved from the intermediate clamping state to the final clamping state is preferably 0.5 mm / sec or more, more preferably 1 mm / sec or more, and further preferably 10 mm / sec or more. A molded article having a higher L / D requires a higher mold capacity enlargement ratio and requires a higher moving speed. This is because in order to reduce the distortion of the molded product, it is important to end the compression process up to a predetermined final clamping state while the change in the thermal distribution of the molten resin inside the mold is small. The higher the moving speed, the larger the compression stroke can be handled. Therefore, it is preferable that the moving speed is as high as possible, but at present, about 40 mm / sec is a practical limit. If the level is 35 mm / sec, sufficiently precise speed control is possible. The moving speed is obtained by dividing the compression stroke from the intermediate clamping state to the final clamping state by the time required for compression, and does not necessarily have to be a constant speed. In addition, as the compression stroke is larger and the moving speed of the mold is larger as described above, the galling of the mold is more likely to occur. Therefore, maintaining the parallelism between the molds is an important and essential condition.

  More preferably, the injection molded product of the present invention has only one gate on the side surface of the molded product. Such an injection-molded product usually tends to have a large flow length and is often subjected to a higher heat load (since all the resin passes through a single gate through a long flow path, shear heat generation tends to be excessive). As a result, the light transmittance of the molded product becomes non-uniform, or the inherent hue is hindered. The pellet made of the resin composition of the present invention has improved thermal stability. Therefore, a molded article having only one gate on the side part of the molded article is a particularly preferable molded article shape in the present invention. An injection press molding method suitable for injection molding of a large molded product is a molding method that further exhibits the effects of the present invention.

<About large molded products>
Since the polycarbonate resin composition of the present invention has good thermal stability, it is more suitable for larger molded articles. More and particularly large moldings such, the maximum projected area preferably 500～50,000Cm ^2, more preferably 5,000～40,000Cm ^2, more preferably of 10,000～35,000Cm ² It is a molded product. Further, a molded product having a flow length of 30 cm or more is suitable for exhibiting the effects of the present invention, and more preferably 35 cm or more. On the other hand, 200 cm or less is appropriate as the upper limit of the flow length, and 180 cm or less is more appropriate.

  As a more preferable molded product shape, the ratio L / D of the distance (L (mm)) from the gate portion to the flow end with respect to the thickness (D (mm)) of the molded product is preferably 75 or more. The above is more preferable, 130 or more is further preferable, and 150 or more is particularly preferable. On the other hand, the upper limit is suitably 1,000 or less, preferably 800 or less, and more preferably 600 or less.

  The molded article made of the polycarbonate resin composition of the present invention described above may have a surface shape such as a Fresnel lens shape or a cylindrical lens shape. The molded product may be formed by laminating such shapes with other materials separately. By having a light scattering effect on the surface, it is also possible to enhance the heat ray shielding effect. Further, the same effect can be obtained by laminating a layer containing a luster pigment on the molded product.

  The obtained molded product is attached to the final product by various methods. When the molded product is a window material, it is usually attached to a window frame material. For such attachment, a method using a two-color molding method or an insert molding method is known. Furthermore, laser welding, hot plate welding, ultrasonic welding, and adhesion with an adhesive are known. The molded product made of the resin composition of the present invention is attached to a member such as a window frame member by such various methods.

<About surface modification>
The molded product formed from the polycarbonate resin composition of the present invention can be further imparted with other functions by surface modification. “Surface modification” as used herein means the surface layer of a resin molded product by means of vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, and printing. It means to form a new layer on top. Such surface modification can be performed by a method used for ordinary resin molded products. Further, such a surface modification method includes any one of (i) a method of directly applying to the vehicle exterior molded article of the present invention, and (ii) a method of laminating the treated resin film on the vehicle exterior molded article of the present invention. This method is also applicable.

  Examples of the method for laminating a metal layer or metal oxide layer on the surface of a resin molded product (including the resin film in the case of (ii) above) include physical vapor deposition, chemical vapor deposition, thermal spraying, and plating. It is done. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method. By such a method, it is possible to form a hard film such as diamond-like carbon. Examples of the thermal spraying method include an atmospheric pressure plasma spraying method and a low pressure plasma spraying method. Examples of the plating method include an electroless plating (chemical plating) method, a hot dipping method, and an electroplating method. In the electroplating method, a laser plating method can be used.

  Among the above methods, the vapor deposition method and the plating method are preferable for forming a metal layer on a molded article made of the resin composition of the present invention, and the vapor deposition method is preferable for forming a metal oxide layer. Surface modification with metal oxides typified by ATO, ITO, tin oxide and the like is preferable. This is because the surface-modified resin molded article has a relatively good light transmittance and hue of transmitted light, and has a high heat ray shielding rate. Such heat ray shielding can maintain, for example, the temperature in the vehicle compartment more appropriately. Such surface modification by the metal oxide may be performed on any side corresponding to the outer side and the inner side of the molded article.

  Next, the hard coat layer of the present invention will be described. In the present invention, various hard coat agents can be used as the hard coat treatment, and examples of the hard coat agent used in the present invention include a silicone resin hard coat agent and an organic resin hard coat agent. The hardness of the hard coat layer is not particularly limited as long as it is higher than the hardness of polycarbonate.

  The silicone resin hard coat agent forms a cured resin layer having a siloxane bond. For example, partial hydrolysis of a compound mainly composed of a compound corresponding to a trifunctional siloxane unit (trialkoxysilane compound, etc.). Condensates, preferably partially hydrolyzed condensates further containing compounds corresponding to tetrafunctional siloxane units (tetraalkoxysilane compounds etc.), and further partially hydrolyzed condensates filled with metal oxide fine particles such as colloidal silica Is mentioned. The silicone resin hard coat agent may further contain a bifunctional siloxane unit and a monofunctional siloxane unit. These include alcohol generated during the condensation reaction (in the case of a partially hydrolyzed condensate of alkoxysilane), etc., but if necessary, may be dissolved or dispersed in any organic solvent, water, or a mixture thereof. Good. Examples of the organic solvent for this purpose include lower fatty acid alcohols, polyhydric alcohols and ethers thereof, and esters. In addition, in order to obtain a smooth surface state, various surfactants such as siloxane-based and alkyl fluoride-based surfactants may be added to the hard coat layer.

  Examples of the organic resin hard coat agent include melamine resin, urethane resin, alkyd resin, acrylic resin, and polyfunctional acrylic resin. Here, examples of the polyfunctional acrylic resin include resins such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, and phosphazene acrylate. Among these, an ultraviolet curable hard coat agent is particularly preferable. Furthermore, it is more preferable that the hard coat agent contains a structural unit obtained by copolymerizing an ultraviolet absorbing monomer and / or a photostable monomer. A more suitable organic resin hard coat agent is one in which a hard coat layer is formed by copolymerizing such a monomer and an alkyl (meth) acrylate monomer. Such an ultraviolet curable hard coat agent is preferable in that its processing is simple, and in addition, it is easy to include a structural unit obtained by copolymerizing an ultraviolet absorbing monomer and / or a light stable monomer. This is preferable in that the light resistance of the product can be greatly improved. As a commercial item of an acrylic hard coat agent, for example, Origin Electric series manufactured by Origin Electric Co., Ltd. and Nippon Shokubai Co., Ltd. Udouble series are exemplified. These can be used by mixing with a crosslinking agent component.

  On the other hand, when a glass-like hardness is required for a molded product, a silicone resin-based hard coat agent having excellent long-term weather resistance and relatively high surface hardness is preferable. In particular, it is preferable to form a primer layer (first layer) made of various resins and then form a top layer (second layer) prepared from a silicone resin hard coat agent thereon.

  Examples of the resin that forms such a primer layer (first layer) include urethane resins, acrylic resins, polyester resins, epoxy resins, melamine resins, amino resins, and polyester acrylates, urethane acrylates, and epoxy resins, which are composed of various blocked isocyanate components and polyol components. Various polyfunctional acrylic resins such as acrylate, phosphazene acrylate, melamine acrylate, amino acrylate and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, an acrylic resin and a polyfunctional acrylic resin preferably include 50% by weight, more preferably 60% by weight or more, and those composed of an acrylic resin and a urethane acrylate are particularly preferable. These can be applied either by applying a predetermined reaction after application of an unreacted material to obtain a cured resin, or by directly applying the reacted resin to form a cured resin layer. In the latter case, the resin is usually dissolved in a solvent to form a solution, which is then applied and then the solvent is removed. In the former case, a solvent is generally used.

  Further, the resin forming the primer layer of the silicone resin hard coat agent of the present invention includes the above-mentioned light stabilizer and ultraviolet absorber, silicone resin hard coat agent catalyst, thermal / photopolymerization initiator, polymerization inhibitor. , Silicone antifoaming agents, leveling agents, thickeners, suspending agents, anti-sagging agents, flame retardants, various additives of organic / inorganic pigments / dyes, and auxiliary additives.

The hard coat layer of the present invention preferably contains an ultraviolet absorber because it has good durability (particularly durability against adhesion). Furthermore, the more suitable aspect of the hard-coat layer of this invention is as follows. That is, a hard coat layer having a configuration in which the first layer is formed on the surface of the vehicle exterior molded article or aromatic polycarbonate resin film of the present invention, and the second layer is formed on the surface of the first layer,
The first layer is composed of a crosslinked acrylic copolymer (acrylic copolymer-I) and an ultraviolet absorber, and the second layer is composed of a crosslinked organosiloxane polymer,
The crosslinked acrylic copolymer (acrylic copolymer-I) is 50 mol% or more of the following formula (X-1)

（式中Ｒ^１はメチル基またはエチル基である。）
で表される繰り返し単位、
５〜３０モル％の下記式（Ｘ−２）

(In the formula, R ¹ is a methyl group or an ethyl group.)
A repeating unit represented by
5-30 mol% of following formula (X-2)

（式中Ｒ^２は炭素数２〜５のアルキレン基である。式（Ｘ−２）で表される繰り返し単位において少なくとも一部のＲ^ａは単結合であり、残りが水素原子である。Ｒ^ａが単結合の場合はウレタン結合を介して、他の式（Ｘ−２）で表される繰り返し単位と結合している。）
で表される繰り返し単位、および
０〜３０モル％の下記式（Ｘ−３）

(In the formula, R ² is an alkylene group having 2 to 5 carbon atoms. In the repeating unit represented by the formula (X-2), at least a part of ^Ra is a single bond, and the remainder is a hydrogen atom. ^{When a} is a single bond, it is bonded to a repeating unit represented by the other formula (X-2) via a urethane bond.)
And a repeating unit represented by formula (X-3) of 0 to 30 mol%

（但し、式中Ｙは水素原子またはメチル基であり、Ｒ^３は水素原子、炭素数２〜５のアルキル基、紫外線吸収残基からなる群より選ばれる少なくとも一種の基である。但し、Ｙがメチル基であり、かつＲ^３がメチル基またはエチル基である場合を除く。）で表される繰り返し単位からなり、ウレタン結合と式（Ｘ−１）〜（Ｘ−３）で表される繰り返し単位の合計量とのモル比が４／１００〜３０／１００の範囲にある架橋したアクリル共重合体であり、
該架橋したオルガノシロキサン重合体は、下記式（ｐ−４）〜（ｐ−６）

(Wherein, Y is a hydrogen atom or a methyl group, and R ³ is at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 2 to 5 carbon atoms, and an ultraviolet absorbing residue. Is a methyl group, and R ³ is a methyl group or an ethyl group.), And is represented by a urethane bond and formulas (X-1) to (X-3). A cross-linked acrylic copolymer having a molar ratio with the total amount of repeating units in the range of 4/100 to 30/100,
The crosslinked organosiloxane polymer has the following formulas (p-4) to (p-6):

（式中、Ｑ^１、Ｑ^２は、それぞれ炭素数１〜４のアルキル基、ビニル基、またはメタクリロキシ基、アミノ基、グリシドキシ基および３，４−エポキシシクロヘキシル基からなる群より選ばれる少なくとも一種の基で置換された炭素数１〜３のアルキル基である。）
で表される繰り返し単位からなり、該繰り返し単位の全量を１００モル％としたとき、式（ｐ−４）：８０〜１００モル％、式（ｐ−５）：０〜２０モル％、および式（ｐ−６）：０〜２０モル％である架橋したオルガノシロキサン重合体である、ハードコート層である。

(In the formula, Q ¹ and Q ² are each at least one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, or a methacryloxy group, an amino group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. A C 1-3 alkyl group substituted with a group.)
When the total amount of the repeating units is 100 mol%, the formula (p-4): 80 to 100 mol%, the formula (p-5): 0 to 20 mol%, and the formula (P-6): It is a hard coat layer which is a crosslinked organosiloxane polymer of 0 to 20 mol%.

  As a coating method, a method such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, or a roller coating method is appropriately selected depending on the shape of a molded product to be coated. be able to. Of these, the dip coating method, the flow coating method, and the spray coating method, which can easily cope with complicated molded product shapes, are preferable.

  The polycarbonate resin composition of the present invention is a polycarbonate resin composition containing a very small amount of inorganic fine particles typified by a heat ray shielding agent, and solves the problem caused by the uneven color of the mass-produced pellets, and is a large injection molding It is suitable for applications such as window materials, which have good production efficiency and thermal stability at the time of molding. Therefore, the polycarbonate resin composition pellets of the present invention are useful in applications for building / vehicle glazing materials, so-called window materials.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these. The following items were evaluated.
(I) Evaluation method (I-1) O _1S / C _1S measurement on the surface of a molded product X-ray surface of a disk-shaped molded product formed from a composition-S composed of each fatty acid ester prepared by the method specified in the text measured by photoelectron spectroscopy (ESCA) device, it was determined and the _{O 1S / C} 1S. From the calibration line between the fatty acid ester concentration calculated beforehand from O _1S / C _1S and O _1S / C _1S , the surface concentration of the molded product was calculated. ECSA measurement was performed using an ESCALAB 200S apparatus manufactured by VG, UK, excitation source MgKα ray (300 W), energy 20 eV, step width 0.1 eV, photoelectron extraction angle 45 °, Wide (survey, 1100 to 1.0 eV) & Narrow (O, C, etc. / 0.1eV) performed under the condition Scan, the area ratio of the _{O 1S} peak obtained ESCA spectrum and _{C 1S} peak from _{(O 1S / C} 1S peak area ratio) _{O 1S / C} 1S Asked. This measurement was performed five times by sampling five locations in the vicinity of a radius of about 35 mm of the disk-shaped molded product, and the average value was O _1S / C _1S in each fatty acid ester.

(I-2) Arithmetic average roughness measurement of the surface of the molded product The surface roughness meter Surfcom 1400A manufactured by Tokyo Seimitsu Co., Ltd. was used.

(I-3) Measurement of generated amount of pellet cut waste 5 kg of pellets of the polycarbonate resin composition produced by the following production method-I were weighed to obtain 2 polyethylene bags having a width of 500 mm, a length of 864 mm and a thickness of 0.08 mm. I put them in a stack of sheets. The bag was further sealed with compressed air in an internal volume of about 38 liters. The bag was put into a tumbler type blender (capacity: about 50 liters), and the pellets in the bag were shaken and mixed by rotating at a rotational speed of 25 rpm for 60 minutes. The pellets were divided into 25 times of 200 g and treated with a vibrating sieve (TM-70-2S manufactured by Deoksugaku Kosakusho) for 5 minutes. A standard sieve (16 mesh) having an opening of 1 mm was used as the sieve of the vibration sieve machine. Such treatment was carried out by repeating the procedure of discarding the sample remaining on the sieve after treatment for 5 minutes and treating with a new sample. In addition, cut scraps (obviously large enough to pass through the sieve) remain on the inner surface of the polyethylene bag that cannot be removed. The weight of the cut waste was calculated by washing the polyethylene bag with water, filtering with a filter paper, drying at 60 ° C. for 24 hours, and then subtracting the initial filter paper weight from the weight of the filter paper. The total amount of the cut waste collected with the vibration sieve and the amount of cut waste attached to the polyethylene bag was taken as the amount of cut waste after shaking, and the cut waste content (B (ppm)) was obtained. . Similarly, the cut waste content (A (ppm)) was calculated from the amount of cut waste of the pellets not subjected to the blender treatment. By subtracting A (ppm) from the B (ppm), an index of the ease with which the pellet cut waste is generated was obtained. It can be said that the higher this value is, the easier it is to generate cut waste during pellet transportation or pipe transportation.

(I-4) Evaluation of thermal stability of pellets Large molding machine capable of injection press molding pellets of polycarbonate resin composition produced by the following production method-II and equipped with a platen 4-axis parallel control mechanism (Co., Ltd.) A transparent roof for automobiles shown in FIG. 1 was manufactured by injection press molding using a machine manufactured by Meiki Seisakusho: MDIP2100, maximum clamping force 33540 kN). Such a molding machine is equipped with a hopper dryer facility that can be dried to the same level as described above, and the dried pellets were supplied to the molding machine supply port by compressed air transportation and used for molding. Molding was performed at a cylinder temperature of 300 ° C., a hot runner set temperature of 290 ° C., a mold temperature of 120 ° C. on the fixed side, 110 ° C. on the movable side, filling time of 24 seconds, press stroke: 5 mm, and cooling time: 150 seconds. Further, the movable mold parting surface was not in contact with the fixed mold parting surface in the final forward position. The runner was a valve gate type hot runner (diameter 7 mmφ) manufactured by Moldmasters. The mold compression started immediately before the completion of filling, the valve gate was closed immediately after the filling was completed, and the molten resin did not flow back from the gate to the cylinder. did. The thermal stability was confirmed by observing the appearance of the molded product thus obtained. A case where appearance defects such as silver streak and yellowing were slightly observed was evaluated as “X”, a remarkable one was evaluated as “XX”, and a case where there was no such appearance defect was evaluated as “◯”.

(II) Preparation method of sample for evaluation (II-1) Preparation of composition-S Each of four kinds of fatty acid esters (FAE-1 to FAE-4) to be described later, 0.1 part by weight and a viscosity average molecular weight of 22,5000 Bisphenol A type polycarbonate resin powder (the following symbol PC) 99.9 parts by weight was uniformly dry blended. The PC was dried with hot air at 120 ° C. for 5 hours prior to dry blending. The blend was supplied to a vent type twin screw extruder (manufactured by Nippon Steel Works, Ltd .: TEX30α, fully meshed, rotated in the same direction, double thread screw) to produce pellets. One kneading zone of the extruder was provided in front of the vent port. The extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, and a vent vacuum of 3 kPa. The extrusion temperature was a temperature configuration in which the first supply port was gradually raised from 220 ° C. to the die portion 270 ° C. The extruded strand is cooled with water and then cut with a pelletizer to produce four types of pellets of composition-S corresponding to each fatty acid ester (all major axis is 3.4 mm, minor axis is 2.3 mm, and length is 2.7 mm). did.

(II-2) Preparation of ESCA and molded product for surface roughness measurement It was prepared by the method described in detail in the section “Means for Solving the Problems”. That is, the pellet of the composition-S was dried with hot air at 120 ° C. for 5 hours. Thereafter, a sample for ESCA measurement was prepared from the pellet using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .: SG260MP-HP) having a clamping force of 2548 kN. The stability of the molding was confirmed from the measurement of the molded product weight of 36.5 g in all cases. Furthermore, it was confirmed whether or not the obtained molded product was a product sufficiently transferring the smoothness of the mold surface. Such confirmation was made by measuring the arithmetic average roughness of the surface of the molded article molded at the time of measuring the release force, and the Ra of the surface was 0.01 μm. The arithmetic average roughness was measured using a surface roughness meter Surfcom 1400A manufactured by Tokyo Seimitsu Co., Ltd.

(II-3) Preparation of pellets for measuring the amount of cut waste generated Various additives were blended with 100 parts by weight of polycarbonate resin powder produced from bisphenol A and phosgene by the interfacial condensation polymerization method. The amount of each additive was as shown in Table 1. The mixture was homogenized with a blender. The obtained mixture was supplied to a vent type twin screw extruder and melt kneaded to obtain pellets. The polycarbonate resin powder was used after sufficiently dried through a paddle dryer. All the additives contained were mixed with polycarbonate resin powder to obtain a master agent containing 10% by weight of the additive. A predetermined amount of the master agent was supplied to the extruder using a separate meter. The extruder used was a vent type twin screw extruder (manufactured by Nippon Steel Works, Ltd .: TEX77CHT (completely meshing, rotating in the same direction, two-thread screw)) with a screw diameter of 77 mmφ. The extruder has a kneading zone comprising a combination of a feeding kneading disc and a reverse feeding kneading disc in order at an L / D of about 8 to 11 when viewed from the screw root, and thereafter an L / D of about 16 It had a kneading zone consisting of a feeding kneading disk in the portion -17. Further, the extruder had a reverse flight full flight zone of L / D 0.5 length immediately after the latter kneading zone. One vent port was provided in the portion of L / D of about 18.5-20. The extrusion conditions were a discharge rate of 320 kg / h, a screw rotation speed of 160 rpm, and a vent vacuum of 3 kPa. In addition, the extrusion temperature was a temperature configuration in which the temperature was gradually increased from the first supply port 230 ° C. to the die portion 280 ° C.

  The strand extruded from the die was cooled in a hot water bath, cut by a pelletizer and pelletized. The pellet immediately after pelletization was received in a bucket having an internal volume of 5 liters, and a thermocouple was inserted to measure the temperature. As a result, the temperature was about 125 ° C. (this temperature was the same for all samples). In addition, the pellet immediately after being cut | disconnected was removed about what was removable among the long pellet and cut waste with insufficient cutting | disconnection by passing a vibration-type sieve part for about 10 second. The process until obtaining the pellet after passing through the vibrating sieve section is referred to as Production Method-I.

After that, the obtained pellets were pneumatically transported through a pipe and put into a gravity mixer (so-called octopus foot blender) having a capacity of about 16 m ³ . The mixing was performed so that the renewal capacity was 200%. The process until obtaining such mixed pellets is referred to as Production Method-II.

(III) Sample raw materials The contents of the components indicated by symbols in Table 1 are as follows.
(A component)
PC: Polycarbonate resin powder having a viscosity average molecular weight of 23,700 produced from bisphenol A and phosgene by an interfacial condensation polymerization method (manufactured by Teijin Chemicals Ltd .: Panlite L-1250WP (trade name))

(Compound for comparison similar to B component and B component; calculation method of B-1 / B-2 ratio will be described later)
FAE-1 (for comparison): Pentaerythritol tetrastearate obtained by reacting pentaerythritol and stearic acid (made by Wako Pure Chemical Industries, Ltd., special grade reagent) by a conventional method. The ester had an acid value of 0.8 mgKOH / g and a hydroxyl value of 10 mgKOH / g. The ratio of fatty acid ester component to free fatty acid (B-1 / B-2) was 96.3 / 3.7 (molar ratio). Furthermore, the surface concentration of the fatty acid ester in Composition-S was 3.5% by weight.
FAE-2: A mixture of the above FAE-1: 95% by weight and 5% by weight of stearic acid (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent). The mixture is an ester obtained by dissolving FAE-1 by heating to 80 ° C., adding stearic acid to the dissolved material, and mixing uniformly using an electric blender (Brown). The ester had an acid value of 8.5 mgKOH / g and a hydroxyl value of 9.5 mgKOH / g. The ratio of fatty acid ester component to free fatty acid component (B-1 / B-2) was 79.8 / 20.2 (molar ratio). Furthermore, the surface concentration of the fatty acid ester in Composition-S was 5.5% by weight.
FAE-3: Full ester of pentaerythritol and aliphatic carboxylic acid (mainly stearic acid and palmitic acid) (manufactured by Riken Vitamin Co., Ltd .: Riquester EW-400). The ester had an acid value of 10.4 mg KOH / g and a hydroxyl value of 6.9 mg KOH / g. The ratio (B-1 / B-2) between the fatty acid ester component and the free fatty acid component was 75.7 / 24.3 (molar ratio). Furthermore, the surface concentration of the fatty acid ester in Composition-S was 5.2% by weight.
FAE-4 (for comparison): Glycerin mono fatty acid ester (manufactured by Riken Vitamin Co., Ltd .: Riquemar S-100A). The ester had an acid value of 0.8 mgKOH / g and a hydroxyl value of 327 mgKOH / g.

(Calculation method of B-1 / B-2 ratio)
B-1 / B-2 = P / Q was calculated by the method described in the text. The NMR measurement for calculating the basic Ff / Fe = y was performed as follows. A 35 mg sample (FAE-1 to FAE-3) was weighed. This sample was dissolved in 0.5 ml of deuterated chloroform. The obtained solution was put into an ampule tube for ¹ H-NMR measurement. The ampule tube was used as a sample for ¹ H-NMR measurement. The measurement sample was subjected to ¹ H-NMR measurement using an NMR measuring apparatus (JNM-alpha600, manufactured by JEOL) having a frequency of 600 MHz. Measurement conditions were set to 2048 times of integration and about 4 hours of measurement time per sample.

From this measurement, Ff / Fe was calculated as follows. That is, the signal of the hydrogen atom of the methylene group bonded to the carboxyl group of the aliphatic carboxylic acid component (including both acid and ester) appears at about 2.3 ppm. The peak area of this region was Sc. On the other hand, the hydrogen atom signal of the methylene group in the pentaerythritol component bonded to the ester bond appears at about 4.1 ppm. The peak area of this region was Se. From these,
Ff / Fe = y = (Sc / 2-Se / 2) / (Se / 2)
From the relationship, Ff / Fe (= y) was calculated.

(C component)
LAB: Heat ray shielding agent comprising about 20% by weight of LaB ₆ fine particles having an average particle size of 70 nm, about 24% by weight of ZrO ₂ and a resin binder (KHDS-06 manufactured by Sumitomo Metal Mining Co., Ltd.)

(Other ingredients)
PEPQ: Phosphonite heat stabilizer (manufactured by Sandoz: Sandstub P-EPQ)
IRGF: Phosphite heat stabilizer (Ciba Specialty Chemicals: Irgafos 168)
IRGN: Hindered phenol antioxidant (Ciba Specialty Chemicals: Irganox 1076)
UV1577: 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol (manufactured by Ciba Specialty Chemicals: Tinuvin 1577)
BL: Brewing agent (manufactured by Bayer: Macrolex Violet B)

  As is clear from the above table, it can be seen that the resin composition pellets that satisfy the requirements of the present invention have a reduced amount of cut waste and exhibit good thermal stability in large molded articles.

  As described above, the polycarbonate resin composition of the present invention contains a fatty acid ester having a specific surface concentration in the reference composition and inorganic fine particles having a specific particle size typified by a heat ray shielding agent. Such a resin composition has thermal stability suitable for a large-sized injection-molded product with reduced cutting waste and high heat load. Taking advantage of such properties, the resin composition of the present invention is a glazing material for vehicles, such as a back door window, a sunroof, a roof panel, a detachable top, a window reflector, a winker lamp lens, a room lamp lens, and a display display front plate. Can be suitably used. In addition to glazing materials for vehicles, window glass for construction machinery, windows for buildings, houses, and greenhouses, roofs for garages and arcades, lighting lenses, traffic light lenses, optical equipment lenses, mirrors, glasses, Goggles, sound deadening walls, motorcycle windshields, nameplates, solar cell covers or solar cell substrates, display device covers, touch panels, and parts for game machines (such as pachinko machines) (circuit covers, chassis, pachinko ball transport guides, etc.), etc. It can be used for a wide range of applications. Therefore, the polycarbonate resin molded body of the present invention is useful for various applications such as various electronic / electrical equipment, OA equipment, vehicle parts, machine parts, other agricultural materials, fishery materials, transport containers, packaging containers, playground equipment, and miscellaneous goods. The industrial effects that it plays are exceptional.

The schematic of the molded article of the transparent roof for motor vehicles shape | molded in the Example is shown. As shown in the drawing, the transparent roof has a three-dimensional shape composed of gentle curved surfaces. [1-A] shows a front view (projected on the platen surface during molding), [1-B] shows a side view in the longitudinal direction, and [1-C] shows a side view from the flow end side.

Explanation of symbols

11 Transparent roof molded product main body (main body is 5 mm thick, maximum projected area is about 11,000 cm ² )
12 Portion corresponding to the tip of the hot runner nozzle 13 Gate of the molded product (the gate is a flat plate having a thickness of 5 mm)
14 Molded product gate side length (corresponds to the maximum width of the molded product and is 1000 mm)
15 Length of molded product flow end side (900mm)
16 Length of molded product (1240mm)
17 Total length of the molded product including the gate (1350mm)
18 Height of molded product (90mm)
19 Mounting claw

Claims (6)

100 parts by weight of a polycarbonate resin (component A), 0.01 to 0.5 parts by weight of a fatty acid ester (component B) composed mainly of a full ester composed of a higher fatty acid and a polyhydric alcohol, and an inorganic having an average particle size of 2 to 500 nm Polycarbonate resin comprising a resin composition comprising fine particles (component C) 0.1 × 10 ⁻⁴ to 1,000 × 10 ⁻⁴ parts by weight, wherein the component B satisfies the following condition-I Composition.
Condition-I: Molded product surface concentration of a resin composition (composition-S) obtained by blending 0.1 part by weight of B component with 99.9 parts by weight of bisphenol A type polycarbonate resin having a viscosity average molecular weight of 22,500 It is in the range of 4 to 11% by weight. Here, the molded product uses a disk-shaped mold cavity having a surface arithmetic mean roughness (Ra) of 0.01 μm, a diameter of 115 mm, a thickness of 3 mm, and a direct gate at the center. , A disk-shaped molded product obtained by injection molding the composition-S under conditions of a cylinder temperature of 300 ° C., a mold temperature of 80 ° C. and an injection time of 1.4 seconds, and the surface concentration is X Calculated by measuring with linear photoelectron spectroscopy. 100 parts by weight of a polycarbonate resin (component A), 0.01 to 0.5 parts by weight of a fatty acid ester (component B) composed mainly of a full ester composed of a higher fatty acid and a polyhydric alcohol, and an inorganic having an average particle size of 2 to 500 nm Fine resin (component C) 0.1 × 10 ⁻⁴ to 1,000 × 10 ⁻⁴ parts by weight of a resin composition, wherein the component B is an ester composed of a higher fatty acid and a polyhydric alcohol (component B-1) ), And at least one selected from higher fatty acids and monoesters of higher fatty acids and monohydric alcohols (component B-2), and the molar ratio of components B-1 and B-2 (B- 1 / B-2) is in the range of 96/4 to 65/35.   The polycarbonate resin composition according to claim 1, wherein the component B is a full ester of a higher fatty acid and pentaerythritol.   The C component is an inorganic fine particle composed of a boride of one or more metals selected from the group consisting of La, Pr, Nd, Ce, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W The polycarbonate resin composition according to any one of claims 1 to 3.   The pellet which consists of a polycarbonate resin composition of any one of the said Claims 1-4. A polycarbonate resin molded article having a maximum projected area of 500 to 50,000 cm ² produced by injection molding the pellets of claim 5.

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