JP4520124B2 - Polycarbonate resin composition and molded product thereof - Google Patents

Description

  The present invention relates to a polycarbonate resin composition and a molded product thereof. More specifically, the molded product made of the resin composition is excellent in transparency and weather resistance, releasability during molding, molding heat resistance, and distortion inside the molded product are improved, and stress cracking of the molded product is greatly increased. The present invention relates to a polycarbonate resin composition which is improved and has excellent design properties, and a molded product thereof.

  Polycarbonate resins have excellent transparency, heat resistance, mechanical strength, etc., and are therefore widely used in electrical, mechanical, automotive, medical applications and the like. Polycarbonate resins are widely used due to the various excellent features described above. In particular, application to a transparent member for vehicles for the purpose of weight reduction has been widely attempted. Examples of such a transparent member for a vehicle include a headlamp lens, a resin window glass, a rear lamp lens, and a meter cover. These members are characterized by complex and large shapes and extremely high demands on the quality of the molded product.

  When these members are formed by injection molding using a polycarbonate resin composition, the following points may be problematic.

  That is, there is a problem that it is difficult to obtain a molded product having good releasability and no occurrence of cracks. More specifically, there is a problem that cracking of the molded product is likely to occur when good release properties are provided. On the other hand, when the release agent is reduced, the occurrence of cracks due to an increase in the release resistance increases. Furthermore, good transparency and molding heat resistance are required, and more preferably, good weather resistance is also required. While the vehicle transparent member is strongly required to be stable at a high quality level, since it is a large molded product, the heat load imposed on the resin material becomes severe.

  Further, in many cases, the vehicle transparent member is subjected to a surface treatment such as a hard coat treatment. However, cracks may occur in the molded product in such hard coat processing. Such cracking of the molded product can occur even if annealing is performed before the hard coat treatment. Therefore, it is considered that some factor in the characteristics of the polycarbonate resin composition during molding and annealing promotes the occurrence of cracking in the molded product. Need to be improved.

  As described above, the transparent member for a vehicle has good releasability, reduced internal distortion of the molded product, and improved crack resistance, in addition to good transparency and molding heat resistance, preferably Further, there is a demand for a polycarbonate resin composition having weather resistance. As described above, the manufacture of a transparent member for a vehicle, particularly a large member, has characteristics different from the manufacture of an optical disk substrate which is a typical optical molded product of polycarbonate resin. The production of an optical disk substrate is a molding that requires a very high processing temperature, but on the other hand, it is a molding with a very short molding cycle and a simple shape (a constant thickness and a resin flow is not complicated). From this point, the resin composition is required to have different characteristics from those of the optical disk substrate.

  Conventionally, a method of blending a fatty acid ester is widely known as a method for improving the mold releasability of a polycarbonate resin, and among them, glycerin monostearate is often used. However, the polycarbonate resin composition to which glycerin monostearate has been added is not sufficient in terms of crack resistance.

  As a release agent used for a polycarbonate resin, a full ester of a polyhydric alcohol and an aliphatic carboxylic acid such as pentaerythritol tetrastearate is also widely known. Various proposals have been made for the purpose of further improving the quality of the polycarbonate resin composition to which the full ester is added. Hereinafter, a full ester of a polyhydric alcohol and an aliphatic carboxylic acid may be simply referred to as “fatty acid full ester”.

  Patent Document 1 discloses a polycarbonate resin composition containing an ester of pentaerythritol in which an OH group content and an acid value of an ester compound are extremely reduced. However, the main purpose of the invention described in the publication is to lower the ductile-brittle transition temperature of the resin composition (that is, the ductile temperature range increases).

  Moreover, in patent document 2, the internal mold release which is polycarbonate resin and full ester 90% or more acid value 0.6-1.6, iodine value 0.1-1.3, and metal element Sn content 5-300 ppm A polycarbonate resin composition comprising an agent is disclosed. Although this publication discloses that the molding heat resistance is lowered when the acid value exceeds 1.6, the further improvement of the mold release property (reduction of the mold release force) and the distortion generated inside the molded product are disclosed. It did not disclose sufficient technical knowledge regarding reduction.

  On the other hand, an attempt to apply a resin composition in which a polycarbonate resin is blended with an ultraviolet absorber having no maximum absorption at 350 to 400 nm and a fluorescent brightening agent to a vehicle lamp lens is also known (see Patent Document 3).

JP-A-2-69556 JP 2001-192543 A Japanese Patent Laid-Open No. 2002-3710

  The present invention has good transparency, weather resistance, releasability during molding, and molding heat resistance, and further has reduced internal distortion and improved crack resistance of the molded product, in addition to the design Another object of the present invention is to provide a polycarbonate resin composition excellent in properties, particularly suitable for a transparent member for vehicles.

  The present inventors diligently studied to solve the above problems. First, since the above problem is that the mold release property imparted by the mold release agent and other characteristics are not compatible, the present inventors have studied the type of the mold release agent as one of the solution factors. Secondly, the cause of cracking was examined. As a result, it was speculated that the cracks during molding may be caused by solvent cracks due to contact of additive components such as a mold release agent partially remaining on the mold surface with a high-temperature molded product during molding. In particular, it was found that cracks are likely to occur on the edge side of the molded product because the distortion tends to increase and the release agent and the like are easily deposited. In addition, the cause of cracking in the hard coat treatment after the annealing treatment may be due to the fact that the residual stress is not removed by the annealing treatment, but from the above points, the resin on the surface of the molded product is partially The possibility of deterioration was also considered. Therefore, the conclusion that the kind of release agent is important also in this point was obtained.

  As a result of further intensive studies under the above-described studies, the inventors have found that a composition in which a specific fatty acid ester is added to a polycarbonate resin can solve the above problems, and has completed the present invention.

  In the present invention, (1) 100 to 5 parts by weight of a polycarbonate resin (component A), 0.005 to 2 parts by weight of an ester of an alcohol and an aliphatic carboxylic acid (component B-1), an ultraviolet absorber (component C) 0 0.01-2 parts by weight, fluorescent brightening agent (component D) 0.0001-3 parts by weight, and at least one selected from phosphorus stabilizers (E component) and hindered phenol stabilizers (F component) A resin composition comprising 0.0001 to 1 part by weight of a stabilizer, wherein the component B-1 has (i) a 5% weight loss temperature in TGA (thermogravimetric analysis) of 250 to 360 ° C. , (Ii) an acid value of 4 to 20 and (iii) a quartering performed under the conditions of a processing temperature of 120 ° C. and a processing time of 24 hours using a polycarbonate resin sheet having a viscosity average molecular weight of 24,500 One ellipse In the test method, the critical stress is relates to the polycarbonate resin composition is not less than 15 MPa.

  According to this configuration (1), by using a specific fatty acid ester that satisfies the specific requirements (i) to (iii), an ultraviolet absorber, a fluorescent brightening agent, and a stabilizer in combination, The polycarbonate resin composition which solved the subject is provided. Here, the requirements (i) to (iii) are all indicators that enable screening of fatty acid esters by a simple method. Further details on the relationship between the index and the structure of the fatty acid ester will be described later. Briefly stated, requirement (i) relates to an improvement in releasability by having a certain amount of volatile components. The requirement (ii) has almost the same meaning as the requirement (i) since the main component of the volatile component is a free aliphatic carboxylic acid. Further, requirement (iii) indicates an indicator that the release agent component adhering to the mold surface does not adversely affect the polycarbonate resin. Because the factors of such adverse effects are complicated by the influence of acid value, hydroxyl value, and impurities contained in it, it is much more rational to specify the limit stress value directly rather than specifying each factor individually. Is. Such an index enables comprehensive selection of appropriate esters without distinguishing between partial esters or total esters (full esters). Hereinafter, the configuration (1) may be simply referred to as “first aspect”.

  The test method for requirement (iii) is a method well known per se, but will be described again. The polycarbonate resin sheet used is a 1 mm thick sheet produced by an unstretched method using a T die by a melt extrusion method. That is, the sheet is substantially free of residual stress. In the test, a polycarbonate resin sheet applied to a quarter ellipse-shaped jig is fixed, a release agent is applied onto the sheet, and left under a predetermined condition (for example, a 120 ° C. hot air dryer in which air is circulated). Store for 24 hours in). If the fatty acid ester has a low viscosity at 120 ° C., it is devised so that it does not sag during the test by bringing it in contact with gauze. Usually, a crack has occurred in the sheet after the test. Among them, the critical stress is determined based on the crack generated at the lowest stress portion. The stress is calculated based on a predetermined calculation formula from the horizontal distance of the generation position. In such measurement, the polycarbonate resin sheet is set on the jig taking care not to apply strong stress locally when it is attached to the jig, and measured with a plurality of samples (for example, n = 5) in consideration of variations caused by such factors. It is appropriate to determine the critical stress value. In the test, since most of the fatty acid esters are solid at room temperature, the fatty acid ester is heated to 60 to 100 ° C. to be melted and then applied to the sheet.

  One of the preferred embodiments of the present invention is that (2) the B-1 component is an aliphatic polyhydric alcohol having 5 to 30 carbon atoms and an aliphatic carboxylic acid having 10 to 22 carbon atoms, which are tetravalent to octavalent. It is a polycarbonate resin composition of said (1) which is ester of this. Since such an ester of a polyhydric alcohol and an aliphatic carboxylic acid has an appropriate molecular weight and an appropriate polarity, it exhibits more suitable characteristics in achieving both good release properties and transparency.

  Another aspect of the present invention is as follows: (3) 100 parts by weight of a polycarbonate resin (component A), a 4 to 8 valent aliphatic polyhydric alcohol having 5 to 30 carbon atoms and an aliphatic carboxylic acid having 10 to 22 carbon atoms Full ester (component B-2) 0.005 to 2 parts by weight, UV absorber (component C) 0.01 to 2 parts by weight, fluorescent brightener (component D) 0.0001 to 3 parts by weight, and phosphorus A resin composition comprising 0.0001 to 1 part by weight of at least one stabilizer selected from a system stabilizer (E component) and a hindered phenol stabilizer (F component), the free fat in the composition Resin composition in which the molar ratio (Ff: Fe) of the number of moles (Ff) of the carboxyl group of the aromatic carboxylic acid to the number of moles (Fe) of the ester bond of the component B-2 is in the range of 8:92 to 30:70 It depends on things.

  In the present invention, as apparent from the configuration (1), the fatty acid ester has an appropriate volatile component, thereby providing the composition with good releasability. The main body is a free aliphatic carboxylic acid. Therefore, a resin composition containing such an aliphatic carboxylic acid in an appropriate ratio, particularly pellets used for injection molding, has good properties for solving the above problems as well as good release properties. Hereinafter, the configuration (3) may be simply referred to as “second aspect”.

  One of the preferred embodiments of the present invention is that (4) the B-1 component or the aliphatic carboxylic acid in the B-2 component includes a palmitic acid component and a stearic acid component, and gas chromatograph-mass spectrometry thereof. In the peak area in (GC / MS method), the sum of the area of the palmitic acid component (Sp) and the area of the stearic acid component (Ss) is 80% or more of the total aliphatic carboxylic acid component, and the area ratio ( It is a polycarbonate resin composition of said (1)-(3) whose Ss / Sp) is 1.3-30. By having such a specific aliphatic carboxylic acid component, there is provided a polycarbonate resin composition that has a better releasability and solves the above problems.

  One of the preferred embodiments of the present invention is: (5) the polycarbonate of the above (2) to (4), wherein the aliphatic polyhydric alcohol is at least one polyhydric alcohol selected from pentaerythritol and dipentaerythritol. It is a resin composition. According to this configuration (5), there is provided a polycarbonate resin composition that solves the above-described problems and is excellent in both heat resistance and releasability.

  One of the preferred embodiments of the present invention is as follows. (6) The component (C) is at least one ultraviolet absorber selected from benzotriazole-based UV absorbers and triazine-based UV absorbers. It is a polycarbonate resin composition of (5). According to this structure (6), the polycarbonate resin composition which has the better weather resistance and solves the said subject is provided.

  One of the preferred embodiments of the present invention is the polycarbonate resin composition of the above (1) to (6), wherein (7) the component D is a fluorescent whitening agent represented by the following formula (1).

（但し、上記式中Ｒ_１はアミノ基、アルキル基置換アミノ基、水酸機、および下記式（２）、（３）または（４）のいずれかを示し、Ｒ_２は水素原子またはフルオロアルキル基を示し、Ｒ_３は水素原子、アルキル基、またはアリール基のいずれかを示す。）

(In the above formula, R ₁ represents an amino group, an alkyl group-substituted amino group, a hydroxyl group, and any one of the following formulas (2), (3) or (4), and R ₂ represents a hydrogen atom or a fluoroalkyl. And R ₃ represents a hydrogen atom, an alkyl group, or an aryl group.)

  According to this configuration (7), there is provided a polycarbonate resin composition that solves the above-described problems, which is superior in luminous efficiency by the fluorescent whitening agent and, as a result, is superior in design.

  One of the preferred embodiments of the present invention is that (8) the polycarbonate resin composition has a smooth flat plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm in a range of 0.1 to 1%. It is a polycarbonate resin composition of said (1)-(7) which shows haze value and does not contain a filler substantially. In the present invention, a polycarbonate resin composition having good transparency can be provided by the essential components. Among them, as described in the configuration (8), the mold release property and the above-mentioned releasability can be achieved while achieving very good transparency. A polycarbonate resin composition satisfying characteristics such as a cracking system is provided. The polycarbonate resin composition having such characteristics can be suitably used in various fields, and can be suitably used especially for a vehicle transparent member, particularly a vehicle lamp lens that requires good transparency.

  One of the preferred embodiments of the present invention is (9) pellets comprising the polycarbonate resin composition of (1) to (8) above, and (10) manufactured by injection molding the pellet of (9) above. It is a molded product. The resin composition of the present invention is in the form of pellets, and exhibits the characteristics most when the pellets are molded. And a favorable molded article is provided by using this pellet.

  One of the preferred embodiments of the present invention is (11) the molded product according to (10) above, wherein the molded product is subjected to a hard coat treatment. The molded product of the present invention has low distortion and is excellent in crack resistance. Therefore, the occurrence of cracks in the hard coat treatment is suppressed, and as a result, hard coat treatment (including primer treatment) that is more aggressive against the polycarbonate resin is possible. Such a highly aggressive hard coat treatment provides a molded product having a hard coat layer with good adhesion.

  One of the preferred embodiments of the present invention is (12) the molded product according to (10) to (11) above, wherein the molded product is a transparent member for a vehicle, and more preferably (13) the transparent for vehicle. The member is a molded article of (12) which is a vehicle lamp lens. According to the configurations (12) and (13), the quality requirements are extremely severe, and even in a transparent member for a vehicle that is a large molded product and the heat load is severe, especially in a vehicle lamp lens for which the hue and other requirements are severe, A good molded article is provided.

The details of the present invention will be further described below.
(First aspect)
In the first aspect of the present invention, 0.005 to 2 parts by weight of an ester of alcohol and an aliphatic carboxylic acid (B-1 component) and an ultraviolet absorber (C component) with respect to 100 parts by weight of the polycarbonate resin (A component) ) 0.01 to 2 parts by weight, at least 1 selected from 0.001 to 3 parts by weight of optical brightener (D component), and a phosphorus stabilizer (E component) and a hindered phenol stabilizer (F component) A resin composition comprising 0.0001 to 1 part by weight of a stabilizer, wherein the component B-1 has (i) a 5% weight loss temperature in TGA (thermogravimetric analysis) of 250 to 360 ° C. (Iii) The acid value is 4 to 20, and (iii) a polycarbonate resin sheet having a viscosity average molecular weight of 24,500 is used under the conditions of a treatment temperature of 120 ° C. and a treatment time of 24 hours. Quarter In one oval test method, the critical stress is a polycarbonate resin composition is not less than 15 MPa.

(Polycarbonate resin: Component A)
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.

  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 may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or may be a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid, 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 ratio is 0.001-1 mol%, preferably 0.005-0.5 mol%, particularly preferably 0.01-0, in the total amount of the aromatic polycarbonate. .3 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. 5 mol%, particularly preferably 0.01 to 0.3 mol% is preferable. Such a ratio can be calculated by ¹ H-NMR measurement.

  The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Preferred examples of the aliphatic difunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid.

  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 ⁻⁸ to 1 × 10 ⁻³ equivalent, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalent, relative to 1 mol of dihydric phenol as a raw material. 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 books and patent publications.

  The viscosity average molecular weight of the polycarbonate resin is preferably 13,000 to 40,000, more preferably 14,000 to 30,000, and still more preferably 15,000 to 27,000. It is. When a polycarbonate resin having such a viscosity average molecular weight is used, the resin composition of the present invention has sufficient strength and good melt fluidity during molding. Such good melt fluidity is preferable because it enables further reduction of molding strain. Moreover, when it is in the above range, resistance to secondary processing such as hard coat treatment is sufficient. 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 (PC1) having a viscosity average molecular weight of 70,000 to 300,000 and an aromatic polycarbonate (PC2) having a viscosity average molecular weight of 10,000 to 30,000, and the viscosity average molecular weight is 15,000 to An aromatic polycarbonate having a viscosity of 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 a high molecular weight component-containing aromatic polycarbonate increases the entropy elasticity of the polymer due to the presence of PC1, and is more advantageous at the time of injection press molding suitably used in the case of a large-sized molded product. 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 PC2 component lowers the overall melt viscosity, promotes relaxation of the resin, and enables molding with lower strain. A similar effect is also observed in a polycarbonate resin containing a branched component.

(Fatty acid ester: B-1 component)
The B-1 component used in the present invention is an ester of an alcohol and an aliphatic carboxylic acid, and the following requirements (i) to (iii), that is, (i) 5% weight in TGA (thermogravimetric analysis) The processing temperature is 120 ° C. and the processing time is 24 using a polycarbonate resin sheet having a reduction temperature of 250 to 360 ° C., (ii) an acid value of 4 to 20 and (iii) a viscosity average molecular weight of 24,500. In the quarter ellipse test method performed under time conditions, the critical stress is satisfied to be 15 MPa or more.

(TGA)
In the present invention, the B-1 component has a 5% weight loss temperature (hereinafter simply referred to as “weight loss temperature”) in TGA (thermogravimetric analysis) measurement of 250 to 360 ° C. It has been found that the release force can be reduced (release property can be improved). Moreover, a full ester satisfying such conditions is excellent in crack resistance. The range of the weight reduction temperature is more preferably 280 to 360 ° C, still more preferably 300 to 350 ° C, and particularly preferably 310 to 340 ° C. When the weight reduction temperature exceeds 360 ° C., it is difficult to reduce the release force. On the other hand, if the weight loss temperature is lower than the above range, the heat resistance is insufficient, which may cause discoloration, and generally tends to be disadvantageous in crack resistance. The weight reduction temperature is determined as a temperature at which a 5% weight reduction is observed in a measurement condition in which the temperature is increased from 23 ° C. in a nitrogen gas atmosphere to 600 ° C. at a temperature increase rate of 20 ° C./min.

(Acid value)
Furthermore, this invention discovered that it can satisfy | fulfill both favorable mold release force and thermal stability by satisfy | filling the range whose acid value is 4-20 in B-1 component. The acid value is more preferably in the range of 4-18, and still more preferably in the range of 5-15. Further, when the full ester is more suitable as the fatty acid ester of the present invention, it is possible to reduce distortion inside the molded product. If the acid value is less than 4, it is difficult to reduce the releasing force, and those having an acid value exceeding 20 are not preferable in terms of thermal stability. The main component that expresses the acid value is a free aliphatic carboxylic acid contained in the fatty acid ester (hereinafter may be simply referred to as free fatty acid), and therefore the fatty acid ester that is the B-1 component used in the present invention. Among them, an acid component such as a free fatty acid is present in an amount corresponding to its acid value. 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.

  The reason why the fatty acid ester satisfying the requirements (i) and (ii) makes it possible to reduce the releasing force (improving the releasing property) is not clear, but is considered as follows. When the weight reduction temperature is in the range corresponding to the melt processing temperature of the polycarbonate resin of 360 ° C. or less, the fatty acid ester has good heat resistance but produces a certain amount of volatile matter. It is considered that the volatile matter is gasified at the time of the molding process, so that it tends to be biased toward the tip of the fountain flow generated when the resin mold is filled, and as a result, it is biased at a high concentration on the surface of the molded product. Thereby, the further improvement of mold release property is achieved. Further, the object to be measured by the acid value is mainly free fatty acid, which is gasified at the time of molding process from its molecular weight, and it is considered that the deviation to the surface of the molded product occurs as described above, and contributes to the improvement of the releasability. Therefore, there is a certain degree of correlation between the acid value and the weight loss temperature.

  As described above, it is possible to improve the mold release force by allowing a certain amount of gasification component to move to the surface, and the preferred embodiment of the present invention is a complex mixture of various components. Therefore, it is very reasonable to specify the fatty acid ester in requirements (i) and (ii).

  As mentioned above, the fatty acid ester of the component B-1 referred to in the present invention is a generic term for not only the ester compound itself but also a mixture of the compound and a free aliphatic carboxylic acid compound. Furthermore, by utilizing the fact that the value of acid value and weight reduction temperature varies depending on the proportion of free aliphatic carboxylic acid as described above, an aliphatic carboxylic acid is added separately to a fatty acid ester having a low acid value or a high weight reduction temperature. Thus, it is possible to adjust a fatty acid ester having a target acid value and weight reduction temperature. Similarly, it is also 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 and weight reduction temperatures.

(Limit stress)
The requirement (iii) directly indicates the influence of the fatty acid ester used on the polycarbonate resin. The fatty acid ester having a low critical stress value itself is highly aggressive against the polycarbonate resin, and as a result, causes cracks. Therefore, if the fatty acid ester having a low critical stress value is biased to the surface of the molded product during molding, the fatty acid ester may be deposited on a part of the mold and cause cracks in the molded product. As described above, since the fatty acid ester is required to be biased to the surface of the molded product to some extent for good releasability, crack suppression by suppressing such bias is not a preferable method. Therefore, it is necessary to use a fatty acid ester that satisfies the condition that the aggressiveness against the polycarbonate resin is low in order to improve the cracking resistance. As described above, the aggressiveness of the fatty acid ester to the polycarbonate resin is mainly affected by the acid value, hydroxyl value, impurities contained in the ester, etc. Rather than defining the factors individually, it is very reasonable to define the critical stress values directly. Moreover, whether or not such a requirement is satisfied can be easily confirmed by a method well known to those skilled in the art.

  The limit stress of the polycarbonate resin with respect to the fatty acid ester in the requirement (iii) is 15 MPa or more, more preferably 16 MPa or more. On the other hand, as described above, free fatty acids contributing to releasability are required to some extent, but since such free fatty acids are aggressive against polycarbonate resin, it is appropriate that the value of critical stress is not more than a certain upper limit value. It becomes. The upper limit of the critical stress value in requirement (iii) is preferably 20 MPa, and more preferably 19 MPa.

(Fatty acid full ester)
The fatty acid ester of the B-1 component of the present invention may be any of a partial ester and a full ester (full ester) as long as the conditions (i) to (iii) are satisfied. However, the partial ester usually has a higher hydroxyl value, and the range satisfying the requirement (iii) is limited. Therefore, the full ester is more preferable. In the present invention, the term “full ester” does not necessarily mean that the esterification rate is 100%, but may be 80% or more, preferably 85% or more. Such a full ester reduces the frictional force between the resins inside the resin, realizes a smoother resin flow, and as a result, can reduce the distortion inside the molded product.

(Method for producing fatty acid ester)
The manufacturing method of said specific fatty acid ester is not specifically limited, Alcohol and aliphatic carboxylic acid can utilize conventionally well-known various methods. 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.

(alcohol)
The alcohol used for the component B-1 is preferably a polyhydric alcohol, particularly preferably an aliphatic polyhydric alcohol having a valence of 4 to 8 and 5 to 30 carbon atoms. . The valence of the aliphatic polyvalent 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.

(Aliphatic carboxylic acid)
The aliphatic carboxylic acid used for the component B-1 has 3 to 32 carbon atoms, and an aliphatic carboxylic acid having 10 to 22 carbon atoms is particularly preferable. Examples of the aliphatic carboxylic acid 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, And saturated aliphatic carboxylic acids such as docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and setoleic acid. Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred.

  Aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats (such as beef tallow and pork fat) and vegetable fats (such as palm oil). Accordingly, an aliphatic carboxylic acid such as stearic acid is usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. In the production of the B-1 component 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.

(Ss / Sp)
The aliphatic carboxylic acid constituting the B-1 component contains a palmitic acid component and a stearic acid component, and the peak area in the pyrolysis methylated GC / MS (gas chromatography-mass spectrometry) method is the area of the palmitic acid component ( The total of Sp) and the area (Ss) of the stearic acid component 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.

  The total of Sp and Ss is preferably 85% or more, more preferably 90% or more, and still more preferably 91% or more in the total aliphatic carboxylic acid component. 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 range of 1.3-10 is more preferable, the range of 1.3-4 is further more preferable, and the range of 1.3-3 is particularly preferable. These mixing ratios need not be satisfied with a single aliphatic carboxylic acid, but may be satisfied by mixing two or more aliphatic carboxylic acids.

  The fats and oils used as the raw material for the aliphatic carboxylic acid satisfying the above mixing ratio include animal fats and oils such as beef tallow and lard, and linseed oil, safflower oil, sunflower oil, soybean oil, corn oil, and peanut oil. And vegetable oils such as cottonseed oil, 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.

(Hydroxyl value)
The hydroxyl value of the component B-1 is preferably low from the viewpoint of thermal stability, release force reduction and crack resistance, while too low is not preferable because the cost increases due to the increase in production time. The range of 0.1-30 is suitable for the hydroxyl value of B-1 component, the range of 1-30 is preferable, and the range of 2-20 is more preferable. 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. .

(Iodine number)
In the B-1 component of the present invention, the iodine value is preferably low from the viewpoint of thermal stability. The iodine value of the component B-1 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.

  The fatty acid ester of component B-1 used in the present invention is 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight, preferably 0.05 to 0.5 parts by weight, based on the polycarbonate resin. Part. When the fatty acid ester of the component B-1 exceeds the above range and is too small, the releasability is not sufficiently improved and the cracking resistance is also lowered. On the other hand, when the amount of the fatty acid ester of the component B-1 exceeds the above range, the transparency of the molded product is impaired, and the cracking resistance may be decreased due to a decrease in molding heat resistance.

(Ultraviolet absorber: component C)
Specific examples of the C component ultraviolet absorber of the present invention include benzophenone-based compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2- Hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxy Benzophenone, bis (5-benzoyl-4-hydroxy Ci-2-methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone and the like are exemplified.

  Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5- tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p -Phenylenebis (1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and co-polymerized with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

  Specifically, the ultraviolet absorber is, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4, 4-hydroxyphenyltriazine). 6-diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) ) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

  Specifically, in the case of the cyclic imino ester, the ultraviolet absorber is, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1). -Benzoxazin-4-one), 2,2'-p, p'-diphenylenebis (3,1-benzoxazin-4-one) and the like.

  Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

  Furthermore, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbent monomer and / or the light stable monomer and a single amount of alkyl (meth) acrylate or the like can be obtained. It may be a polymer type ultraviolet absorber copolymerized with a body. Preferred examples of the ultraviolet 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) acrylic acid ester. The

  Among these, benzotriazole and hydroxyphenyltriazine are preferable, and benzotriazole is particularly preferable for a headlamp lens. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

  The compounding quantity of a ultraviolet absorber is 0.01-2 weight part with respect to 100 weight part of polycarbonate resin (A component), Preferably it is 0.03-2 weight part, More preferably, it is 0.02-1 weight part, Furthermore, Preferably it is 0.05-0.5 weight part.

(Fluorescent brightener: D component)
Examples of the fluorescent whitening agent for component D include coumarin-based, naphthalimide-based, and benzoxazolyl-based fluorescent whitening agents. Among them, a coumarin-based fluorescent whitening agent is preferable, and is represented by the following formula (1). An optical brightener is preferred.

（但し、上記式中Ｒ_１はアミノ基、アルキル基置換アミノ基、水酸機、および下記式（２）、（３）または（４）のいずれかを示し、Ｒ_２は水素原子またはフルオロアルキル基を示し、Ｒ_３は水素原子、アルキル基、またはアリール基のいずれかを示す。）

(In the above formula, R ₁ represents an amino group, an alkyl group-substituted amino group, a hydroxyl group, and any one of the following formulas (2), (3) or (4), and R ₂ represents a hydrogen atom or a fluoroalkyl. And R ₃ represents a hydrogen atom, an alkyl group, or an aryl group.)

Among the above formulas (1), an embodiment in which R ₁ is a substituent of formula (3) is preferable. Further, coumarin derivatives of the following formulas (5) and (6) are preferred, and formula (6) is particularly preferred. The said ultraviolet absorber can be used individually or in combination of 2 or more types.

  The compounding amount of the optical brightener is 0.0001 to 3 parts by weight, preferably 0.0005 to 1 part by weight, more preferably 0.0005 to 0.5 parts by weight, based on 100 parts by weight of the polycarbonate resin (component A). More preferably, the amount is 0.001 to 0.5 parts by weight, and particularly preferably 0.001 T or 0.1 parts by weight. When the fluorescent brightening agent of component D is too much less than the above range, good weather resistance and appearance cannot be obtained. On the other hand, when it exceeds the above range, the transparency is lowered.

(Phosphorus stabilizer: E component)
Examples of the phosphorus stabilizer for the E component include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof.

  Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylpheny) ) Phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite Phyto, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is 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.

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphite compounds or phosphonite compounds are preferable. In particular, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite and bis (2,4-di-) tert-Butylphenyl) -phenyl-phenylphosphonite is preferred. A combination of these and a phosphate compound is also a preferred embodiment.

(Hindered phenol stabilizer: F component)
Examples of the F component hindered phenol stabilizers include α-tocopherol, butylhydroxytoluene, sinapy alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert. -Butylfell) propionate, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4 -(N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2, 2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebis ( 2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2 2,2′-ethylidene-bis (4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-) 6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert -Butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1 , -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3 -Methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 '-Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thi Diethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di -Tert-butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N'-bis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,3 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxypheny) ) Isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanate 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and tetrakis [methylene-3- (3 ′, 5′-di) -Tert-butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  The blending amount of at least one stabilizer selected from the E component and the F component is 0.0001 to 1 part by weight, preferably 0.001 to 0.1 part by weight, based on 100 parts by weight of the polycarbonate resin (component A). More preferably, it is 0.005 to 0.1 parts by weight. When the amount of the stabilizer is too much less than the above range, it is difficult to obtain a good stabilizing effect. When the amount exceeds the above range, the physical properties of the composition may be lowered.

(Haze value)
In the polycarbonate resin composition of the present invention, a smooth flat plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm exhibits a value in the range of 0.1 to 1%, and is substantially free of filler. Is preferred. The haze value is more preferably in the range of 0.1 to 0.5%.

  The haze value is measured using a haze meter. Such a smooth flat plate is obtained by subjecting the pellets to predetermined drying, and then injection-molding the pellets into a cavity constituted by a mold surface having an arithmetic average roughness (Ra) of 0.03 μm. The arithmetic average roughness (Ra) of the mold surface is measured using a surface roughness meter.

(Light stabilizer)
The polycarbonate resin composition of the present invention includes bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis. (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1 , 2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2, 2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, and polymethylpropyl 3-oxy- [4- (2,2,6, - it may also include tetramethyl) piperidinyl] hindered amine light stabilizer represented by a siloxane.

The above light stabilizers may be used alone or in a mixture of two or more. The amount of the light stabilizer used is preferably from 0.0005 to 3 parts by weight, more preferably from 0.01 to 2 parts by weight, still more preferably from 0.02 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin (component A). .
That's right.

(Bluing agent)
The polycarbonate resin composition of the present invention preferably further uses 0.05 to 3 ppm (weight ratio) of a blueing agent in the polycarbonate resin composition. This is effective for eliminating the yellow color of the polycarbonate resin molded product. In particular, since UV absorbers are used, there is a reality that resin products tend to be yellowish due to the "action and color of UV absorbers". Therefore, in order to give natural transparency to molded products, Use is very effective.

  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. By blending the bluing agent, the polycarbonate resin composition of the present invention achieves a better hue. The important point here is the blending amount of the bluing agent. In the resin composition, if the bluing agent is less than 0.05 ppm, the hue improving effect may be insufficient. On the other hand, if it exceeds 3 ppm, the light transmittance is not suitable. A more preferable blending amount of the bluing agent is in the range of 0.5 to 2.5 ppm, more preferably 0.5 to 2 ppm in the resin composition.

  Representative examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR from Bayer, and Terrasol Blue RLS from Sand.

(Dye and pigment)
In the polycarbonate resin composition of the present invention, various dyes and pigments can be used in addition to the bluing agent as long as the object of the invention is not impaired. In particular, a dye is preferable from the viewpoint of maintaining transparency. Preferred dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindo Examples thereof include linone dyes and phthalocyanine dyes. The amount is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight per 100 parts by weight of the polycarbonate resin (component A).

(Antistatic agent)
The polycarbonate resin composition of the present invention may be required to have antistatic performance. In such a case, it is preferable to include an antistatic agent. Examples of the antistatic agent include (i) an organic sulfonic acid phosphonium salt such as an aryl sulfonic acid phosphonium salt typified by dodecylbenzenesulfonic acid phosphonium salt and an alkyl sulfonic acid phosphonium salt. The phosphonium salt has an appropriate composition ratio of 5 parts by weight or less per 100 parts by weight of component A, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and 1.5 to 3 parts by weight. A range of parts is more preferred.

  Examples of the antistatic agent include (ii) 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. Organic sulfonate alkali (earth) metal salts of Specifically, for example, metal salts of dodecylbenzenesulfonic acid, metal salts of perfluoroalkanesulfonic acid, and the like are exemplified. The organic sulfonate alkali (earth) metal salt has a composition ratio of 0.5 parts by weight or less per 100 parts by weight of component A, preferably 0.001 to 0.3 parts by weight, and 0.005 to 0.005. 2 parts by weight is more preferred. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

  Examples of the antistatic agent include (iii) organic sulfonic acid ammonium salts such as alkyl sulfonic acid ammonium salt and aryl sulfonic acid ammonium salt. The composition ratio of the ammonium salt is 0.05 parts by weight or less per 100 parts by weight of the component A. Examples of the antistatic agent include (iv) glycerin derivative esters such as maleic anhydride monoglyceride and maleic anhydride diglyceride. The ester has a composition ratio of 0.5 parts by weight or less per 100 parts by weight of component A. Examples of the antistatic agent include (v) 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 per 100 parts by weight of component A. Examples of other antistatic agents include (vi) non-organic compounds such as carbon black, carbon fiber, carbon nanotube, graphite, metal powder, and metal oxide powder. The composition ratio of the non-organic compound is 0.05 parts by weight or less per 100 parts by weight of the component A.

(Compound with heat-absorbing ability)
In the polycarbonate resin composition of the present invention, a compound having a heat-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, various metal compounds having excellent near infrared absorption ability such as ATO and ITO, and carbon fillers. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of carbon fillers include carbon black, graphite (including both natural and artificial, and whiskers), carbon fibers (including those produced by vapor phase growth), carbon nanotubes, and fullerenes, preferably carbon. Black and graphite. These can be used alone or in combination of two or more. The phthalocyanine-based near infrared absorber is preferably 0.005 to 0.2 parts by weight, more preferably 0.008 to 0.1 parts by weight, and 0.01 to 0 parts per 100 parts by weight of the polycarbonate resin (component A). 0.07 part by weight is more preferable. In the resin composition of the present invention, the metal oxide near-infrared absorber and the carbon filler are preferably in the range of 0.1 to 200 ppm (weight ratio), more preferably in the range of 0.5 to 100 ppm, and in the range of 1 to 50 ppm. Is more preferable.

(Flame retardants)
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 flame retardants include halogenated bisphenol A polycarbonate flame retardants, organic salt flame retardants, aromatic phosphate ester flame retardants, and halogenated aromatic phosphate ester flame retardants. It can be used above.

  Specifically, the polycarbonate type flame retardant of halogenated bisphenol A is a polycarbonate type flame retardant of tetrabromobisphenol A, a copolymer polycarbonate type flame retardant of tetrabromobisphenol A and bisphenol A, or the like.

  Specifically, organic salt flame retardants include dipotassium diphenylsulfone-3,3′-disulfonate, potassium diphenylsulfone-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, 2,4,5-trisulfonate. Potassium chlorobenzenesulfonate, potassium bis (2,6-dibromo-4-cumylphenyl) phosphate, sodium bis (4-cumylphenyl) phosphate, potassium bis (p-toluenesulfone) imide, potassium bis (diphenylphosphate) imide, Potassium bis (2,4,6-tribromophenyl) phosphate, potassium bis (2,4-dibromophenyl) phosphate, potassium bis (4-bromophenyl) phosphate, potassium diphenylphosphate, sodium diphenylphosphate, Potassium perfluorobutane sulfonate, sodium lauryl sulfate Um or potassium hexadecyl sulfate, sodium or potassium.

  Specifically, the halogenated aromatic phosphate ester type flame retardant is tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, etc. is there.

  Specifically, the aromatic phosphate ester flame retardant is triphenyl phosphate, tris (2,6-xylyl) phosphate, tetrakis (2,6-xylyl) resorcin diphosphate, tetrakis (2,6-xylyl) hydroquinone diphosphate. , Tetrakis (2,6-xylyl) -4,4′-biphenol diphosphate, tetraphenylresorcin diphosphate, tetraphenylhydroquinone diphosphate, tetraphenyl-4,4′-biphenol diphosphate, aromatic ring source is resorcin and phenol Aromatic polyphosphates that do not contain phenolic OH groups, aromatic ring sources are resorcin and phenol, aromatic polyphosphates that contain phenolic OH groups, aromatic ring sources are hydroquinone and phenol, and are phenolic Aromatic polyphosphates containing no H groups, aromatic polyphosphates containing similar phenolic OH groups, ("Aromatic polyphosphates" shown below are aromatic polyphosphates containing phenolic OH groups and aromatic polyphosphates not containing Aromatic polyphosphates whose aromatic ring sources are bisphenol A and phenol, aromatic polyphosphates whose aromatic ring source is tetrabromobisphenol A and phenol, aromatic ring sources are resorcin and 2 , 6-xylenol aromatic polyphosphate, aromatic polyphosphates whose aromatic ring sources are hydroquinone and 2,6-xylenol, aromatic polyphosphates whose aromatic ring sources are bisphenol A and 2,6-xylenol, aromatic rings The source is tetrabromobisph Aromatic polyphosphates such a Nord A and 2,6-xylenol.

(Other resins and elastomers)
In the polycarbonate resin composition of the present invention, other resins and elastomers can be used in a small proportion within a range where the object of the present invention is not impaired.

  Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethylene, and polypropylene. And other resins such as polyolefin resin, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, and epoxy resin.

  As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / sterene / butadiene) which is a core-shell type elastomer. Examples thereof include rubber and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

(Other additives)
Various inorganic fillers, flow modifiers, antibacterial agents, photocatalytic antifouling agents, infrared absorbers, photochromic agents, and the like can be blended in the polycarbonate resin composition of the present invention.

(Manufacture of polycarbonate resin composition)
Arbitrary methods are employ | adopted in order to manufacture the polycarbonate resin composition of this invention. For example, component A to component F, and optionally other additives, are thoroughly mixed using premixing means such as a V-type blender, Henschel mixer, mechanochemical apparatus, extrusion mixer, etc., and optionally an extrusion granulator And granulating with a briquetting machine or the like, and then melt-kneading with a melt-kneader represented by a vent type twin-screw extruder and pelletizing with a device such as a pelletizer.

  In addition, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of the method of premixing a part of each component include a method of premixing components other than the polycarbonate resin of component A of the present invention in advance and then mixing the polycarbonate resin or supplying it directly to an extruder.

  In addition, as a premixing method, for example, when a component having a powder form is included as the component A, a part of the powder and an additive to be blended are blended to form a master batch of the additive diluted with powder. Is mentioned. Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder.

  As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. 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.

  Examples of the melt kneader include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw extruder.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder.

  Although the shape of the obtained pellet can take general shapes, such as a cylinder, a prism, and a spherical shape, it is more preferably a cylinder. 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. 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.

(Second aspect)
As mentioned above, since the fatty acid ester of the component B-1 of the present invention mainly comprises an ester compound as a main component and a free fatty acid as a subcomponent, the polycarbonate resin composition of the present invention has a resin composition containing these two compounds. It can be said that it is a thing. Therefore, according to this invention, the resin composition of the following 2nd aspect is provided from this point. That is, in the second aspect of the present invention, polycarbonate resin (component A) 100 parts by weight, tetravalent to octavalent C5-C30 aliphatic polyhydric alcohol and C10-C22 aliphatic carboxylic acid, Full ester (component B-2) 0.005 to 2 parts by weight, UV absorber (component C) 0.01 to 2 parts by weight, fluorescent brightener (component D) 0.0001 to 3 parts by weight, and phosphorus A resin composition comprising 0.0001 to 1 part by weight of at least one stabilizer selected from a system stabilizer (E component) and a hindered phenol stabilizer (F component), the free fat in the composition Resin composition in which the molar ratio (Ff: Fe) of the number of moles (Ff) of the carboxyl group of the aromatic carboxylic acid to the number of moles (Fe) of the ester bond of the component B-2 is in the range of 8:92 to 30:70 It is a thing. In particular, the resin composition is preferably in the form of pellets used to produce the desired molded article. The relationship between the second aspect and the first aspect is as follows. In the second aspect, the fatty acid full ester is a preferable aspect among the fatty acid esters in the first aspect. By using a full ester, the aggressiveness to the polycarbonate resin based on the hydroxyl group is sufficiently reduced. In addition, since Ff: Fe below specifies the carboxylic acid component in the composition, the acid value factor is similarly defined in the specific range. Although there is not a little aggressiveness to the polycarbonate resin based on the impurities, it may be considered that the influence of the impurities is less on the influence of the carboxylic acid and the hydroxyl group in the commonly used fatty acid ester.

(Ff: Fe)
The ratio of the fatty acid full ester compound and the aliphatic carboxylic acid compound in the resin composition is calculated by ¹ H-NMR measurement of the resin composition. In addition, since the ratio of the aliphatic carboxylic acid compound in a pellet is very small, this measurement needs to be measured using an NMR measuring apparatus having a frequency of 600 MHz or more. The molar ratio (Ff: Fe) between the number of moles of carboxyl groups of free aliphatic carboxylic acid (Ff) and the number of moles of ester bonds (Fe) in the aliphatic carboxylic acid ester compound calculated from such measurement is 10 : The range of 90-25: 75 is suitable, and the range of 12: 88-22: 78 is more suitable. For example, in the case of pentaerythritol ester, Ff: Fe can be 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 free acid compounds and ester compounds) 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 = (Sc / 2-Se / 2) :( Se / 2)
From the relationship, Ff: Fe can be calculated (converted so that the sum of Ff and Fe is 100).

  In addition, this molar ratio is not necessarily the same as that ratio in the fatty acid ester blended at the time of pellet production. This is presumably because the ester bond of the fatty acid ester compound may be decomposed by heating or the like during pellet production.

  In the second aspect of the present invention, the polycarbonate resin of component A is the same as in the first aspect. The 4- to 8-valent aliphatic polyhydric alcohol having 5 to 30 carbon atoms and the aliphatic carboxylic acid having 10 to 22 carbon atoms constituting the component B-2 are the same as the preferred embodiment of B-1 in the first embodiment. is there. The aliphatic carboxylic acid of the component B-2 includes a palmitic acid component and a stearic acid component, and the peak area in the gas chromatograph-mass spectrometry (GC / MS method) shows the area (Sp) of the palmitic acid component and the stearic acid. It is preferable that the total of the area (Ss) of the acid component is 80% or more in the total aliphatic carboxylic acid component, and the area ratio (Ss / Sp) of both is 1.3 to 30. The method for measuring the area ratio (Ss / Sp) is as described above.

  The C component, D component, E component, and F component are the same as those in the first embodiment. Furthermore, the ratio of the B-2 component to the F component to the A component is the same as that in the first embodiment.

(Molding)
The molded article comprising the polycarbonate resin composition of the first or second aspect of the present invention can be usually obtained by injection molding the pellet. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat insulation Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Moreover, according to this invention, a polycarbonate resin composition can be extrusion-molded and it can also be made into shapes, such as various profile extrusion molded articles, a sheet | seat, and a film. 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.

(surface treatment)
Further, the molded article of the present invention can be subjected to various surface treatments. As the surface treatment, various surface treatments such as a hard coat, a water / oil repellent coat, a hydrophilic coat, an antistatic coat, an ultraviolet absorption coat, an infrared absorption coat, and metalizing (evaporation) can be performed. Examples of the surface treatment method include liquid deposition, vapor deposition, thermal spraying, and plating. As the vapor deposition method, either a physical vapor deposition method or a chemical vapor deposition method can be used. 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.

  The molded article of the present invention is very suitable for performing such surface treatment because its crack resistance is improved. In particular, the polycarbonate resin composition of the present invention is suitable for surface treatment including a factor that adversely affects the polycarbonate resin such as a solvent, and particularly suitable for a hard coat.

  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 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 containing compounds corresponding to tetrafunctional siloxane units (tetraalkoxysilane compounds, etc.), and partially hydrolyzed condensates further 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 alcohols 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 hard coat agents, silicone resin hard coat agents with excellent long-term durability and relatively high surface hardness, or UV curable acrylics that can be processed with a relatively simple and good hard coat layer. A resin or a polyfunctional acrylic resin is preferred. The silicone resin hard coat agent can be selected from a so-called two-coat type composed of a primer layer and a top layer and a so-called one-coat type formed from only one layer.

  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.

  Furthermore, the resin that forms the hard coat layer includes the above-mentioned light stabilizer and ultraviolet absorber, catalyst, thermal / photopolymerization initiator, polymerization inhibitor, silicone antifoaming agent, leveling agent, thickener, precipitation prevention. Agents, sag-preventing agents, flame retardants, various additives of organic / inorganic pigments / dyes, and auxiliary additives can be included.

  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 suitable for various transparent members that require high quality because it is excellent in transparency, hue, releasability, weather resistance, and crack resistance. Examples of such transparent members include various vehicle transparent members (head lamp lenses, winker lamp lenses, tail lamp lenses, resin window glass, meter covers, etc.), illumination lamp covers, resin window glasses (for construction, etc.), solar cell covers, Examples include solar cell substrates, lenses for display devices, touch panels, and parts for game machines (such as pachinko machines) (front covers, circuit covers, chassis, pachinko ball conveyance guides, and the like). Furthermore, among these, a molded article that is subjected to a hard coat treatment is particularly suitable for the polycarbonate resin composition of the present invention.

  That is, according to the present invention, there is provided a molded product of the resin composition comprising the above predetermined amounts of the A to F components of the present invention, and more preferably, a molded product having a hard coat treatment on the surface thereof.

  More preferably, among these, there is a high demand for quality as described above, and a transparent member for a vehicle that is a large molded article is preferably mentioned. In particular, a vehicle lamp lens such as a headlamp lens, more specifically, a transparent headlamp. A lens is preferably used. Here, the through-type headlamp lens includes a lamp cover that performs a condensing function with a reflector, a lamp unit cover that has the lamp unit as an integral unit, and the like. Thus, the vehicular lamp lens referred to in the present invention may be a transparent member through which light from a light source that functions as a vehicular lamp, particularly a headlamp, passes, and the lens may be disposed at any position on the vehicle. Any shape may be used. For example, a rod-like lens that transmits light in the longitudinal direction is also included.

  As described above, the polycarbonate resin composition of the present invention is useful for various applications such as various electronic / electrical equipment, OA equipment, vehicle parts, machine parts, other agricultural materials, transport containers, playground equipment, miscellaneous goods, and the like. The above effect is exceptional.

  The form of the present invention considered to be the best by the present inventors 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.

The following examples further illustrate the present invention. Evaluation was carried out by the following method.
(I) Evaluation method of fatty acid ester (1) Acid value of fatty acid ester The acid value (KOHmg / g) was determined by neutralization titration in accordance with JIS K 0070.

(2) 5% weight reduction temperature by thermogravimetric measurement of fatty acid ester Using Hi-Res TGA2950 Thermographic Analyzer manufactured by TA-instruments, the temperature was increased at 20 ° C./min under N2 atmosphere, and the weight of the sample was charged. The temperature when 5 wt% of TGA was measured as the TGA 5 wt% weight loss temperature.

(3) Measurement of limit stress of polycarbonate resin with respect to release agent Polycarbonate resin sheet having a viscosity average molecular weight of 24,500 which is produced by extrusion molding having a thickness of 1 mm, a width of 40 mm and a length of 120 mm and which is not stretched (flexural modulus) Eb = 2,040 MPa) was measured for limit strain using a quarter ellipse instrument shown in FIG.

A polycarbonate resin sheet was attached to the instrument, fixed with a pressing metal fitting along an elliptical curved surface, and a release agent previously melted was applied to the sheet surface. Thereafter, the temperature was maintained at 120 ° C. for 24 hours, and the distance X (cm) to the crack generation limit point was measured. Using this distance X, the strain ε of the polycarbonate resin sheet was calculated. Table 1 shows the properties of the fatty acid esters other than the B-1 component and the B-1 component and the results of this critical strain.
^{ε = 0.02 × (1-0.0084X 2)} -3/2 t
t: Polycarbonate resin sheet thickness 0.1 (cm)
X: Distance from the center of the ellipse to the crack initiation limit point (cm)
Therefore, the strain ε can be obtained from the following equation.
^{ε = 0.02 × (1-0.0084X 2)} -3/2 × 10 -3
The critical strain at the crack initiation limit point was determined by the following formula.
Limit strain (MPa) = ε × Eb
Eb: Flexural modulus (MPa) of polycarbonate resin

(4) GC / MS measurement area ratio of aliphatic carboxylic acid component (Ss / Sp)
The measurement by the pyrolysis methylation GC / MS method of the aliphatic carboxylic acid component of the fatty acid ester was carried out by the following procedure.

  The GC / MS apparatus used was a GC: HP6890 type and MS: HP5973 type (both manufactured by Hewlett-Packard), and the thermal decomposition apparatus used was JHP-3 (manufactured by Nippon Analytical Industries).

  A solution in which the sample was dissolved in chloroform was weighed, and then about 20 μg of the sample was weighed on a pyrofoil for thermal decomposition equipment (“F358” (for 358 ° C.) manufactured by Nihon Analytical Industries). Furthermore, after adding 10 μl of a 2.5 wt% methanol solution of tetramethylammonium hydroxide (TMAH) as a reaction reagent to such a sample, the solvent was removed by heating to about 60 ° C., and then 358 ° C. using the above thermal decomposition apparatus. The reaction pyrolysis was carried out under the conditions of 10 seconds.

  The conditions for the GC / MS measurement were as follows. The column was a capillary type DB-5MS (30 m × 0.25 mm × 0.25 μm, manufactured by J & W), and helium gas was used as the carrier gas. The carrier gas was set to a constant value of 72.4 KPa (10.5 psi) using the constant pressure mode, and the (initial) gas flow rate at 40 ° C. was set to 1.3 ml / min. Further, the split ratio was 50/1, the inlet temperature was 300 ° C., and the GC / MS connection temperature was 280 ° C. The column bath temperature was maintained at 40 ° C. for 5 minutes, then heated to 320 ° C. at a temperature increase rate of 20 ° C./min, and further held at 320 ° C. for 5 minutes for measurement. Moreover, the MS apparatus used the electron impact ionization (EI) mode as an ionization mode, and measured in mass / charge number (m / z): 20-500. The number of scans per second was about 3. Further, the ion acceleration voltage and the like were set by auto-tuning using a standard sample of PFTBA. From the above measurement, the total ratio of Ss and Sp in the total aliphatic carboxylic acid component and the area ratio (Ss / Sp) were calculated.

(II) Evaluation method of resin composition The following (5)-(12) evaluation was implemented regarding the resin composition manufactured by the method mentioned later.

(5) ¹ H-NMR measurement (Ff: Fe)
From the pellets prepared in each example by the method described later, a 35 mg sample is weighed, the sample is dissolved in 0.5 ml of deuterated chloroform, and the resulting solution is placed in an ampule tube for ¹ H-NMR measurement. Thus, a sample for ¹ H-NMR measurement was prepared. The measurement sample was subjected to ¹ H-NMR measurement using an NMR measurement apparatus (JNM-alpha600, manufactured by JEOL Ltd.) 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 = (Sc / 2-Se / 2) :( Se / 2)
From the relationship, Ff: Fe was calculated (converted so that the sum of Ff and Fe was 100).

(6) Transparency of molded product Using Nippon Denshoku Co., Ltd. haze meter NDH-300A, the total light transmittance and Haze of the molded plate of thickness 2.0mm were measured. The higher the numerical value of the total light transmittance, the higher the transparency. Haze is the turbidity of the molded product. The lower the value, the less turbidity.

(7) Weather resistance Sunshine weather using a 50 mm square plate with a thickness of 2 mm in a molding cycle of 60 seconds on an injection molding machine with a maximum mold clamping force of 150 Ton and a cylinder temperature of 340 ° C. and a mold temperature of 80 ° C. -Using a meter (Suga Test Instruments Co., Ltd .: WEL-SUN: HC-B), the black panel temperature was 63 ° C, the humidity was 50%, water sprayed for 18 minutes and sprayed for 102 minutes for a total of 120 minutes for 1000 hours. The difference between the subsequent hue (YI) and the hue before processing (YI) is indicated as ΔYI.
YI = [100− (1.28X−1.06Z)] / Y
ΔYI = YI after treatment-YI before treatment

(8) Molding heat resistance A 2mm-thick 50mm square plate molded in a molding cycle of 60 seconds on a cylinder temperature of 340 ° C and a mold temperature of 80 ° C on an injection molding machine with a maximum clamping force of 150 Ton. The difference between the hue of the square plate and the hue of the molded product molded after being retained in the cylinder for 10 minutes at a cylinder temperature of 340 ° C. is obtained as ΔE from the following equation using Z-101DP manufactured by Nippon Denshoku Co., Ltd. Indicated.
ΔE = ((L−L ′) ² + (aa ′) ² + (bb ′) ² ) ^1/2
(In the above, the (L, a, b) value represents the hue before residence, and the (L ′, a ′, b ′) value represents the hue after residence)

(9) Measurement of releasability Using an injection molding machine with a maximum clamping force of 75 Ton, a cup-shaped molded product of 70 mmφ x 20 mm and 4 mm thickness is molded under conditions of a cylinder temperature of 300 ° C, a mold temperature of 80 ° C, and an injection pressure of 118 MPa. The projecting load applied to the projecting pin was measured, and the average value obtained by molding 30 shots was shown as the release load.

(10) Designability (fluorescence development)
The head lamp of the automobile shown in FIG. 1 was created, and an HID lamp (HID Handy Light Pro; white metal halide lamp: manufactured by Matsushita Electric Works Co., Ltd.) was used, and 30 cm from the downward direction (concave surface) of the 1-B drawing. When irradiating at a distance, visually observed from an angle of 45 °, “○” indicates that the outer periphery of the lens is bluish due to fluorescence, “×” indicates that no color is generated, and the entire lamp is A case where the color was developed and the irradiation light was slightly bluish was evaluated by confirming “Δ”.

(11) Stress crack test 1000 shots of cup-shaped molded products were continuously molded under the same conditions as the measurement of releasability.

(12) Strain measurement of molded product Using a square plate created by a molding heat resistance test, the strain state of the molded product was visually confirmed by a polarizing plate (as for visual judgment, Comparative Example 3 was set as x, and improved) △ and ○).

[Examples 1-7, Comparative Examples 1-5]
In 100 parts by weight of a polycarbonate resin produced from bisphenol A and phosgene by an interfacial polycondensation method, various additives shown in Table 2 were added in various amounts, and further a blueing agent (manufactured by Bayer: Macrolex Violet B) was added to 0.1 parts. After mixing 0005 parts by weight and mixing with a blender, the mixture was melt-kneaded using a vented twin screw extruder to obtain pellets. The additives to be added to the polycarbonate resin were preliminarily prepared with a polycarbonate resin in advance with a concentration of 10 to 100 times the blending amount as a guide, and then the whole was mixed by a blender. The vent type twin screw extruder used was TEX30α (completely meshing, rotating in the same direction, two-thread screw) manufactured by Nippon Steel Works. The kneading zone was of one type before the vent opening. The extrusion conditions were a discharge rate of 30 kg / h, a screw rotation speed of 150 rpm, and a vent vacuum of 3 kPa, and the extrusion temperature was 280 ° C. from the first supply port to the die part.

  The obtained pellets were dried in a hot air circulation dryer at 120 ° C. for 5 hours, and then, using an injection molding machine, the cylinder temperature was 340 ° C. and the mold temperature was 80 ° C. A square plate was formed. As the injection molding machine, T-150D manufactured by FANUC CORPORATION was used. The evaluation results of the obtained molded plate are shown in Table 2.

  Also, the pellets obtained in the examples were dried in the same manner, and then the through-type headlamp lens shown in FIG. 2 was injected into an injection molding machine (Sumitomo Heavy Industries) under conditions of a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C. It was created using SG260M-HP manufactured by Kogyo Co., Ltd. This headlamp lens had good appearance such as hue and transparency.

  The headlamp lens was annealed at 120 ° C. for 5 hours, and then the coating composition (i-1) shown below was applied by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then at 120 ° C. for 30 minutes. Heat cured. Next, the coating composition (ii-1) shown below is further applied to the lens molded article by a dip coating method, left to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 2 hours to perform a hard coat treatment. It was. In the obtained headlamp lens, when the distortion inside the molded product was observed in the same manner as described above, no abnormality such as occurrence of cracks was observed.

The fatty acid esters and other additives represented by symbols in Table 2 are as follows.
(A component)
PC: Polycarbonate resin powder having a viscosity average molecular weight of 22,500 produced from bisphenol A and phosgene by an interfacial condensation polymerization method (manufactured by Teijin Chemicals Ltd .: Panlite L-1225WP)
(Other than B-1 component and B-1 component)
b-1: Full ester of pentaerythritol and aliphatic carboxylic acid (manufactured by Riken Vitamin Co., Ltd .: Riquester EW-400)
b-2: Full ester of pentaerythritol and aliphatic carboxylic acid (manufactured by Cognis Japan Co., Ltd .: Roxyol VPG-861)
b-3: Full ester of pentaerythritol and an aliphatic carboxylic acid (mainly stearic acid and palmitic acid) (manufactured by Riken Vitamin Co., Ltd .: Riquester EW-440A)
b-4: Stearin monostearate (Riken Vitamin Co., Ltd .: Riquemar S-100A)
b-5: 95 parts by weight of the above b-2: a commercially available fatty acid full ester and a reagent aliphatic carboxylic acid are mixed, and stearic acid (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) 2.5 parts by weight And 2.5 parts by weight of palmitic acid (made by Wako Pure Chemical Industries, Ltd., special grade reagent) and mixed and homogenized by an electric blender (Brown) fatty acid ester

(C component)
C-1: Benzotriazole-based ultraviolet absorber (Kemipro Kasei Co., Ltd .: Chemisorb 79)
C-2: Triazine-based UV absorber (Ciba Specialty Chemicals: Tinuvin 1577)
(D component)
D-1: Coumarin-based fluorescent whitening agent (manufactured by Hakkol Chemical: Hakkol PSR)
(E component)
E-1: Phosphonite heat stabilizer (manufactured by Sandoz: Sandstub P-EPQ)
E-2: Phosphite heat stabilizer (Ciba Specialty Chemicals, Inc .: Irgafos 168)
(F component)
F-1: Hindered phenol antioxidant (Ciba Specialty Chemicals: Irganox 1076)
F-2: Hindered phenol antioxidant (Ciba Specialty Chemicals: Irganox 1010)

(Composition for hard coat)
(1) Coating composition (i-1)
A flask equipped with a reflux condenser and a stirrer and purged with nitrogen was 70 parts by weight methyl methacrylate (hereinafter abbreviated as MMA), 39 parts by weight of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), azobisisobutyronitrile. 0.18 parts by weight (hereinafter abbreviated as AIBN) and 200 parts by weight of 1,2-dimethoxyethane were added, mixed and dissolved. Subsequently, it was made to react under stirring at 70 degreeC in nitrogen stream for 6 hours. The obtained reaction solution was added to n-hexane and purified by reprecipitation to obtain 90 parts by weight of a copolymer (acrylic resin (I)) having a composition ratio of MMA / HEMA of 70/30 (molar ratio). The weight average molecular weight of the copolymer was 80,000 in terms of polystyrene based on GPC measurement (column; Shodex GPCA-804, eluent: THF).

  Next, as a composition for the hard coat first layer, 8 parts of the acrylic resin (I) is 40 parts by weight of methyl ethyl ketone, 20 parts by weight of methyl isobutyl ketone, 5.2 parts by weight of ethanol, 14 parts by weight of isopropanol and 10-ethoxyethanol. Dissolve in a mixed solvent consisting of parts by weight, and then add 10 parts by weight of methyltrimethoxysilane hydrolysis condensate solution (X) to this solution, stir at 25 ° C. for 5 minutes, and add melamine resin (Mitsui Cytec to this solution). 1 part by weight of Cymel 303 manufactured by Co., Ltd. was added and stirred at 25 ° C. for 5 minutes to prepare a coating composition (i-1).

(2) Coating composition (ii-1)
Using the same apparatus as above, 142 parts by weight of methyltrimethoxysilane, 72 parts by weight of distilled water, and 20 parts by weight of acetic acid were mixed with cooling with ice water, and the mixture was stirred at 25 ° C. for 1 hour, and 116 parts by weight of isopropanol. Then, 350 parts by weight of methyltrimethoxysilane hydrolyzed condensate solution (X) was obtained. On the other hand, 208 parts by weight of tetraethoxysilane and 81 parts by weight of 0.01N hydrochloric acid were mixed with cooling with ice water, and this mixture was stirred at 25 ° C. for 3 hours, diluted with 11 parts by weight of isopropanol and hydrolyzed with tetraethoxysilane. 300 parts by weight of the product solution (Y) was obtained.

  Furthermore, as a composition for the hard coat second layer, a water-dispersed colloidal silica dispersion (Snowtex 30 solid content concentration: 30% by weight, manufactured by Nissan Chemical Industries, Ltd.) is added to 12 parts by weight of distilled water and 20 parts by weight of acetic acid. Then, 134 parts by weight of methyltrimethoxysilane was added to this dispersion while cooling in an ice-water bath. To this reaction liquid obtained by stirring this mixed liquid at 25 ° C. for 1 hour, 20 parts by weight of a tetraethoxysilane hydrolysis condensate solution (Y) and 1 part by weight of sodium acetate as a curing catalyst were added and diluted with 200 parts by weight of isopropanol. Thus, a coating composition (ii-1) was prepared.

  As is clear from the above table, the polycarbonate resin composition of the present invention is excellent in transparency and weather resistance of the molded product, releasability at the time of molding, molding heat resistance, dry heat resistance of the molded product, It can be seen that the strain is improved, the stress cracking of the molded product is greatly improved, and the design is improved. It can be seen that the mold release property, molding heat resistance, and resistance to cracking of a molded product that occurs when exposed to a poor environment after molding are not sufficiently compatible.

The schematic diagram of the jig | tool for the quarter ellipse test method for measuring the limit stress of fatty acid ester is shown. The molded article of the through-head type headlamp lens of the automobile molded in the example is shown. As shown, the lens has a dome shape. [2-A] is a front view (a figure projected on the platen surface at the time of molding. Therefore, this area is the maximum projected area), and [2-B] is a cross-sectional view taken along the line AA.

Explanation of symbols

1 Ellipse center 2 Ellipse major axis radius (10cm)
3 Ellipse minor axis radius (4cm)
4 Jig width (4cm)
5 Presser brackets (each 1 cm wide)
6 Horizontal distance from the center of the ellipse to the cracked part with the least distortion (cm)
7 Polycarbonate resin sheet 8 Cracked portion with the least amount of distortion 11 Head lamp lens body 12 Lens dome-shaped portion 13 Lens outer peripheral portion 14 Molded product gate (width 30 mm, gate portion thickness 4 mm)
15 Sprue (Gate diameter 7mmφ)
16 Lens outer diameter (220mm)
17 Lens dome diameter (200mm)
18 Lens dome height (20mm)
19 Lens molded product thickness (4mm)

Claims (13)

For 100 parts by weight of polycarbonate resin (component A) produced by the interfacial condensation polymerization method, 0.005 to 2 parts by weight of an alcohol / aliphatic carboxylic acid ester (component B-1), UV absorber (component C) 0.01 to 2 parts by weight, fluorescent brightening agent (component D) 0.0001 to 3 parts by weight, and at least one selected from a phosphorus stabilizer (E component) and a hindered phenol stabilizer (F component) A resin composition comprising 0.0001 to 1 part by weight of a stabilizer, wherein the component B-1 is (i) a 5% weight loss temperature in TGA (thermogravimetric analysis) is 250 to 360 ° C. Yes, (ii) the acid value is 4-20, and (iii) a polycarbonate resin sheet having a viscosity average molecular weight of 24,500 is used under the conditions of a treatment temperature of 120 ° C. and a treatment time of 24 hours. In quarter ellipse test method, the polycarbonate resin composition that limits the stress is not less than 15 MPa.   2. The polycarbonate resin composition according to claim 1, wherein the component B-1 is an ester of a 4 to 8 valent aliphatic polyhydric alcohol having 5 to 30 carbon atoms and an aliphatic carboxylic acid having 10 to 22 carbon atoms. .   100 parts by weight of polycarbonate resin (component A) Full ester of 4- to 8-valent aliphatic polyhydric alcohol having 5 to 30 carbon atoms and aliphatic carboxylic acid having 10 to 22 carbon atoms (component B-2) 005 to 2 parts by weight, ultraviolet absorber (C component) 0.01 to 2 parts by weight, fluorescent brightener (D component) 0.0001 to 3 parts by weight, and phosphorus stabilizer (E component) and hindered phenol A resin composition comprising 0.0001 to 1 part by weight of at least one stabilizer selected from a system stabilizer (component F), wherein the number of moles of carboxyl groups of the free aliphatic carboxylic acid in the composition (Ff ) And the molar ratio (Ff: Fe) of the number of moles of ester bonds (Fe) of the component B-2 to the range of 8:92 to 30:70.   The aliphatic carboxylic acid in the B-1 component or the B-2 component contains a palmitic acid component and a stearic acid component, and has a palmitic acid component in the peak area in gas chromatography-mass spectrometry (GC / MS method). The sum of the area (Sp) and the area (Ss) of the stearic acid component is 80% or more of the total aliphatic carboxylic acid component, and the area ratio (Ss / Sp) of both is 1.3 to 30. The polycarbonate resin composition according to any one of 1 to 3.   The polycarbonate resin composition according to any one of claims 2 to 4, wherein the aliphatic polyhydric alcohol is at least one polyhydric alcohol selected from pentaerythritol and dipentaerythritol.   The polycarbonate resin composition according to any one of claims 1 to 5, wherein the component C is at least one ultraviolet absorber selected from a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber. . The polycarbonate resin composition according to any one of claims 1 to 6, wherein the component D is a fluorescent brightener represented by the following formula (1).

(In the above formula, R ₁ represents an amino group, an alkyl group-substituted amino group, a hydroxyl group, and any one of the following formulas (2), (3) or (4), and R ₂ represents a hydrogen atom or a fluoroalkyl. And R ₃ represents a hydrogen atom, an alkyl group, or an aryl group.)

  The polycarbonate resin composition contains a filler, in which a smooth flat plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm exhibits a haze value in the range of 0.1 to 1%. The polycarbonate resin composition according to any one of claims 1 to 7.   The pellet which consists of a polycarbonate resin composition of any one of Claims 1-8.   A molded product produced by injection molding the pellet according to claim 9.   The molded article according to claim 10, wherein the molded article is hard-coated on the surface thereof.   The molded article according to claim 10 or 11, wherein the molded article is a transparent member for a vehicle.   The molded article according to claim 12, wherein the vehicle transparent member is a vehicle lamp lens.

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