JP2005298720A - Molded article for exterior use of vehicles formed from light-scattering polycarbonatre resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded article for exterior use of vehicles having adequate light shielding properties and white light transparency, particularly a large molded article for use such as roofing for vehicles, and also provide such a molded article from an aromatic polycarbonate resin composition that furnishes a combination of light weight, high rigidity and high dimensional stability, and that can solve problems related to large molded articles. <P>SOLUTION: This molded article for exterior use of vehicles is made of a light-scattering polycarbonate resin composition comprising 100 pts.wt. of an aromatic polycarbonate (component A) and 0.1-30 pts.wt. of minute polymer particles (component B) having an average particle size of 0.01-50 μm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a vehicle exterior molded article formed from a polycarbonate resin composition having light diffusibility. More specifically, it is a vehicle exterior molded article formed from a resin composition comprising an aromatic polycarbonate resin and specific polymer fine particles, and has a good hue and allows soft natural light to be taken into the vehicle interior. It relates to molded products. Preferably, the composition further comprises a layered silicate (particularly an organically modified layered silicate) and a compound having an affinity for an aromatic polycarbonate and having a hydrophilic component, thereby providing rigidity, dimensional stability and surface smoothness. The present invention relates to a vehicle exterior molded article having a relatively large area, which is excellent in performance.

  Aromatic polycarbonate resins have excellent transparency, heat resistance, mechanical strength, and the like, and are therefore widely used in electrical, mechanical, automotive, medical applications and the like. 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 vehicles include a headlamp lens, a resin window glass, a rear lamp lens, a meter cover such as a meter cover, a sunroof, a moon roof, a detachable top, a window reflector, a winker lamp lens, Examples include a room lamp lens and a member with a slightly low degree of transparency, such as a display display front plate.

  In such a transparent member for a vehicle, it may be preferable to incorporate soft natural light into the vehicle, and in such a case, an appropriate light blocking property and transmission of white light are required. For example, as a member for such a function, White Campus Top in Demio (trade name) manufactured by Mazda Motor Corporation, which is a commercial vehicle, is known. Such a campus top is made of a fibrous material, but there are cases where the same characteristics are required for a material having excellent surface smoothness and rigidity such as glass. That is, there is a need for a roofing material for vehicles, which has an appropriate light shielding property and transmission of white light, and the provision thereof has been a problem.

  On the other hand, replacement of a conventional glass member with an aromatic polycarbonate has recently become popular in order to reduce the weight of the vehicle body. Since aromatic polycarbonate is inferior in bending rigidity compared with glass, an improvement in bending elastic modulus may be required. In particular, the demand is high for an external member that receives wind pressure and is loaded during traveling. On the other hand, the improvement of the flexural modulus can reduce the thickness of the product and further reduce the weight of the member. However, the improvement due to the blending of the inorganic filler that is usually used has caused problems such as offsetting the merit of weight reduction by increasing the specific gravity, and reducing the surface smoothness so that it cannot be used in the same manner as glass. As a method for solving the disadvantages of such ordinary inorganic fillers, it has an affinity with aromatic polycarbonates, layered silicates ion-exchanged with organic onium ions, and aromatic polycarbonates such as styrene-maleic anhydride copolymers. In addition, it is known that a molded article made of a resin composition comprising a compound having a hydrophilic component and satisfying a specific total light transmittance can be applied to a transparent member for vehicles (see Patent Document 1).

  A molded product having a light diffusing function in which an aromatic polycarbonate resin is mixed with a light diffusing agent composed of inorganic fine particles or polymer fine particles includes an electric lamp cover, a meter, a signboard (especially internally illuminated), a resin window glass, an image reading device, Wide range of light diffusion plates for display devices (eg, light diffusion plates used for backlight modules such as liquid crystal display devices, light diffusion plates used for screens of projection display devices such as projector TVs) Used in the field. Such a molded product is advantageous in that it is superior in heat resistance and dimensional stability as compared with conventional acrylic resins.

  A resin composition comprising an aromatic polycarbonate, a layered silicate ion-exchanged with an organic onium ion, and a compound having a hydrophilic component and an affinity with an aromatic polycarbonate such as a styrene-maleic anhydride copolymer. Furthermore, it is known that a light diffusing agent can be further blended (see Patent Document 2). However, even in this document, further studies are necessary in order to obtain a vehicle exterior molded product for taking soft natural light into the vehicle.

JP 2004-051858 A WO03 / 010235 pamphlet

  An object of the present invention is to provide a vehicular exterior molded article having an appropriate light shielding property and white light transmission, particularly a large molded article such as a vehicle roofing material. Furthermore, it is providing the molded article which consists of an aromatic polycarbonate resin composition which has the weight reduction, high rigidity, and high dimensional stability which are a problem in a large molded article.

The present inventors diligently studied to solve this problem. Based on the above findings, it was considered easy to add an additive that satisfies the above characteristics to an aromatic polycarbonate excellent in transparency, and an additive typified by calcium carbonate particles was added. However, since roofing materials for vehicles are extremely large molded products, it has been found that poor appearance such as silver and burnt lines and uneven transmitted light often occur and good molded products cannot be obtained. On the other hand, it has been found that a large injection molded article having a projected area exceeding 10,000 cm ² can be obtained from an aromatic polycarbonate resin composition containing polymer fine particles typified by polymethylsilsesquioxane particles. Furthermore, by blending a specific layered silicate and a specific compound, a molded article having good thermal stability, rigidity and dimensional stability can be obtained without impairing the surface smoothness and without reducing light diffusibility. As a result, the present invention was completed.

  The present invention relates to a light diffusing polycarbonate resin composition comprising (1) 100 parts by weight of an aromatic polycarbonate (component A) and 0.1 to 30 parts by weight of polymer fine particles (component B) having an average particle size of 0.01 to 50 μm. The present invention relates to a vehicle exterior molded product formed from a product. According to the configuration (1), a vehicle exterior molded product having an appropriate light shielding property and white light transmission, particularly a large molded product such as a vehicle roofing material is provided.

One of the preferred embodiments of the present invention is that (2) the vehicle exterior molded product has a maximum projected area of 500 to 50,000 cm ² , wherein the vehicle exterior molding of the configuration (1) is provided. It is a product. The present invention makes it possible to provide such a large molded article. Take up projected area is preferably 5,000～40,000Cm ^2, more preferably 10,000~35,000cm ^2. Here, the maximum projected area is the maximum projected area in the molded product, and often corresponds to the projected area of the mold cavity.

  One of the preferred embodiments of the present invention is (3) the vehicle exterior molded article having the configuration (2), wherein the vehicle exterior molded article is manufactured by an injection press molding method. According to the configuration (3), a large-sized molded article such as a vehicle exterior molded article having a large size and appropriate light-shielding property and white light transmission, particularly a vehicle roofing material, is provided. In addition, the resin composition comprising the A component and the B component, and the resin composition comprising the A component to the D component, which will be described later, have preferable properties in injection press molding in terms of their melt viscoelastic properties, and better molded products. Can be obtained.

  One of preferred embodiments of the present invention is: (4) The light diffusing polycarbonate resin composition further comprises a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g based on 100 parts by weight of component A. (C component) It is an exterior molded article for vehicles of the said structure (1)-(3) which is a resin composition containing 0.1-20 weight part. In a more preferred embodiment, (5) the light diffusing polycarbonate resin composition further comprises a compound having an affinity for an aromatic polycarbonate and a hydrophilic component (D component) based on 100 parts by weight of the A component. It is a vehicle exterior molded article having the above-mentioned constitution (4) which is a resin composition. In a more preferred embodiment, the component C has a cation exchange capacity of 50 to 200 meq / 100 g, and at least 40% of the cation exchange groups are exchanged with organic onium ions. This is an exterior molded article for a vehicle having the configurations (4) to (5). A more preferred embodiment is (7) the vehicle exterior molded article having the constitution (6), wherein the organic onium ion in the component C is represented by the following general formula (I).

〔上記一般式（Ｉ）中、Ｍは窒素原子またはリン原子を表わす。また、Ｒ^１〜Ｒ^４は互いに同一もしくは相異なる有機基を表わし、その少なくとも１つは炭素原子数６〜２０のアルキル基または炭素原子数６〜１２のアリール基であり、残りの基は炭素原子数１〜５のアルキル基である。〕

[In the general formula (I), M represents a nitrogen atom or a phosphorus atom. R ^{1 to} R ⁴ represent the same or different organic groups, at least one of which is an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, and the remaining groups are carbon atoms. It is an alkyl group having 1 to 5 atoms. ]

  According to the configurations (4) to (7), an exterior molded article for a vehicle that is excellent in surface smoothness, rigidity, and dimensional stability while satisfying the light transmittance is provided.

  One of the preferred embodiments of the present invention is characterized in that (8) the component D is an aromatic vinyl polymer (component D-1) having a functional group comprising a carboxyl group and / or a derivative thereof. The vehicle exterior molded article according to any one of the configurations (5) to (7), and more preferably (9) the component (D-1) is a styrene-maleic anhydride copolymer. 8) The vehicle exterior molded product. According to the configurations (8) and (9), a vehicle exterior molded product that is more excellent in thermal stability and adaptable to an increase in size is provided.

  One of the preferred embodiments of the present invention is that (10) the resin composition comprising the A component to the D component is prepared by melt-kneading the C component and the D component in advance, and then the melt-kneaded product and the A component. And an exterior molded article for a vehicle having the constitution (5) to (9), which is prepared by melt-kneading and B component. According to the configuration (10), an exterior molded article for a vehicle that is further excellent in thermal stability and can be adapted to an increase in size and has excellent rigidity and dimensional stability is provided.

  One of the preferred embodiments of the present invention is: (11) The vehicle having the above-described configuration (1) to (10), wherein the vehicle exterior molded product is subjected to a hard coat treatment on the surface thereof. It is an exterior molded product. While it is practically preferable that the vehicle exterior molded article of the present invention is subjected to a hard coat treatment in order to impart scratch resistance and improved weather resistance, the molded article of the present invention is sufficiently hard. Applicable to coat processing. Therefore, according to the configuration (11), a vehicle exterior molded product having a more practical and appropriate light shielding property and white light transmission, particularly a large molded product such as a vehicle roofing material is provided.

Details of the present invention will be described below.
<About component A>
The aromatic polycarbonate which is the component A of the present invention is usually obtained by reacting a dihydric phenol and a carbonate precursor, and the reaction method includes an interfacial polycondensation method, a melt transesterification method, a carbonate prepolymer. Solid phase transesterification method and ring-opening polymerization method of a cyclic carbonate compound.

  Specific examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (commonly known as “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-phenylenediisopropylidene) Phenol, 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, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Is mentioned. Among these, bis (4-hydroxyphenyl) alkane, particularly bisphenol A (hereinafter sometimes abbreviated as “BPA”) is widely used.

  In the present invention, in addition to the bisphenol A polycarbonate which is a general-purpose polycarbonate, for example, a special fragrance using other dihydric phenols for the purpose of further reducing the dimensional change due to water absorption or for further improving the rigidity. It is also possible to use a group polycarbonate as the A component.

  For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Aromatic polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) Appropriate for applications where dimensional changes due to dimensional requirements and form stability are demanded. These dihydric phenols are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the aromatic polycarbonate.

In particular, when a molded product having high rigidity and low water absorption rate (and therefore small dimensional change due to water absorption) is required, it is particularly preferable that the component A is a copolymerized polycarbonate of the following (a) to (c). Is preferred.
(A) In 100 mol% of the dihydric phenol component constituting the aromatic polycarbonate, BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%), A copolymeric polycarbonate having a BCF of 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).
(B) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, further preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the aromatic polycarbonate, A copolymer polycarbonate having a BCF content of 5 to 90 mol% (more preferably 10 to 50 mol%, still more preferably 15 to 40 mol%).
(C) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the aromatic polycarbonate, Copolymer polycarbonate in which Bis-TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, and further preferably 35 to 55 mol%).

  These special aromatic polycarbonates may be used alone or in combination of two or more. These can also be used by mixing with a widely used bisphenol A-based aromatic polycarbonate.

  The production method and characteristics of these special aromatic polycarbonates are described in detail, for example, in JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. Has been described.

Of the various polycarbonates, those having a water absorption and Tg (glass transition temperature) within the following ranges by adjusting the copolymer composition and the like have good hydrolysis resistance and low warpage. Is also particularly suitable because it is remarkably superior.
(A) an aromatic polycarbonate having a Tg of 120 to 180 ° C. and a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13%, or
(B) Tg is 160 to 250 ° C., preferably 170 to 230 ° C., and water absorption is 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to Aromatic polycarbonate that is 0.27%.

  Here, the water absorption of the aromatic polycarbonate was measured by using a disk-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm, and immersing it in water at 23 ° C. for 24 hours in accordance with ISO 62-1980. Value. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

  Further, as the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, or the like can be mentioned.

  In producing a polycarbonate from the dihydric phenol and the carbonate precursor by an interfacial polymerization method, if necessary, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, etc. May be used.

Moreover, the aromatic polycarbonate used as A component which comprises this invention resin composition may be the branched polycarbonate which copolymerized the polyfunctional aromatic compound more than trifunctional. Examples of the trifunctional or higher polyfunctional aromatic compound include 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, and the like. Can be used. When the polyfunctional compound which produces a branched structure is included, the proportion thereof is 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, particularly preferably 0.01 to 0, based on the total amount of the aromatic polycarbonate. 0.8 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The ratio of the branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0, in the total amount of the aromatic polycarbonate. It is preferable that the content is 0.9 mol%, particularly preferably 0.01 to 0.8 mol%. In addition, the ratio of the branched structure amount in the aromatic polycarbonate can be calculated by ¹ H-NMR measurement.

  Furthermore, the functional carboxyl is added to a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, and a copolymer polycarbonate obtained by copolymerizing a bifunctional alcohol (including alicyclic). Polyester carbonate obtained by copolymerizing an acid and a bifunctional alcohol may be used. The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include, for example, sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and other linear saturated aliphatic dicarboxylic acids, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as acids. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol. In the present invention, it is also possible to use a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units.

  Component A (aromatic polycarbonate) in the resin composition of the present invention includes various aromatic polycarbonates such as polycarbonates having different dihydric phenol components, polycarbonates containing branched components, polyester carbonates, and polycarbonate-polyorganosiloxane copolymers. Two or more kinds may be mixed. Also, two or more kinds of polycarbonates having different production methods, polycarbonates having different end terminators, and the like can be mixed and used.

  The reaction by the interfacial polycondensation method in the production of the aromatic polycarbonate 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, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound can be used. . At that time, it is preferable that the reaction temperature is usually 0 to 40 ° C., the reaction time is about 10 minutes to 5 hours, and the pH during the reaction is kept at 9 or more.

  In this polymerization reaction, a terminal terminator is usually used. Monofunctional phenols can be used as such end terminators. As specific examples of monofunctional phenols, for example, monofunctional phenols such as phenol, p-tert-butylphenol, and p-cumylphenol are preferably used. Furthermore, examples of monofunctional phenols include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol, and the like. Such end terminators may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the alcohol or phenol produced by mixing the dihydric phenol and the carbonate ester with heating in the presence of an inert gas. Is carried out by distilling the water. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the reaction system is reduced in pressure to about 1.33 × 10 ^{3 to} 13.3 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

  Examples of the carbonate ester include esters such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms which may have a substituent, and among them, diphenyl carbonate is preferable.

A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt of dihydric phenol, potassium salt; alkaline earth metal compounds such as calcium hydroxide, barium hydroxide, magnesium hydroxide; Various catalysts such as nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, and triethylamine can be used. In addition, alkali (earth) metal alkoxides, alkali (earth) metal organic acid salts, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds, etc. The catalyst used for the exchange reaction can be used. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is preferably selected in the range of 1 × 10 ⁻⁹ to 1 × 10 ⁻⁵ equivalent, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ equivalent, relative to 1 mol of dihydric phenol as a raw material. It is.

  In the reaction by the melt transesterification method, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate, 2-ethoxycarbonyl is used at the later stage or after completion of the polycondensation reaction for the purpose of reducing the phenolic end groups of the produced polymer. Compounds such as phenylphenyl carbonate can be added.

  Furthermore, 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. Moreover, 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 polycarbonate after polymerization. Preferred examples of the deactivator include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.

  The viscosity average molecular weight of the aromatic polycarbonate is not limited. However, when the viscosity average molecular weight is less than 10,000, the strength of the molded product is lowered, and when it exceeds 50,000, the molding process characteristics are lowered. Therefore, the range of 10,000 to 50,000 is preferable. The range of 12,000 to 30,000 is more preferable, and the range of 14,000 to 28,000 is more preferable.

  The viscosity average molecular weight may be satisfied as the whole component A, and includes those satisfying such a range by a mixture of two or more kinds having different molecular weights. In particular, mixing of an aromatic polycarbonate having a viscosity average molecular weight exceeding 50,000 (more preferably 80,000 or more, more preferably 100,000 or more) may be advantageous in terms of increasing entropy elasticity at the time of melting. For example, it is effective in suppressing hesitation in injection press molding. Therefore, the mixing of aromatic polycarbonates having a viscosity average molecular weight exceeding 50,000 is one of the preferred choices when these improvements are required and when these molding methods are applied. Such an effect becomes more prominent as the molecular weight of the aromatic polycarbonate is higher, but the upper limit of the molecular weight is practically 2 million, preferably 300,000, more preferably 200,000.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of aromatic polycarbonate in 100 ml of methylene chloride at 20 ° C. with a specific viscosity (η _SP ) calculated by the following formula. ,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is determined by inserting the determined specific viscosity (η _SP ) according to 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

In addition, when measuring the viscosity average molecular weight in the resin composition of this invention, it carries out in the following way. That is, the composition is dissolved in 20 to 30 times its weight of methylene chloride, and the soluble component is collected by Celite filtration, and then the solution is removed and dried sufficiently to obtain a solid component of methylene chloride soluble component. . From a solution obtained by dissolving 0.7 g of this solid in 100 ml of methylene chloride, the specific viscosity (η _SP ) at 20 ° C. is obtained using an Ostwald viscometer, and the viscosity average molecular weight M is calculated by the above formula.

<About B component>
The B component of the present invention is polymer fine particles having an average particle size of 0.01 to 50 μm. The average particle size is preferably in the range of 0.1 to 10 μm, more preferably in the range of 0.1 to 8 μm. The average particle diameter is represented by a 50% value (D ₅₀ ) of the cumulative distribution of particle sizes obtained by the laser diffraction / scattering method. Further, a narrow particle size distribution is preferable, and a particle having an average particle size of ± 2 μm has a distribution of 70% by weight or more of the total particle size.

  The refractive index of the polymer fine particles is preferably 1.33 to 1.7, more preferably 1.35 to 1.67. In order to obtain a good hue, the refractive index is preferably lower than that of the A component aromatic polycarbonate. Therefore, the refractive index of the D component is more preferably 1.35 to 1.55, and still more preferably 1.35 to 1.45.

  The shape of the polymer fine particles is preferably close to a sphere from the viewpoint of light diffusibility, and more preferably a shape close to a true sphere. Such a sphere includes an elliptical sphere. Furthermore, examples of the polymer fine particles include organic crosslinked particles obtained by polymerizing a non-crosslinkable monomer and a crosslinkable monomer. Examples of non-crosslinkable monomers include non-crosslinkable vinyl monomers such as acrylic monomers, styrene monomers, and acrylonitrile monomers, and olefin monomers. These can be used alone or in admixture of two or more. Furthermore, other copolymerizable monomers other than such monomers can also be used. Examples of the other organic crosslinked particles include silicone-based crosslinked particles. On the other hand, amorphous heat-resistant polymer particles such as polyethersulfone particles can also be cited as the polymer fine particles of the present invention. In the case of such polymer particles, the form of the fine particles is not impaired even when heated and melt-kneaded with the component A, so that a crosslinkable monomer is not necessarily required. Furthermore, as the polymer fine particles of the present invention, various epoxy resin particles, urethane resin particles, melamine resin particles, benzoguanamine resin particles, phenol resin particles, and the like can be used.

  Among the light diffusing agents composed of polymer fine particles used as the component B, organic crosslinked particles can be suitably used from the viewpoint of heat resistance. A more preferable B component is a silicone-based crosslinked particle represented by polymethylsilsesquioxane from the viewpoint of its hue.

  Examples of the acrylic monomer used as the non-crosslinkable vinyl monomer in the organic crosslinked particles include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate. , 2-ethylhexyl methacrylate, phenyl methacrylate and the like can be used alone or in combination. Of these, methyl methacrylate is particularly preferable. As the styrene monomer, styrene, α-methyl styrene, methyl styrene (vinyl toluene), alkyl styrene such as ethyl styrene, and halogenated styrene such as brominated styrene can be used, and styrene is particularly preferable. As the acrylonitrile monomer, acrylonitrile or methacrylonitrile can be used. Moreover, ethylene, various norbornene-type compounds, etc. can be used as an olefin monomer. Furthermore, glycidyl methacrylate, N-methylmaleimide, maleic anhydride, and the like can be exemplified as other copolymerizable monomers, and as a result, units such as N-methylglutarimide can be included.

  On the other hand, examples of the crosslinkable monomer for the non-crosslinkable vinyl monomer include divinylbenzene, allyl methacrylate, triallyl cyanurate, triallyl isocyanate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and propylene glycol. (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane (meth) acrylate, pentaerythritol tetra (meth) acrylate, bisphenol A di (meth) acrylate, dicyclopentanyl di (meth) acrylate , Dicyclopentenyl di (meth) acrylate, N-methylol (meth) acrylamide and the like.

  As a method for producing organic crosslinked particles composed of acrylic monomers, etc., a general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, a two-stage swelling polymerization method, etc. Can be mentioned. Also in the suspension polymerization method, the water phase and the monomer phase are separately maintained and both are accurately supplied to a continuous disperser, and the particle diameter is controlled by the number of revolutions of the disperser. In the continuous production method, a method in which the monomer phase is supplied by passing it through a small diameter orifice of several to several tens of μm or a porous filter in an aqueous liquid having dispersibility, and the particle size can be controlled.

  On the other hand, silicone-based crosslinked particles are those having a siloxane bond as the main skeleton and an organic substituent on the silicon atom, and those having a high degree of crosslinking represented by polymethylsilsesquioxane and those represented by methylsilicone rubber particles. In the present invention, those having a high degree of crosslinking such as polymethylsilsesquioxane are preferred. Examples of the organic group substituted on the silicon atom of the silicone-based crosslinked particles include alkane groups such as a methyl group, ethyl group, propyl group, and butyl group, aryl groups such as a phenyl group, aralkyl groups such as a benzyl group, and the like. A group, a carbonyl group, an ester group, an ether group or the like can be used.

  As a method for producing such silicone-based crosslinked particles, there is generally used a method of forming three-dimensionally crosslinked particles while growing siloxane bonds by hydrolysis and condensation reaction of trifunctional alkoxysilane or the like in water. The diameter can be controlled by the alkali amount of the catalyst, the stirring step, and the like.

  Moreover, as a manufacturing method of polymer fine particles other than the organic crosslinked particles, spray drying method, submerged curing method (coagulation method), phase separation method (coacervation method), solvent evaporation method, reprecipitation method, etc., A combination of the nozzle vibration method and the like when performing these can be mentioned.

  As the form of the B component polymer fine particles, in addition to the single-phase polymer, it is also possible to take the form of a core-shell polymer or an IPN structure in which two or more components are intertwined with each other. In addition, composite particles using inorganic fine particle cores and organic cross-linked particle components as shells, or composite particles using organic cross-linked particles as cores and epoxy resin, urethane resin, etc. as shells can also be used.

<About component C>
The C component of the present invention is a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g. Preferably, a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g, and 40% or more, particularly 50 to 100%, of the cation exchange capacity is ion-exchanged with an organic onium ion. (Hereinafter, this layered silicate may be abbreviated as “organized layered silicate”).

The layered silicate of component C consists of a layer composed of a combination of a SiO ₄ tetrahedral sheet structure composed of SiO ₂ chains and an octahedral sheet structure containing Al, Mg, Li, etc., and exchangeable cations are arranged between the layers. Silicate (silicate) or clay mineral (clay). These silicates (silicates) or clay minerals (clays) are typified by smectite minerals, vermiculite, halloysite, and swellable mica. Specifically, examples of the smectite mineral include montmorillonite, hectorite, fluorine hectorite, saponite, beidellite, and stevensite. Examples of the swellable mica include Li-type fluorine teniolite, Na-type fluorine teniolite, and Na-type tetrasilicon. Examples include swellable synthetic mica such as fluorine mica and Li-type tetrasilicon fluorine mica. These layered silicates can be either natural products or synthetic products. The synthetic product is produced by, for example, hydrothermal synthesis, melt synthesis, or solid reaction.

  Among the layered silicates, from the viewpoint of cation exchange capacity, etc., smectite clay minerals such as montmorillonite and hectorite, Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica have swelling properties. Fluorine mica is preferably used, and montmorillonite obtained by purifying bentonite and synthetic fluorine mica are more preferable in terms of purity and the like. Among these, synthetic fluorine mica that can provide good mechanical properties is particularly preferable.

The cation exchange capacity (also referred to as cation exchange capacity) of the layered silicate is required to be 50 to 200 meq / 100 g, preferably 80 to 150 meq / 100 g, more preferably 100 to 150 mm. Equivalent / 100 g. The cation exchange capacity is measured as a CEC value by the modified Schöllenberger method, which is a domestic official method as a soil standard analysis method. The outline of this method is as follows. Fill the infiltration tube of a soil leaching device with a length of 12 cm and an inner diameter of 1.3 cm with a layered silicate sample to a thickness of about 8 cm, and use 100 ml of 1N aqueous ammonium acetate solution with a pH of 7 for infiltration over 4-20 hours. And leaching exchange cations. It is then washed with 100 ml of 80% methanol at pH 7 to remove excess ammonium acetate. Next, the sample is washed with 100 ml of a 10% aqueous potassium chloride solution, and ammonium ions (NH ₄ ⁺ ) adsorbed on the sample are exchanged and leached. Finally, NH ₄ ⁺ in the leachate is quantified by steam distillation or Conway microdiffusion, and CEC is calculated. What is marketed as a glass set can be used for the soil leaching device. The Schoenberger method, which is the basis of the improved method, is referred to in Soil Sci., 59, 13-24 (1945).

  The cation exchange capacity of the layered silicate needs to be 50 meq / 100 g or more in order to obtain good dispersibility in the aromatic polycarbonate as the component A, but when it exceeds 200 meq / 100 g, the aromatic polycarbonate It is easy to heat deterioration of. The layered silicate preferably has a pH value of 7 to 11.5. When pH value becomes larger than 11.5, the tendency for the thermal stability of the aromatic polycarbonate resin composition of this invention to fall will appear.

  As the layered silicate of component B, an organic onium ion obtained by ion exchange between layers of the layered silicate (organized layered silicate) is preferable. The organic onium ion is usually handled as a salt with a halogen ion or the like. The organic onium ion is introduced into the layered silicate by reacting the salt compound of the organic onium ion with the layered silicate. Examples of organic onium ions include ammonium ions, phosphonium ions, sulfonium ions, onium ions derived from heteroaromatic rings, and the like. Any of primary, secondary, tertiary and quaternary ions can be used, but quaternary onium ions are preferred, and quaternary ammonium ions and quaternary phosphonium ions are preferred as onium ions.

  As the ionic compound, those having various organic groups bonded thereto can be used. The organic group is typically an alkyl group, but may have an aromatic group, and may be an ether group, an ester group, a double bond portion, a triple bond portion, a glycidyl group, a carboxylic acid group, an acid anhydride, or the like. It may contain various functional groups such as a physical group, a hydroxyl group, an amino group, an amide group, and an oxazoline group.

  Specific examples of organic onium ions include quaternary ammonium having the same alkyl group such as tetraethylammonium and tetrabutylammonium; trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethyltetradecylammonium, trimethylhexadecylammonium, trimethyl Trimethylalkylammoniums such as octadecylammonium and trimethylicosanylammonium; trimethylalkenylammoniums such as trimethyloctadecenylammonium; trimethylalkadienylammoniums such as trimethyloctadecadienylammonium; triethyldodecylammonium, triethyltetradecylammonium and triethyl Hexadecyl ammoniu Triethylalkylammonium such as triethyloctadecylammonium; tributylalkylammonium such as tributyldodecylammonium, tributyltetradecylammonium, tributylhexadecylammonium, tributyloctadecylammonium; dimethyldioctylammonium, dimethyldidecylammonium, dimethylditetradecylammonium, dimethyldi Dimethyldialkylammonium such as hexadecylammonium and dimethyldioctadecylammonium; dimethyldialkenylammonium such as dimethyldioctadecenylammonium; dimethyldialkadienylammonium such as dimethyldioctadecadienylammonium; diethyldidodecylammonium and diethyldi Tetra Diethyldialkylammonium such as silammonium, diethyldihexadecylammonium, diethyldioctadecylammonium; dibutyldialkylammonium such as dibutyldidodecylammonium, dibutylditetradecylammonium, dibutyldihexadecylammonium, dibutyldioctadecylammonium; trioctylmethylammonium Trialkylmethylammonium such as tridodecylmethylammonium and tritetradecylmethylammonium; trialkylethylammonium such as trioctylethylammonium and tridodecylethylammonium; trialkylbutylammonium such as trioctylbutylammonium and tridecylbutylammonium Can be mentioned.

  Examples thereof include methylbenzyl dialkylammonium such as methylbenzyldihexadecylammonium; quaternary ammonium having an aromatic ring such as dibenzyldialkylammonium such as dibenzyldihexadecylammonium and trimethylbenzylammonium. Further, quaternary ammoniums derived from aromatic amines such as trimethylphenylammonium; trialkyl [PAG] ammoniums such as methyldiethyl [PEG] ammonium and methyldiethyl [PPG]; dialkylbis [PAGs such as methyldimethylbis [PEG] ammonium. Ammonium; alkyltris [PAG] ammonium such as ethyltris [PEG] ammonium. Moreover, the phosphonium ion which substituted the nitrogen atom of the said ammonium ion by the phosphorus atom can also be used.

  These organic onium ions can be used either alone or in combination of two or more. The notation of “PEG” indicates polyethylene glycol, the notation of “PPG” indicates polypropylene glycol, and the notation of “PAG” indicates polyalkylene glycol. The molecular weight of the polyalkylene glycol can be 100 to 1,500.

  The molecular weight of these organic onium ion compounds is preferably 100 to 600. More preferably, it is 150-500. When the molecular weight is more than 600, there is a tendency that the thermal degradation of the aromatic polycarbonate or the heat resistance of the resin composition is impaired in some cases. The molecular weight of the organic onium ion refers to the molecular weight of a single organic onium ion that does not include counter ions such as halogen ions.

  In this invention, the suitable aspect of C component is what was ion-exchanged with the organic onium ion shown by the following general formula (I).

In the general formula (I), M represents a nitrogen atom or a phosphorus atom. R ^{1 to} R ⁴ represent the same or different organic groups, at least one of which is an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, and the remaining groups are carbon atoms. It is an alkyl group having 1 to 5 atoms. As long as these R ^{1 to} R ⁴ satisfy the above conditions, a part of them may be the same group, or a part or all of them may be different from each other.

A more preferable embodiment of the organic onium ion used in the component C of the present invention satisfies the following condition in the general formula (I). That is, M is a nitrogen atom or a phosphorus atom, and R ¹ and R ² are each an alkyl group having 6 to 16 carbon atoms. R ³ is an alkyl group having 1 to 16 carbon atoms, and R ⁴ is an alkyl group having 1 to 4 carbon atoms. R ¹ and R ² may be the same or different from each other, and R ³ and R ⁴ may be the same or different from each other. Good.

A more preferred embodiment of the organic onium ion represented by the general formula (I) is when (i) R ³ is an alkyl group having 1 to 4 carbon atoms. More preferably, (ii) R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² are each an alkyl group having 7 to 14 carbon atoms. More preferably, (iii) R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² are 7 to 12 carbon atoms, particularly preferably 8 to 11 carbon atoms. This is the case with an alkyl group. Of these, R ³ and R ⁴ are particularly preferably alkyl groups having 1 to 3 carbon atoms, more preferably methyl groups or ethyl groups, and even more preferably quaternary ammonium ions of methyl groups.

  According to these more preferable embodiments (including further preferable embodiments) of (i) to (iii), the hydrolysis resistance of the resin composition is particularly excellent, which is favorable for the vehicle exterior molded article of the present invention. Gives long-term practical characteristics.

In the above formula (I), R ^{1 to} R ⁴ can be either linear or branched.

  Examples of such suitable quaternary ammonium ions include dimethyl dioctyl ammonium, dimethyl didecyl ammonium, dimethyl didodecyl ammonium, dimethyl ditetradecyl ammonium, dimethyl dihexadecyl ammonium, diethyl didodecyl ammonium, diethyl ditetradecyl ammonium, diethyl Examples include dihexadecyl ammonium, dibutyl dioctyl ammonium, dibutyl didecyl ammonium, dibutyl didodecyl ammonium and the like.

  Ion exchange of organic onium ions into layered silicate can be made by adding an organic onium ion compound to layered silicate dispersed in a polar solvent and collecting the precipitated ion exchange compound. . Usually, this ion exchange reaction is carried out by adding an organic onium ion compound at a ratio of 1.0 to 1.5 equivalents to 1 equivalent of the ion exchange capacity of the layered silicate, and almost all of the metal ions between the layers are added to the organic onium. It is common to exchange with ions. However, controlling the exchange rate with respect to the ion exchange capacity within a certain range is also effective in suppressing thermal degradation of the aromatic polycarbonate. Here, the ratio of ion exchange with organic onium ions is preferably 40% or more with respect to the ion exchange capacity of the layered silicate. The ratio to such ion exchange capacity is preferably 40 to 95%, particularly preferably 40 to 80%. Here, the exchange rate of the organic onium ions can be calculated by obtaining a weight reduction due to thermal decomposition of the organic onium ions using a thermogravimetric apparatus or the like for the compound after the exchange.

  In a more preferred embodiment of the organically modified layered silicate which is a preferred C component of the present invention, the total content of chlorine atoms and bromine atoms is preferably 300 ppm or less, more preferably 250 ppm or less, still more preferably 220 ppm or less. Satisfied. By suppressing the content of chlorine atoms and bromine atoms below a specific value, even better thermal stability is achieved, and as a result, it is possible to provide a larger exterior molded article for a vehicle. In particular, the chlorine atom content is preferably small. On the other hand, as will be described later, it is also possible in the present invention to use a salt compound containing no chlorine ion or bromine ion as the organic onium ion source in the organically modified layered silicate. In such a case, the content of chlorine atoms or bromine atoms can be made substantially zero. However, in practice, it is advantageous in terms of handling and cost to use an organic onium salt compound having chlorine ions and bromine ions, especially chlorine ions as counter ions. A resin composition containing atoms, particularly chlorine atoms, is a practically preferable embodiment. Therefore, the lower limit of the total content of chlorine atoms and bromine atoms in the component B and the lower limit of the content of chlorine atoms are preferably 10 ppm or more, preferably 50 ppm or more, more preferably 100 ppm or more.

  The content of chlorine atoms and bromine atoms in the organically modified layered silicate is measured by ion chromatography.

  The following method is illustrated as a specific measuring method. That is, about 2 g of the organically modified layered silicate is precisely weighed, placed in a 300 ml beaker, and 200 ml of distilled water is added. It is stirred for 1 hour at 1000 rpm with a stirrer using a stir bar. After stirring, the extracted suspension was diluted 10-fold with distilled water, and the filter (ADVANTEC: “Dismic-13cp” pore size: 0.20 μm and Nippon Dionex: “Dillex-IC” pore size: 0.22 μm) Then, the amount of chlorine is quantified with an ion chromatograph (Dionex: “DX-100”).

  In order to produce an organically modified layered silicate having a reduced content of chlorine and bromine atoms as described above, (i) use of an organic onium ion compound containing no chlorine ion or bromine ion as a counter ion, (ii) ) Use of organic onium ion compounds containing less chlorine and bromine ions, (iii) Ion exchange using organic onium ion compounds containing chlorine and bromine ions as counter ions (ie, organic onium salt compounds) The organic layered silicate after the washing is sufficiently washed and washed, as well as a combination thereof. In particular, from the viewpoint of work efficiency and productivity, it is important that the method (iii), that is, the produced organically modified layered silicate is sufficiently washed with water until a predetermined chlorine atom and bromine atom content is obtained. Due to the use of organic onium ion compounds, which are the main cause of contamination of chlorine and bromine atoms in organic layered silicates, their removal is also reduced to the specified amount of the present invention by washing with water with a small amount of impurities. Is possible.

  That is, in a preferred embodiment as the component C of the present invention, a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g is chlorinated or brominated with an organic onium ion, and 40% of the cation exchange capacity. The organic layered silicate (C ′ component) obtained by ion exchange at the above ratio and having a total content of chlorine atoms and bromine atoms of 300 ppm or less, and a more preferable embodiment is the C ′ The component is an ion exchange of a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g with a chlorinated or brominated organic onium ion at a ratio of 40% or more of the cation exchange capacity. It is the organically modified layered silicate obtained by washing the layered silicate after the exchange until the total content of chlorine atoms and bromine atoms becomes 300 ppm or less.

<About D component>
The component D of the present invention is a compound having an affinity with an aromatic polycarbonate and having a hydrophilic component, and is more preferably used in the present invention. This D component produces good affinity for both aromatic polycarbonates and layered silicates. The affinity for both improves the compatibility of the two components, and the layered silicate is finely and stably dispersed in the matrix aromatic polycarbonate (component A).

  The function of the D component relating to the dispersion of the layered silicate is presumed to be the same as that of the compatibilizer for polymer alloy (compatible) used for compatibilizing different polymers. Accordingly, the component D is preferably a polymer rather than a low molecular compound. The polymer is also excellent in thermal stability during kneading. The average number of repeating units of the polymer is preferably 5 or more, and more preferably 10 or more. On the other hand, the upper limit of the average molecular weight of the polymer is preferably 2,000,000 or less in terms of number average molecular weight. If the upper limit is not exceeded, good moldability can be obtained.

When D component mix | blended with the resin composition of this invention is a polymer, as the basic structure, the following are mentioned, for example.
A) When the component having affinity for the aromatic polycarbonate is α and the hydrophilic component is β, a graft copolymer comprising α and β (the main chain is α, the graft chain is β, and the main chain is β Any of the graft chains α can be selected.), A block copolymer comprising α and β (di-, tri-, etc., the number of equal block segments can be selected to be 2 or more, including a radial block type, etc.) and A random copolymer comprising α and β. Here, α and β mean both a polymer segment unit and a monomer unit, but the α component is preferably a polymer segment unit from the viewpoint of affinity with an aromatic polycarbonate.
A) A polymer having a structure in which the function of α is expressed by the whole polymer and β is included in α when α is a component having affinity for the aromatic polycarbonate and β is a hydrophilic component. That is, α alone is not sufficient in affinity with the aromatic polycarbonate, but a good affinity is expressed by combining α and β together. In the case of α alone, the affinity with the aromatic polycarbonate is good, and the affinity may be further improved by combination with β. Therefore, these structures a) and a) may overlap in some of them.

  As the component D in the present invention, a component having a high affinity for an aromatic polycarbonate even when only α component is present, and that having a higher affinity in the entire C component added with β is preferable.

  Here, a component having an affinity for the aromatic polycarbonate in the component D (hereinafter sometimes referred to as α) will be described. As described above, the component D is considered to have the same function as the compatibilizing agent in the polymer alloy, and therefore α is required to have the same affinity for the polymer as the compatibilizing agent. Therefore, α can be roughly classified into a non-reactive type and a reactive type.

The non-reactive type has good affinity when it has the following factors. That is, between the aromatic polycarbonate and α, (i) chemical structure similarity, (ii) solubility parameter approximation (solubility parameter difference is within 1 (cal / cm ³ ) ^1/2 , ie about 2 .05 (MPa) ^{1/2 or} less) (iii) Intermolecular interactions (hydrogen bonds, ionic interactions, etc.) and random polymer-specific quasi-attractive interactions Is desired. These factors are also known as indicators for judging the affinity between the compatibilizing agent and the polymer which is the base of the polymer alloy.

  As the reactive type, a compatibilizer having a functional group reactive with an aromatic polycarbonate can be exemplified. For example, a carboxyl group, a carboxylic acid anhydride group, an epoxy group, an oxazoline group, an ester group, an ester bond, a carbonate group, a carbonate bond and the like having reactivity with an aromatic polycarbonate can be exemplified.

  On the other hand, when the aromatic polycarbonate and α have a good affinity, as a result, the mixture of the aromatic polycarbonate and α exhibits a single glass transition temperature (Tg), or the Tg of the aromatic polycarbonate is α Therefore, the component (α) having an affinity for the aromatic polycarbonate can be discriminated by this behavior.

  As described above, the component (α) having an affinity for the aromatic polycarbonate in the component D useful as a component of the composition of the present invention is preferably a non-reactive type, and in particular, the solubility parameter is approximated. It is preferable to exhibit good affinity. This is because the affinity with the aromatic polycarbonate is superior to the reaction type. In addition, the reaction type has a drawback that when the reactivity is excessively increased, thermal degradation of the polymer is promoted by a side reaction.

The α solubility parameter of the aromatic polycarbonate (component A) and component C preferably has the following relationship: That is, the solubility parameter of the aromatic polycarbonate (component A) is δ _A ((MPa) ^1/2 ), and the solubility parameter of α in the C component or the solubility parameter of the entire C component is δ _α ((MPa) ^1/2 ). The following formula:
δ _α = δ _A ± 2 ((MPa) ^1/2 )
It is preferable to have the following relationship.

For example, since the solubility parameter of the component A is usually about 10 (cal / cm ³ ) ^1/2 (that is, about 20.5 ((MPa) ^1/2 )), δ _α is 18.5 to 22 0.5 ((MPa) ^1/2 ) is preferable, and a range of 19 to 22 ((MPa) ^1/2 ) is more preferable.

Specific examples of the polymer component satisfying such solubility parameter [delta] _alpha, styrene polymers, alkyl (meth) acrylate polymers, vinyl polymers, such as acrylonitrile polymers (e.g., polystyrene, styrene - maleic anhydride copolymer, poly Methyl methacrylate, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, etc.). Among these, in order to maintain the heat resistance of the resin composition of the present invention, it is preferable to use a polymer component having a high Tg.

  Here, the solubility parameter is a theoretical estimation method based on the group contribution methods using Small values described in “Polymer Handbook 4th Edition” (A WILEY-INTERSCIENCE PUBLICATION, 1999). Is available. The Tg of the aromatic polycarbonate can be determined by differential scanning calorimetry (DSC) measurement based on JIS K7121 as already described.

  The component α having an affinity for the aromatic polycarbonate of the component A is preferably 5% by weight or more in the component D, more preferably 10% by weight or more, further preferably 30% by weight or more, and 50% by weight or more. Is particularly preferred. Since the aspect which makes (alpha) the whole D component is also possible, an upper limit may be 100 weight%.

On the other hand, the hydrophilic component (hereinafter sometimes referred to as β) in component D is composed of a monomer having a hydrophilic group (an organic atomic group having a strong interaction with water) and a hydrophilic polymer component (polymer). Segment). Hydrophilic groups are widely known per se, and the following groups are exemplified.
1) Strongly hydrophilic group: —SO ₃ H, —SO ₃ M, —OSO ₃ H, —OSO ₃ H, —COOM, —NR ₃ X (R: alkyl group, X: halogen atom, M: alkali metal) , _-NH 4), etc.,
2) slightly smaller hydrophilic group _{having: -COOH, -NH 2, -CN,} -OH, -NHCONH 2 or the like,
3) Non-hydrophilic or small groups: —CH ₂ OCH ₃ , —OCH ₃ , —COOCH ₃ , —CS, etc.

  As the component C to be blended in the composition of the present invention, those having a hydrophilic group classified in the above 1) or 2) are used, and in particular, the hydrophilic group in 2) is a heat generated during the melt processing of an aromatic polycarbonate. It is preferable because it is more stable. If the hydrophilicity is too high, thermal degradation of the aromatic polycarbonate tends to occur. This is because such a hydrophilic group directly reacts with a carbonate bond to cause a thermal decomposition reaction.

  The hydrophilic group may be a monovalent group or a bivalent or higher group. When the component D is a polymer, a divalent or higher functional group means a group in which the main chain does not constitute a main chain, and a constituent constituting the main chain is distinguished from a functional group as a bond. Specifically, a group added to an atom such as carbon constituting the main chain, a side chain group, and a molecular chain terminal group are functional groups even if they are divalent or higher.

A more specific indicator of hydrophilic groups is the solubility parameter. It is widely known that the greater the solubility parameter value, the higher the hydrophilicity. The solubility parameter for each group can be calculated from the cohesive energy (E _coh ) for each group by Fedors and the molar volume (V) for each group ("Polymer Handbook 4th Edition" (A WILEY-INTERSCIENCE PUBLICATION), VII / 685, 1999, Polym. Eng. Sci., 14, 147 and 472, 1974, etc.). Furthermore, from the viewpoint of comparing only the magnitude relationship of hydrophilicity, a value obtained by dividing the cohesive energy (E _coh ) by the molar volume (V) (E _coh / V; hereinafter the unit is “J / cm ³ ”) is hydrophilic. Can be used as a sex indicator.

The hydrophilic group contained in β in the D component needs to have E _coh / V of 600 or more, and preferably E _coh / V is 800 or more. In the case of 800 or more, it exceeds E _coh / V of the carbonate bond in the aromatic polycarbonate of the component A, and has higher hydrophilicity than the carbonate bond. E _coh / V is more preferably 900 or more, and further preferably 950 or more.

As described above, when the hydrophilicity is too high, thermal degradation of the aromatic polycarbonate tends to occur. Therefore, E _coh / V is preferably 2,500 or less, more preferably 2,000 or less, and even more preferably 1,500 or less.

  A hydrophilic polymer component (polymer segment) can also be selected as the hydrophilic component (β) of the D component. As the hydrophilic polymer in which the hydrophilic polymer segment contained in the polymer of component D becomes β, for example, polyalkylene oxide, polyvinyl alcohol, polyacrylic acid, polyacrylic acid metal salts (including chelate type) And polyvinylpyrrolidone, polyacrylamide, polyhydroxyethyl methacrylate, and the like. Among these, polyalkylene oxide, polyvinyl alcohol, polyacrylic acid, polyvinyl pyrrolidone, and polyhydroxyethyl methacrylate are preferably exemplified. This is because both good hydrophilicity and thermal stability with respect to the aromatic polycarbonate (inhibition of decomposition of the aromatic polycarbonate during melt processing) can be achieved. Polyalkylene oxide is preferably polyethylene oxide or polypropylene oxide.

  In both the monomer having a hydrophilic group and the hydrophilic polymer component, β preferably has an acidic functional group (hereinafter sometimes simply referred to as “acidic group”). Such an acidic group suppresses thermal deterioration during melt processing of the resin composition constituting the vehicle exterior molded article of the present invention. In particular, an acidic group containing no nitrogen atom is more preferable. Suitable examples of the acidic group include a carboxyl group, a carboxylic acid anhydride group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, and a phosphinic acid group.

  In comparison, functional groups containing nitrogen atoms such as amide groups and imide groups may not sufficiently suppress the thermal degradation of the aromatic polycarbonate during melt processing. This is presumably because the nitrogen atom is locally basic and causes thermal decomposition of the carbonate bond.

  When β is a monomer having a hydrophilic group, the ratio of β in component D is 60 to 10,000, preferably 70 to 8,000, as the functional group equivalent, which is the molecular weight per functional group, 80-6,000 are more preferable, and 100-3,000 are more preferable. Further, when β is a hydrophilic polymer segment, it is appropriate that β is 5 to 95% by weight in 100% by weight of D component, preferably 10 to 90% by weight, more preferably 30 to 70% by weight, More preferably, it is 30 to 50% by weight.

  As a method for producing an organic compound (component D) having a component (α) having affinity for an aromatic polycarbonate and a hydrophilic component (β), a monomer of β and a monomer constituting α And a method in which a polymer component of β is block or graft copolymerized with α, a method in which β is directly reacted with α, and the like.

  Specific examples of component D include a polymer having an affinity for an aromatic polycarbonate and an acidic functional group, a polymer having an affinity for an aromatic polycarbonate and having a polyalkylene oxide segment, an aromatic polycarbonate And a polymer having an oxazoline group, or a polymer having an affinity with an aromatic polycarbonate and having a hydroxyl group. In the polymer preferable as these D components, the molecular weight is preferably in the range of 10,000 to 1,000,000, more preferably in the range of 50,000 to 500,000 in terms of weight average molecular weight. The weight average molecular weight is calculated as a value in terms of polystyrene by GPC measurement using a calibration straight line with a standard polystyrene resin.

<About D-1 component>
Among the components D, a polymer having an affinity for an aromatic polycarbonate and having an acidic functional group is preferable, and a functional group having an affinity and consisting of a carboxyl group and / or a derivative thereof is more preferable. It is a polymer having Particularly preferred component D is an aromatic vinyl polymer (component D-1) having a carboxyl group and / or a functional group composed of a derivative thereof (hereinafter simply referred to as “carboxyl groups”). Here, the aromatic vinyl polymer refers to a polymer whose main constituent unit is a repeating unit derived from an aromatic vinyl compound such as styrene. In addition to the structural unit containing a carboxyl group, the component D-1 can contain a small proportion of other structural units. The carboxyl group content in the component D (preferably the component D-1) is preferably 0.1 to 12 meq / g, more preferably 0.5 to 5 meq / g. Here, 1 equivalent in the C component means that 1 mol of carboxyl groups is present, and the value can be calculated by back titration with potassium hydroxide or the like.

The functional group comprising a derivative of a carboxyl group includes (i) metal salts (including chelate salts) in which the hydroxyl group of the carboxyl group is substituted with metal ions, (ii) acid chlorides substituted with chlorine atoms, (iii) -OR An ester substituted with (R is a monovalent hydrocarbon group), (iv) an acid anhydride substituted with —O (CO) R (R is a monovalent hydrocarbon group), (v) substituted with —NR ₂ Amides (R is hydrogen or a monovalent hydrocarbon group), (vi) Imidos (R is hydrogen or a monovalent hydrocarbon group) in which the hydroxyl groups of two carboxyl groups are substituted with NR. Particularly preferred is an acid anhydride.

  Various conventionally known methods can be used as a method for producing an aromatic vinyl polymer having a carboxyl group. Examples include (a) a method of copolymerizing a compound having a carboxyl group and an aromatic vinyl compound, and (b) a method of bonding or copolymerizing a compound having a carboxyl group to an aromatic vinyl polymer. It is done.

  The copolymer (a) may take various forms such as an alternating copolymer, a block copolymer, and a tapered copolymer in addition to a random copolymer. Also in the copolymerization method, various polymerization methods such as anion living polymerization method and group transfer polymerization method can be used in addition to radical polymerization methods such as solution polymerization, suspension polymerization and bulk polymerization. Furthermore, a method of once forming a macromonomer and then polymerizing is also possible.

  As the method (b), radical generation such as peroxide and 2,3-dimethyl-2,3-diphenylbutane (commonly called dicumyl) is generally used as required for aromatic vinyl polymers or copolymers. A method of adding an agent and reacting or copolymerizing at a high temperature is typically exemplified. In this method, a reactive site is thermally generated in an aromatic vinyl polymer or copolymer, and a compound that reacts with the active site is reacted. Other methods for generating active sites required for the reaction include irradiation with radiation and electron beam, and application of external force by mechanochemical technique. Furthermore, as a method for generating active sites, there may be mentioned a method in which a monomer that generates active sites required for the reaction is copolymerized in advance in an aromatic vinyl copolymer. Examples of active sites for the reaction include unsaturated bonds, peroxide bonds, steric hindrance and thermally stable nitroxide radicals. Furthermore, a method of grafting a polymer having these active sites onto a polymer as a main chain is also mentioned as a copolymerization method in the above (b).

  The structural unit derived from the other compound is a method in which another compound is graft-copolymerized to the copolymer obtained by the method (a) or (b), and the other unit in the copolymerization in the method (a). A method of copolymerizing in the presence of a compound, and a method of applying the method of (b) using the aromatic vinyl polymer in the method of (b) as a copolymer of an aromatic vinyl and another compound, etc. -It can be contained in a one-component aromatic vinyl polymer.

  Examples of the compound having a carboxyl group include unsaturated monocarboxylic acids and derivatives thereof (for example, acrylic acid, methacrylic acid, acrylamide, and methacrylamide), maleic anhydride, citraconic anhydride, and maleic anhydride derivatives ( Examples thereof include N-phenylmaleimide and N-methylmaleimide), glutarimide structures, and chelate structures formed from acrylic acid and polyvalent metal ions. Among these, a compound having a functional group not containing a metal ion or a nitrogen atom is preferable, and a compound having a carboxyl group and a carboxylic anhydride group, particularly maleic anhydride is more preferable.

  Examples of the aromatic vinyl compound in the aromatic vinyl polymer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, tert-butylstyrene, α-methylvinyltoluene, and dimethylstyrene. , Chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, vinylnaphthalene and the like are exemplified, and styrene is particularly preferable. Furthermore, other compounds copolymerizable with these compounds, such as vinyl cyanide compounds, diene compounds, and olefins, may be used as the copolymerization component.

  A more preferable component D-1 in the present invention is a copolymer obtained by copolymerizing a compound having a carboxyl group, an aromatic vinyl compound, and optionally other compounds. This is because such a copolymer can stably contain a relatively large number of carboxyl groups in the aromatic vinyl polymer. A particularly preferred embodiment is a styrene-maleic anhydride copolymer. Since the styrene-maleic anhydride copolymer has high compatibility with both the ionic component and the aromatic polycarbonate in the layered silicate, the layered silicate (C component) is finely dispersed very well. Furthermore, the thermal stability of the resin composition containing a layered silicate, particularly a layered silicate ion-exchanged with an organic onium ion, is improved by the action of the carboxylic acid anhydride group, and as a result, the resin composition becomes larger. It can be applied to molded products of

  Component D-1 is derived from 1 to 30% by weight (preferably 5 to 25% by weight) of a structural unit derived from a compound having a carboxyl group in 100% by weight, and from an aromatic vinyl compound and other compounds. It is preferable that the structural unit contains 99 to 70% by weight (preferably 95 to 75% by weight). Further, the structural units derived from the aromatic vinyl compound and the other compound are 60 to 100% by weight (preferably 70 to 100% by weight) of the former, and the latter is 0 to 100% by weight. 40% by weight (preferably 0 to 30% by weight).

  The molecular weight of the component D-1 is not particularly limited, but the weight average molecular weight is preferably in the range of 10,000 to 1,000,000, and more preferably in the range of 50,000 to 500,000. In addition, the weight average molecular weight shown here is calculated as a value in terms of polystyrene by GPC measurement using a calibration straight line by standard polystyrene resin.

<About other D components>
Other suitable D component includes a styrene-containing copolymer (D-2 component) containing an oxazoline group as a hydrophilic group. Examples of the styrene monomer compound that forms such a copolymer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, tert-butylstyrene, α-methylvinyltoluene, dimethyl Styrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, vinylnaphthalene, and the like can be used. Furthermore, other compounds copolymerizable with these compounds, such as acrylonitrile and methacrylonitrile, may be used as the copolymerization component. A specific example of a particularly suitable D-2 component is a styrene (2-isopropenyl-2-oxazoline) -styrene-acrylonitrile copolymer.

  Another suitable D component is a polyether ester copolymer (D-3 component) having a polyalkylene oxide segment. This polyetherester copolymer is a polymer produced by polycondensation from dicarboxylic acid, alkylene glycol and poly (alkylene oxide) glycol or derivatives thereof. Particularly suitable as such D-3 component is poly (alkylene oxide) glycol having a polymerization degree of 10 to 120 or a derivative thereof, alkylene glycol or a derivative thereof containing 65 mol% or more of tetramethylene glycol, and 60 mol% of terephthalic acid. It is a copolymer produced from the dicarboxylic acid or derivative thereof contained above.

<Composition ratio of each component>
Next, the composition ratio (content) of each component in the light diffusing polycarbonate resin composition constituting the vehicle exterior molded article of the present invention will be described.

  The polymer fine particles of component B are 0.1 to 30 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.00 based on 100 parts by weight of component A (aromatic polycarbonate). 2 to 7 parts by weight. A preferable light diffusion function is realized when the composition ratio of the component B is in the above range. Thus, polymer fine particles are also suitable in that a sufficient effect can be achieved with a relatively small amount. In particular, silicone-based crosslinked particles are preferable in that a sufficient effect can be achieved with a smaller content.

  The layered silicate of component C (including C ′ component) is 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 0, based on 100 parts by weight of component A. 0.5 to 10 parts by weight, particularly preferably 1 to 9 parts by weight. When the composition ratio of the B component is less than the lower limit, the effect of the layered silicate is likely to be insufficient, and therefore insufficient to obtain high rigidity. On the other hand, when the composition ratio of the C component is larger than the above upper limit, the light diffusion function of the composition may be deteriorated, and the hue may be deteriorated due to a decrease in heat resistance and thermal stability, which is not preferable.

  The content of component D (including component D-1, component D-2, and component D-3) is preferably 0.1 to 50 parts by weight based on 100 parts by weight of component A, and more preferably It is 0.5-20 weight part, More preferably, it is 1-12 weight part. Within the above range, good fine dispersion of the layered silicate and improvement in thermal stability are achieved. Therefore, a light diffusing polycarbonate resin composition having higher rigidity and thermal stability can be obtained by including the D component in the above proportion, and as a result, a larger vehicle exterior molded product is provided. And the improvement of this thermal stability makes the hue of the exterior molded article for vehicles good.

  Therefore, the optimal composition ratio of each component in the resin automobile exterior molded article of the present invention is 0.2 to 7 parts by weight of B component, 1 to 9 parts by weight of C component, and 1 to 12 parts of D component per 100 parts by weight of component A. Parts by weight.

<Additional ingredients that can be blended if necessary>
The vehicle exterior molded article of the present invention comprises an A component aromatic polycarbonate and a B component polymer fine particle having a specific particle size as essential components, and more preferably a C component layered silicate and a D component styrene-anhydrous maleic acid. It is comprised from the resin composition containing components, such as an acid copolymer. However, if desired, polymers other than the A component, the B component and the D component, and other various additives may be added as additional components.

(I) Polymers other than A component, B component, and D component Examples of such polymers include styrene-based polymers and aromatic polyesters other than the B component D component.

  Such styrenic polymers include polystyrene (PS) (including syndiotactic polystyrene), acrylonitrile / styrene copolymer (AS copolymer), methyl methacrylate / styrene copolymer (MS copolymer), and polymethyl. Examples include methacrylate. Among these, the AS copolymer is preferable because of excellent compatibility with the aromatic polycarbonate. Such a styrenic polymer may be modified with various functional groups typified by epoxy groups and acid anhydride groups. These styrenic polymers can be used in combination of two or more.

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

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

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

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

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

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

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

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

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

(Iv) Release agent It is preferable that the light diffusable polycarbonate resin composition of this invention contains a release agent. Examples of the release agent include saturated fatty acid esters, unsaturated fatty acid esters, and polyolefin waxes (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification) Examples thereof include silicone compounds, fluorine compounds (fluorine oils typified by polyfluoroalkyl ethers), paraffin wax, beeswax and the like. Such a release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 0.8 parts by weight, based on 100 parts by weight of component A.

  Among such release agents, saturated fatty acid esters are preferred. The resin composition comprising the components A to D of the present invention can further improve its hydrolysis resistance by further containing a partial ester and / or full ester of a higher fatty acid and a polyhydric alcohol. Although the cause of this improvement in hydrolysis resistance is not clear, it is presumed to have an action of capturing and neutralizing an ionic compound that causes hydrolysis.

  Here, the higher fatty acid refers to an aliphatic carboxylic acid having 10 to 32 carbon atoms, and specific examples thereof include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid). ), Heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, docosanoic acid, hexacosanoic acid and other saturated aliphatic carboxylic acids, as well as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaene Mention may be made of unsaturated aliphatic carboxylic acids such as acids and cetoleic acid. Among these, the aliphatic carboxylic acid preferably has 10 to 22 carbon atoms, and more preferably has 14 to 20 carbon atoms. Particularly preferred are saturated aliphatic carboxylic acids having 14 to 20 carbon atoms, particularly stearic acid and palmitic acid. The aliphatic carboxylic acid such as stearic acid is usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Also in the saturated fatty acid ester, ester compounds obtained from stearic acid or palmitic acid which are produced from such natural fats and oils and are in the form of a mixture containing other carboxylic acid components are preferably used.

  On the other hand, as a polyhydric alcohol, a C3-C32 thing is more preferable. Specific examples of such polyhydric alcohols include glycerin, diglycerin, polyglycerin (for example, decaglycerin), pentaerythritol, dipentaerythritol, diethylene glycol, propylene glycol, and the like.

  The acid value in the saturated fatty acid ester of the present invention is preferably 20 or less (can take substantially 0), and the hydroxyl value is more preferably in the range of 20 to 500 (more preferably 50 to 400). Further, the iodine value is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070.

  The light diffusing polycarbonate resin composition of the present invention has hitherto been known as a hydrolysis improving agent for aromatic polycarbonates for the purpose of further improving the hydrolysis resistance, particularly when it contains a C component and a D component. A compound can also be mix | blended in the range which does not impair the objective of this invention. Examples of such compounds include epoxy compounds, oxetane compounds, silane compounds, and phosphonic acid compounds, with epoxy compounds and oxetane compounds being particularly preferred. Examples of the epoxy compound include an alicyclic epoxy compound represented by 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, and a silicon atom-containing epoxy represented by 3-glycidylpropoxy-triethoxysilane. The compound is preferably exemplified. The hydrolysis improver is preferably 1 part by weight or less per 100 parts by weight of component A.

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

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

  Of these, cyclic imino ester compounds and cyanoacrylate compounds are preferred as UV absorbers that have a good hue and are more suitable for taking in soft natural light into the vehicle interior, and are particularly excellent in terms of excellent thermal stability. In the invention, a cyclic imino ester compound is preferred. The content of the ultraviolet absorber is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, still more preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the component A. It is.

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

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

(Vii) White pigment In the light diffusing aromatic polycarbonate resin composition of the present invention, titanium dioxide, zinc oxide, and zinc sulfide can be blended as a white pigment for the purpose of adjusting the light shielding property. Of these white pigments, titanium dioxide is particularly preferred. Such titanium dioxide is preferably surface-treated with an oxide of a metal such as aluminum, silicon, titanium, zirconium, antimony, tin and zinc. As the surface treatment, either a high-density treatment or a low-density (porous) treatment can be applied. Further preferred titanium dioxide is surface treated with an organic compound. As such a surface treatment agent, a surface treatment agent mainly comprising an amine compound, a silicone compound, and a polyol compound is used. In particular, titanium dioxide coated with an alkyl hydrogen polysiloxane is preferably used. In the resin composition of the present invention, the content of titanium dioxide is 0.0001 to 0.5 parts by weight, more preferably 0.0005 to 0.1 parts by weight, based on 100 parts by weight of component A.

(Viii) Carbon black Carbon black can be mix | blended with the light-diffusing aromatic polycarbonate resin composition of this invention in order to adjust the light-shielding property. Preferred carbon black is oil furnace black or channel black. In addition, any type such as HCC, HCF, MCF, LFF, and RCF can be used in such carbon black, but more preferred are HCF, MCF, LFF, and the like. Further, the pH value is more preferably 7 or less, and further preferably in the range of 2-6. Carbon black can be used alone or in combination of two or more. The raw material form of such carbon black is not particularly limited, and in addition to a powder form of carbon filler alone, a form dispersed in oil, a form granulated with a binder resin, and a polycarbonate resin or other resin Various forms such as a master batch form melt-kneaded at a high concentration can be used. Carbon black is preferably in the range of 0.05 to 5 ppm (weight ratio), more preferably in the range of 0.1 to 3 ppm, and still more preferably in the range of 0.2 to 2 ppm in the resin composition of the present invention. Within the above range, an appropriate light shielding property can be obtained efficiently.

(Ix) Other dyes / pigments Various dyes / pigments other than the above can be used in the light-diffusing aromatic polycarbonate resin composition of the present invention as long as the object of the invention is not impaired. Examples of such dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes Examples thereof include dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, fluorescent whitening agents such as bisbenzoxazolyl-stilbene derivatives, bisbenzoxazolyl-naphthalene derivatives, bisbenzoxazolyl-thiophene derivatives, and coumarin derivatives can also be used. Other metallic pigments (for example, metal oxide-coated plate-like filler, metal-coated plate-like filler, and metal flakes) are blended to obtain a better metallic color, and appropriately reflect heat rays to further increase the room temperature. It can also be kept appropriate. The content of the other dyes / pigments is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.8 part by weight, based on 100 parts by weight of the component A.

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

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

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

(Xi) Compound having heat-absorbing ability In the light-diffusing polycarbonate resin composition of the present invention, a compound having heat-absorbing ability in an amount that does not impair the object of the present invention can be used. Examples of the compound include phthalocyanine-based near infrared absorbers, metal oxide-based near infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, and metal boride-based near infrared rays such as lanthanum boride, cerium boride and tungsten boride. Preferred examples include various metal compounds having excellent near-infrared absorption ability such as an absorber, and carbon filler. 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 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and still more preferably 0.001 to 0 parts, based on 100 parts by weight of the component A. .07 parts by weight. The range of 0.1-200 ppm (weight ratio) is preferable in a resin composition, and the range of 0.5-100 ppm is more preferable for a metal oxide near-infrared absorber and a metal boride-type near-infrared absorber. The carbon filler is preferably in the range of 0.05 to 5 ppm (weight ratio) in the resin composition of the present invention.

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

<About the preparation of a light diffusing polycarbonate resin composition>
Arbitrary methods are employ | adopted for preparing the light diffusable polycarbonate resin composition of this invention. For example, as a method for producing a resin composition, there can be mentioned a method in which the above-mentioned components and other components optionally blended are premixed and then melt-kneaded and pelletized. Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. In the preliminary mixing, granulation can be performed by an extrusion granulator, a briquetting machine, or the like, if necessary. After the preliminary mixing, the mixture is melt kneaded with a melt kneader typified by a vent type twin screw extruder and pelletized with a device such as a pelletizer. As the melt kneader, a Banbury mixer, a kneading roll, a constant-temperature stirring vessel, and the like can be used. A multi-screw extruder represented by a vent type twin-screw extruder is preferable. By using such a multi-screw extruder, the polymer fine particles are finely dispersed in the base resin with a strong shearing force.

  Furthermore, in the melt-kneading of the light diffusing polycarbonate resin composition containing the C component and the D component, the following mode is more preferable. That is, a compound (D component) having affinity with a layered silicate (C component) having a cation exchange capacity of 50 to 200 meq / 100 g and an aromatic polycarbonate of component A and having a hydrophilic component, Particularly preferably, an aromatic vinyl polymer having a functional group comprising a carboxyl group and / or a derivative thereof (D-1 component) is previously melt-kneaded, and the melt-kneaded product and the aromatic polycarbonate of component A and The polymer fine particles of component B are melt mixed. The preliminary mixture of the C component and the D component or the B component can be supplied into the molten resin from the middle of the multi-screw extruder using a side feeder or the like, if necessary. Such a melt-kneading method is preferable because it achieves fine dispersion of the layered silicate and further improves the thermal stability of the aromatic polycarbonate.

  In the production of the preliminary mixture of the C component and the D component, it is preferable to reduce the content of chlorine atoms and bromine atoms in the preliminary mixture by sufficiently performing devolatilization from the vent. By performing such a treatment, better thermal stability of the resin composition is achieved, and as a result, it is possible to provide a larger vehicle exterior molded product. The content of chlorine atoms and bromine atoms in the preliminary mixture is more preferably 100 ppm or less. Such content is measured by the above-mentioned ion chromatography.

  A suitable vehicle exterior molded article of the present invention may be formed from a resin composition obtained by another mixing method. For example, pellets of the resin composition of component A and component B, and pellets obtained by previously melting and kneading component C and component D are simultaneously supplied to a molding machine (for example, an injection molding machine) and mixed in the molding machine. A manufacturing method is mentioned.

  As an example of an advantageous production method of a suitable light diffusing polycarbonate resin resin composition of the present invention, (i) a component obtained by melting and kneading a C component and a D component with a vent type twin screw extruder, Method of melt-kneading again with A component and B component, (ii) C component and D component are charged from the main supply port of the vent type twin screw extruder, and part or all of the A component is in the middle of the twin screw extruder Examples thereof include a method in which the C component and the D component are introduced into the melt-kneaded state from the supply port provided in the stage. In the method of melt-kneading these C component and D component in advance, a part of the A component may be included during the melt-kneading. Further, in any of the methods (i) and (ii), the polymer fine particles can be supplied from the screw root portion of the extruder as a resin raw material or the like, or from a position in the middle of the extruder. You can also.

  In addition, since the light diffusing polycarbonate resin exterior molded article of the present invention is often used in a field that usually requires high optical characteristics, the presence of foreign substances that obstruct such optical characteristics should be reduced. Is preferred. In order to obtain a resin composition for such a preferable light diffusing polycarbonate resin exterior molded article for a vehicle, a raw material having a small amount of foreign matter is used, and a manufacturing apparatus such as an extruder or a pelletizer is placed in a clean air atmosphere. In addition to installing the cooling water for the cooling bath, use water with a small amount of foreign matter, and also fill the raw material supply hopper, supply flow path, and storage tank for the obtained pellets with cleaner air. Is preferred. For example, it is appropriate to adopt a method similar to that proposed in JP-A-11-21357.

<About the manufacturing method of exterior molded products for vehicles>
The vehicle exterior molded article of the present invention can be manufactured by various methods. Examples thereof include a method of bending an extruded sheet, a method of press-molding a melt-extruded sheet-shaped resin in a mold, and a method of injection molding. Of these, an injection molding method that can obtain a molded product with the highest accuracy and efficiency is preferred. Here, as the injection molding method, not only a normal injection molding method but also injection compression molding, injection press molding, heat insulating mold molding, rapid heating / cooling mold molding, ultra-high speed injection molding, and the like can be used. Among these, injection press molding is preferable for the following reasons. In addition, either a cold runner method or a hot runner method can be selected for molding.

  In the present invention, injection press molding means that a molten thermoplastic resin is supplied into a mold cavity having a capacity larger than the target molded article capacity at least when the supply is completed, and the mold cavity capacity is reduced after the supply is completed. This is a molding method in which the molded product is reduced to a target molded product capacity and the molded product is taken out after being cooled to a temperature below which the molded product in the mold cavity can be taken out. The reduction of the mold cavity capacity may be started before or after the completion of the resin supply, but is preferably started before the completion of the supply. That is, a mode in which the step of reducing the cavity capacity and the step of filling the resin overlap is preferable.

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

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

  In addition, as is generally known, injection press molding enables molding at an extremely low pressure, so that the level of clamping pressure of the injection molding machine can be greatly reduced. This is a particularly large molded product, and in the molded product having a long flow length, the quality of the product can be improved and the cost of the equipment can be reduced. In another aspect, injection press molding is a molding method capable of reducing the molding temperature. Therefore, the molding method reduces the thermal load even in a large molded product, and as a result, it is possible to provide a good molded product while being a large molded product.

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

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

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

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

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

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

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

  More preferably, the injection molded product of the present invention has only one gate on the side surface of the molded product. Such injection-molded products usually tend to have a large flow length and are often subjected to a higher heat load. As a result, the light transmittance of the molded product becomes non-uniform, or the inherent hue is hindered. The vehicle exterior molded article of the present invention is improved in this respect by applying an injection press molding method. Therefore, it can be said that a molded article having only one gate on the side part of the molded article is a particularly preferable molded article shape in the present invention. Furthermore, since injection press molding solves this point, the application of injection press molding further exhibits the effects of the present invention in producing the molded product of the present invention.

<About vehicle exterior molded products>
The vehicle exterior molded article of the present invention is large in size, has a good hue, and allows soft natural light to be taken into the vehicle compartment. Furthermore, in a preferred embodiment thereof, an exterior molded article for a vehicle having a relatively large area and excellent in rigidity, dimensional stability and surface smoothness is provided. The advantage of the vehicle exterior molded product of the present invention becomes more prominent as the molded product is larger. That is, the larger the size, the higher the heat load at the time of molding, and the thermal stability due to the blending of the B component of the present invention is advantageously exhibited. The resin composition containing the more preferable C component and D component of the present invention is suitable for a larger molded article because the rigidity and dimensional stability are improved. Accordingly vehicle exterior molded article of the present invention as described above, the maximum projected area preferably 500～50,000Cm ^2, more preferably 5,000～40,000Cm ^2, more preferably 10,000~35,000cm ² . Further, a molded product having a flow length of 30 cm or more is suitable for exhibiting the effects of the present invention, and more preferably 35 cm or more. On the other hand, 200 cm or less is appropriate as the upper limit of the flow length, and 180 cm or less is more appropriate.

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

  Therefore, according to the present invention, it is composed of the above light diffusing polycarbonate resin composition, has such a maximum projected area, has high dimensional stability, and has a sufficient shape without warping even when L / D is high. As a result, a large vehicle exterior molded article formed from the light diffusing polycarbonate resin composition is provided.

  The vehicle exterior molded article of the present invention described above may have a surface having a surface shape such as a Fresnel lens shape or a cylindrical lens shape, or a laminated plate in which such a shape is separately laminated with another material. It is also possible. When directly imparting the Fresnel lens shape or the cylindrical lens shape to the resin composition of the light diffusing polycarbonate resin vehicle exterior molded product of the present invention, the resin composition of the light diffusing polycarbonate resin vehicle exterior molded product is injected using the resin composition. It can be molded into a desired shape by a molding method such as molding, injection compression molding, injection press molding, compression molding, and extrusion molding. Furthermore, as a method of forming irregularities for the Fresnel lens on the surface by injection molding, injection compression molding, injection press molding, compression molding, extrusion molding, (1) Fresnel lens shape on the mold cavity surface or transfer roll surface Or a method in which the unevenness is transferred to the surface of the resin molded product, or (2) another material provided with unevenness corresponding to the Fresnel lens shape or the like is inserted into the mold cavity, Alternatively, a method in which, after being laminated at the time of extrusion and integrated with a resin molded product, such other material is removed and the surface of the resin molded product is provided with irregularities, and the like are exemplified.

  In some cases, such a screen can be provided with a layer containing a luster pigment to eliminate a lens due to surface irregularities. Furthermore, the vehicle exterior molded article of the present invention can be formed with various antireflection films in order to prevent light reflection.

  The obtained molded product is attached to the vehicle by various methods. In addition to the method of directly attaching the molded product of the present invention to the vehicle frame, a method of separately attaching a frame material to the molded product of the present invention and attaching the frame material to the vehicle frame through the frame material may be used. Since such a frame material has a good white hue, the molded product of the present invention preferably has a white color or a color close thereto.

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

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

  Among the above methods, the vapor deposition method and the plating method are preferable for forming the metal layer of the molded article made of the resin composition of the present invention, and the vapor deposition method is preferable for forming the metal oxide layer. Surface modification with metal oxides typified by ATO, ITO, tin oxide, etc. has a relatively good light transmittance, a relatively good hue of transmitted light, and cuts heat rays to make the vehicle interior This is preferable in that the temperature can be maintained more appropriately. Such surface modification with a metal oxide may be performed on any side corresponding to the vehicle outer side and the vehicle inner side of the vehicle exterior molded product.

  By applying the hard coat of the present invention, it is further suitable for a vehicle exterior molded article member. The resin composition containing the components A to D, which is a preferred resin composition of the present invention, can exhibit the characteristics of the hard coat layer more effectively because the base molded article also has good surface hardness. Furthermore, since the molded article made of such a suitable resin composition has a reduced coefficient of linear expansion, the adhesiveness with the hard coat layer is also good.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The vehicle exterior molded article of the present invention enables soft natural light to be taken into the vehicle interior by a good hue and light diffusing ability, and is excellent in rigidity, dimensional stability and surface smoothness in a more preferred embodiment. In addition, a vehicle exterior molded article having a relatively large area is provided. Furthermore, the vehicle exterior molded product of the present invention can greatly improve the bending rigidity without increasing the weight of the molded product, and this characteristic contributes to the weight reduction of the product. A further feature is that the light diffusing polycarbonate resin composition of the present invention is excellent in thermal stability and can be applied to a large injection molded product. Due to these characteristics, the exterior molded article for vehicles is particularly suitable as a roofing material for vehicles. It can be suitably used.

  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.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited by these. In addition, evaluation of the resin composition and the molded article was performed by the following methods (1) to (3).
(1) Dimensional accuracy The automobile roof molded product shown in FIG. 1 is molded by an injection press molding method, and whether or not the molded product can be accurately attached to a predetermined vehicle (German smart coupe (Japanese name)). confirmed. About the molded article with a hard coat process and a film lamination process, the confirmation was performed about the molded article after this process. Those that can be attached are indicated by ◯, and those in which the molded product warps and cannot be attached sufficiently are indicated by ×.
(2) Appearance of molded product and uniformity of light in the room The automobile roof molded product shown in FIG. 1 was molded by an injection press molding method, and the appearance was confirmed. The case where the occurrence of silver streak or burnt streak was confirmed at the time of molding was indicated by x. Furthermore, it attached to the predetermined motor vehicle and observed the state of the light in a motor vehicle room under the direct sunlight. In this observation, the roof molded product emits light uniformly, and the light nonuniformity is shown by Δ. In addition, what was shown by (circle) exhibited the comfortable atmosphere in which the room was wrapped up moderately brightly, and both the feeling and open feeling were compatible.
(3) Dimensional Change of Molded Product The automobile roof molded product shown in FIG. 1 is molded by an injection press molding method, annealed in a hot air drying furnace at 105 ° C. for 6 hours, heat treated at 80 ° C. for 30 minutes, and immediately after removal. The dimensional change of was measured. The dimension was measured by marking the molded product on the surface plate and marking the measurement end points on the surface plate, and then measuring the distance between the markings. A smaller dimensional change is preferable because the mounting accuracy is stable.

[Examples 1-9, Comparative Examples 1-3]
(I) Preparation of molding material A resin composition comprising the blending ratios shown in Tables 1 and 2 was converted into a twin-screw extruder with a vent (Toshiba Machine Co., Ltd.) equipped with the raw material having a diameter of 58 mmφ and two kneading zones. ) Manufactured by: TEM-58SS), when not containing the C component and D component, melt extrusion was performed at a cylinder temperature of 290 ° C., and when it was contained, the strand was cut to obtain pellets. The degree of vent pressure reduction during extrusion was 3 kPa. Further, when the C component and the D component are contained, prior to the extrusion, the C component and the D component are dry blended at a blending ratio shown in Table 2, and then the cylinder temperature is set to 200 ° C. and the vent pressure is reduced using the extruder. It was melt-extruded at a temperature of 3 kPa and strand cut to obtain a master pellet. The master pellet was supplied into the molten resin from the second supply port in the middle of the extruder using a twin screw type side feeder. Moreover, what mix | blended glass fiber was also supplied from the 2nd supply port. All other raw materials were uniformly dry blended with a mixer and supplied to the first supply port. In any composition, 0.00007 parts by weight of a bluing agent (manufactured by Bayer: Macrolex Violet B (trade name)), 0.1 parts by weight of phosphite based on 100 parts by weight of component A Stabilizer (Asahi Denka Kogyo Co., Ltd .: ADK STAB PEP-8 (trade name)), 0.05 parts by weight of trimethyl phosphate (Daihachi Chemical Industry Co., Ltd .: TMP (trade name)), and 0.05 A part by weight of a hindered phenol antioxidant (Ciba Specialty Chemicals Co., Ltd .: Irganox 1076 (trade name)) was blended (not shown in the table).

(Ii) Production of molded product Using the obtained pellets, a large molding machine (made by Meiki Seisakusho Co., Ltd .: MDIP2100, maximum clamping force 33540 kN) equipped with a platen 4-axis parallel control mechanism capable of injection press molding. Then, press molding was carried out to produce a car roof molded article shown in FIG. Such a molding machine is accompanied by a hopper dryer capable of sufficiently drying the pellets as described above, and the dried pellets were used for molding.

  For materials that do not contain the C and D components, the cylinder temperature is 300 ° C., the hot runner set temperature is 290 ° C., the mold temperature is 120 ° C. on the fixed side, and 110 ° C. on the movable side. The cylinder temperature was 285 ° C, the hot runner set temperature was 275 ° C, the mold temperature was 115 ° C on the fixed side, and 105 ° C on the movable side. Other conditions were a filling time of 24 seconds, a press stroke of 5 mm, and a cooling time of 150 seconds. Further, the movable mold parting surface was not in contact with the fixed mold parting surface in the final forward position. As the runner, a hot runner having a diameter of 7 mmφ was used.

(Iii) Hard coat treatment Some molded products were subjected to a hard coat treatment (indicated as "present" in the hard coat column in the table).
(Iii-1) Adjustment of hard coating agent (in the following description, “part” means “part by weight”)
(Iii-1-1) Production of acrylic copolymer (EMA-HEMA (I)) 102.7 parts of ethyl methacrylate (hereinafter abbreviated as EMA) in a flask equipped with a reflux condenser and a stirrer and purged with nitrogen. 13 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), 0.18 part of azobisisobutyronitrile (hereinafter abbreviated as AIBN) and 200 parts of 1,2-dimethoxyethane were added and 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 98 parts of a copolymer (EMA-HEMA (I)) having an EMA / HEMA composition ratio of 90/10 (molar ratio). The copolymer had a hydroxyl value of 48.7 mgKOH / g and a weight average molecular weight of 90,000 in terms of polystyrene as measured by GPC (column; Shodex GPCA-804, eluent: THF).

(Iii-1-2) Preparation of first layer acrylic resin composition (HC-1) 10 parts of EMA-HEMA (I) and UV absorber (Ciba Specialty Chemicals Co., Ltd .: “Tinuvin 411L” (product) Name)) 2.00 parts is dissolved in a mixed solvent consisting of 50 parts of methyl isobutyl ketone and 25 parts of 2-butanol, and 1 equivalent of isocyanate group is added to 1 equivalent of hydroxy group of EMA-HEMA (I) in this solution. 2.96 parts of a polyisocyanate compound precursor (Degussa Japan Co., Ltd .: “VESTANATB 1358/100” (trade name)) was added, and 0.005 part of dimethyltindineodecanoate, silane coupling 1.5 parts of an agent (manufactured by Nippon Unicar Co., Ltd .: “APZ-6633 5% ethanol solution” (trade name)) was added. 5 and stirred for 30 min at ° C., acrylic resin composition for the first layer (HC-1) was prepared.

(Iii-1-3) Preparation of organosiloxane resin composition for second layer (HC-2) Water-dispersed colloidal silica dispersion (manufactured by Catalyst Chemical Industries, Ltd .: “Cataloid SN30” (trade name), solid content 100 parts of 30% by weight) 0.1 part of 35% hydrochloric acid was added and stirred, and 136 parts of methyltrimethoxysilane and 20.3 parts of dimethyldimethoxysilane were added to this dispersion while cooling in an ice-water bath. An organosiloxane resin composition is prepared by adding 1 part of a 45% choline methanol solution and 4 parts of acetic acid as a curing catalyst and a pH adjuster to the reaction liquid obtained by stirring this mixed liquid at 25 ° C. for 6 hours, and diluting with 200 parts of isopropanol. A product (HC-2) was prepared.

(Iii-2) Application of hard coat agent The vehicle roof molded article produced above is 1 hour at 130 ° C. for materials not containing C and D components, and about materials containing C and D components. Annealing treatment was performed in a clean oven at 120 ° C. for 2 hours. Thereafter, the acrylic resin composition for the first layer (HC-1) prepared as described above is applied on both sides by a dip coating method so that the liquid does not accumulate, and after standing at 25 ° C. for 20 minutes, it does not contain C component and D component. The material was heat-cured in a hot-air circulating oven at 130 ° C. for 1 hour at 130 ° C. and the material containing the C component and D component at 120 ° C. for 2 hours, and a cured film having a thickness of 4.0 μm was laminated. Next, the second layer organosiloxane resin composition (HC-2) prepared as described above was applied on both surfaces by the dip coating method on the coating surface of the molded article, left at 25 ° C. for 20 minutes, and then 2 ° C. at 120 ° C. A cured film having a thickness of 4.0 μm was laminated by heat curing in a hot air circulating oven.

(Iv) Lamination of heat ray cut film For some molded products, a PET type heat ray cut film (manufactured by Teijin Ltd .: Reftel ZS05G) was laminated on the outside of the molded product ("Yes" in the heat ray film column in the table). ”). In addition, about the thing with a hard-coat process, it laminated after the hard-coat process.
In addition, the symbol which shows each component of Table 1 and Table 2 means the following, respectively.

(Component A: aromatic polycarbonate)
A-1: Bisphenol A type aromatic polycarbonate resin powder produced by the phosgene method having a viscosity average molecular weight of 23,900 and a chlorine content of 40 ppm (manufactured by Teijin Chemicals Ltd .: “Panlite 1-1250WP” (trade name), In addition, bromine content was not recognized)

(B component: polymer fine particles)
B-1: Beaded crosslinked acrylic particles (manufactured by Sekisui Plastics Co., Ltd .: “Techpolymer MBX-5” (trade name), average particle size: 5 μm)
B-2: Bead-like crosslinked silicone particles (manufactured by Toshiba Silicone Co., Ltd .: “Tospearl 120” (trade name), average particle diameter: 2 μm)
(For comparison of B component)
B-3: Glass milled fiber (manufactured by Nitto Boseki Co., Ltd .: “PFE-301” (trade name), fiber diameter 9 μm, average fiber length 40 μm)
B-4: Calcium carbonate particles (manufactured by Sipro Kasei Co., Ltd .: “Sipron A” (trade name), weight average particle diameter 10 μm)

(C component: layered silicate)
C-1: Synthetic mica (manufactured by Topy Industries Co., Ltd .: “DMA-80E” (trade name)) ion-exchanged almost completely with onium ion chloride (didecyldimethylammonium chloride) What was weighed and obtained by filtering again after stirring and washing with 10000 parts by weight of ion-exchanged water using a stirrer. The chlorine content after drying was 208 ppm. The chlorine content was precisely weighed about 2 g of the organically modified layered silicate, placed in a 300 ml beaker, 200 ml of distilled water was added, and the mixture was stirred for 1 hour at 1000 rpm with a stirrer using a stir bar. The extracted suspension was diluted 10-fold with distilled water, and using filters (ADVANTEC: “Dismic-13cp” pore size 0.20 μm and Nippon Dionex: “Dillex-IC” pore size 0.22 μm). After filtration, the obtained filtrate was measured by measuring with an ion chromatograph (Dionex: “DX-100”) and quantifying the amount of chlorine. Note that bromine was not detected.

(D component)
D-1: Styrene-maleic anhydride copolymer (manufactured by Nova Chemical Japan Co., Ltd .: “DYLARK 332-80” (trade name), maleic anhydride amount of about 15% by weight)
D-2: (2-Isopropenyl-2-oxazoline) -styrene-acrylonitrile copolymer (manufactured by Nippon Shokubai Co., Ltd .: “EPOCROS RAS-1005” (trade name), about 2-isopropenyl-2-oxazoline amount 5% by weight)

(For comparison of component C)
GF: Glass fiber (manufactured by Nippon Electric Glass Co., Ltd .: “ECS-03T-511” (trade name), fiber diameter 13 μm, cut length 3 mm)

(Other)
S100A: monoester composed of glycerin and aliphatic carboxylic acid (manufactured by Riken Vitamin Co., Ltd .: “Riquemar S-100A” (trade name))
EW: full ester composed of pentaerythritol and aliphatic carboxylic acid (Riken Vitamin Co., Ltd .: “Ricester EW-400” (trade name))
PSR: Coumarin fluorescent whitening agent (manufactured by Hackol Chemical Co., Ltd .: “Hackol PSR” (trade name))
CEiP: 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) (manufactured by Takemoto Yushi Co., Ltd .: “CEi-P” (trade name))
UVINUL: 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] propane (manufactured by BASF) : "Uvinul 3030" (trade name))
T-1577: 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol (manufactured by Ciba Specialty Chemicals Co., Ltd .: “Tinuvin 1577” (product) Name))
TiO2: Titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd .: “Taipeke PC-3” (trade name))

  From the results shown in Table 1 and Table 2, the roof molded article made of the resin composition according to the present invention achieves good dimensional accuracy, appearance, and light uniformity, and achieves a vehicle interior with an unprecedented atmosphere. You can see that In particular, those containing a C component and a D component satisfy an even lower dimensional change and are more suitable as a roof molded article. These are also excellent in rigidity, and a higher sense of security can be obtained. It can be seen that when other inorganic fillers are used as the light diffusing agent, it is difficult to obtain a good large molded article. Further, when glass fiber was used as a reinforcing agent, the dimensional accuracy was inferior, and the light uniformity was inferior.

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

Explanation of symbols

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

Claims (11)

  For vehicles formed from a light-diffusing polycarbonate resin composition comprising 100 parts by weight of aromatic polycarbonate (component A) and 0.1 to 30 parts by weight of polymer fine particles (component B) having an average particle size of 0.01 to 50 μm Exterior molded product. 2. The vehicle exterior molded product according to claim 1, wherein the vehicle exterior molded product has a maximum projected area of 500 to 50,000 cm ² .   The vehicle exterior molded article according to claim 2, wherein the vehicle exterior molded article is manufactured by an injection press molding method.   The light diffusing polycarbonate resin composition further contains 0.1 to 20 parts by weight of a layered silicate (C component) having a cation exchange capacity of 50 to 200 meq / 100 g based on 100 parts by weight of the component A. The vehicle exterior molded article according to any one of claims 1 to 3, wherein the molded article is a resin composition.   The light diffusing polycarbonate resin composition is a resin composition comprising a compound having an affinity for an aromatic polycarbonate and a hydrophilic component (D component) based on 100 parts by weight of the A component. The vehicle exterior molded article according to claim 4.   The component C is a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g, and at least 40% of the cation exchange groups are exchanged with organic onium ions. Item 6. The vehicle exterior molded article according to Item 4 or Claim 5. 7. The vehicle exterior molded article according to claim 6, wherein the organic onium ion in the component C is represented by the following general formula (I).

[In the general formula (I), M represents a nitrogen atom or a phosphorus atom. R ^{1 to} R ⁴ represent the same or different organic groups, at least one of which is an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, and the remaining groups are carbon atoms. It is an alkyl group having 1 to 5 atoms. ]   The said D component is an aromatic vinyl polymer (D-1 component) which has a functional group which consists of a carboxyl group and / or its derivative (s), The any one of Claims 5-7 characterized by the above-mentioned. Car exterior molded products.   The vehicle exterior molded article according to claim 8, wherein the component D-1 is a styrene-maleic anhydride copolymer.   The resin composition comprising the A component to the D component is prepared by melt-kneading the C component and the D component in advance and then melt-kneading the melt-kneaded product with the A and B components. The vehicle exterior molded article according to any one of claims 5 to 9, wherein the vehicle exterior molded article is provided.   The vehicle exterior molded product according to any one of claims 1 to 10, wherein the vehicle exterior molded product is subjected to a hard coat treatment on a surface thereof.

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