JP2019123441A - Automobile interior-exterior member - Google Patents

Abstract

To provide an automobile interior-exterior member excellent in impact resistance, heat resistance, scratch resistance, and light resistance.SOLUTION: An automobile interior-exterior member is made of a polycarbonate resin composition which comprises: a specific polycarbonate resin; a butadiene-methyl methacrylate-styrene-based rubber; dibutylhydroxytoluene; diphenyl dimethicone having a kinematic viscosity of 4000-5500 cSt at 23°C; a hindered amine-based light resistant stabilizer having a melting point of 125°C-130°C; a benzotriazole-based light resistant stabilizer having a melting point of 102°C-106°C; tris(2,4-di-t-butylphenyl)phosphite; and a hindered phenol-based antioxidant having a molecular weight of 1100-1200, each in a predetermined amount.SELECTED DRAWING: None

Description

  The present invention relates to a specific polycarbonate resin, butadiene-methyl methacrylate-styrene rubber, dibutyl hydroxytoluene, diphenyl dimethicone having a kinematic viscosity of 4000 to 5500 cSt at 23 ° C., hindered amine light stability having a melting point of 125 ° C to 130 ° C. C., a benzotriazole light stabilizer having a melting point of 102.degree. C. to 106.degree. C., a tris (2,4-di-t-butylphenyl) phosphite, and a polycarbonate containing a hindered phenolic antioxidant having a molecular weight of 1100 to 1200 The present invention relates to an automobile interior and exterior member comprising a resin composition.

  BACKGROUND ART Heretofore, aromatic polycarbonate resins are widely used as engineering plastics having excellent heat resistance, impact resistance, and transparency in various applications such as automobiles and OA equipment fields. On the other hand, aromatic polycarbonate resins are generally manufactured using raw materials derived from petroleum resources, but given the recent situation where there is a concern over the exhaustion of petroleum resources, they can be obtained from biomass resources such as plants There is a need to provide plastic molded products using raw materials. In addition, carbon-neutral, plant-derived monomers are used as raw materials, even if they are disposed of after disposal, because it is feared that global warming due to increased carbon dioxide emissions and accumulation will lead to climate change etc. There is a need for the development of plastic moldings made of plastic, particularly in the field of large moldings.

On the other hand, various polycarbonate resins having a plant-derived monomer as a raw material have been developed.
For example, it is proposed to obtain a polycarbonate resin by using isosorbide as a plant-derived monomer and transesterification with diphenyl carbonate (see, for example, Patent Document 1). Further, as a copolycarbonate of isosorbide and another dihydroxy compound, a polycarbonate resin obtained by copolymerizing isosorbite and bisphenol A has been proposed (see, for example, Patent Document 2), and further, copolymerization of isosorbide and an aliphatic diol By doing this, an attempt is made to improve the rigidity of a homopolycarbonate resin composed of isosorbide (see, for example, Patent Document 3).

  Furthermore, by mixing polycarbonate resins having different composition ratios among two or more of polycarbonate resins obtained by copolymerizing isosorbide and a dihydroxy compound, it has high flowability and heat resistance, and it has flow marks and tiger marks at the time of injection molding. And the like, and it is known that a molded article with few molding appearance defects such as, and good impact resistance can be obtained (see Patent Document 4).

  Moreover, it is described that the polycarbonate resin composition which contains the elastomer which is alkyl (meth) acrylate and butadiene as a core layer is excellent in transparency, light resistance, and impact resistance in polycarbonate resin using isosorbide ( Patent Documents 5 and 6).

British Patent No. 1079686 specification JP-A-56-55425 International Publication No. 04/111106 Pamphlet JP, 2014-208800, A WO 2012/132492 pamphlet International Publication No. 2012/132493 brochure

  However, for automobile interior and exterior articles, improvements in heat resistance, scratch resistance and light resistance have been required while maintaining high impact resistance. Therefore, even when the molded articles described in Patent Documents 4 to 6 are used as automobile interior and exterior articles, further improvements in heat resistance, scratch resistance and light resistance have been required.

  That is, the object of the present invention is to solve the above-mentioned conventional problems and to provide an automobile interior and exterior article having excellent impact resistance, heat resistance, scratch resistance and light resistance.

  As a result of investigations by the present inventors, a specific polycarbonate resin in which a carbonate copolymer containing a constituent unit derived from a dihydroxy compound having a specific site is melt mixed with a plurality of carbonate copolymers having different copolymerization ratios, Butadiene-butyl methacrylate-methyl methacrylate type rubber, dibutyl hydroxytoluene, diphenyl dimethicone having a kinematic viscosity of 4000 to 5500 cSt at 23 ° C., hindered amine light stabilizer having a melting point of 125 ° C. to 130 ° C., a melting point of 102 ° C. to A polycarbonate resin composition comprising a benzotriazole-based light stabilizer having a temperature of 106 ° C., tris (2,4-di-t-butylphenyl) phosphite and a hindered phenol-based antioxidant having a molecular weight of 1100 to 1200 has the above problems. Find that it can be solved The present invention has been completed.

That is, the present invention provides the following.
[1] An automobile interior and exterior member comprising a polycarbonate resin composition having a polycarbonate resin and butadiene-methyl methacrylate-styrene rubber, wherein the polycarbonate resin is derived from a dihydroxy compound represented by the following general formula (1) A melt mixture of a plurality of carbonate copolymers having a structural unit (structural unit (1)) and a structural unit (CHDM unit) derived from cyclohexanedimethanol, and having different copolymerization ratios, The content ratio of the molar ratio of the structural unit (1) to the CHDM unit is 61/39 to 63/37 (molar ratio), and the above polycarbonate resin and butadiene-methyl methacrylate in the above polycarbonate resin composition -Butadiene-metac with respect to a total of 100 parts by weight of styrenic rubber It contains 4.0 to 6.0 parts by weight of methyl methacrylate-styrene rubber, and further contains the following components (A) to (F) as total of the polycarbonate resin and butadiene-methyl methacrylate-styrene rubber described above. Interior and exterior members for automobiles containing the following content per 100 parts by weight.
Component (A): Dibutylhydroxytoluene: 0.001 to 0.015 parts by weight.
Component (B): diphenyl dimethicone having a kinematic viscosity at 25 ° C. of 4000 to 5500 cSt: 0.05 to 0.31 parts by weight.
Component (C): A hindered amine light stabilizer having a melting point of 125 ° C. to 130 ° C .: 0.05 to 0.21 parts by weight.
Component (D): a benzotriazole light stabilizer having a melting point of 102 ° C. to 106 ° C .: 0.05 to 0.31 parts by weight.
Component (E): tris (2,4-di-t-butylphenyl) phosphite: 0.049 to 0.051 parts by weight.
Component (F): A hindered phenolic antioxidant having a molecular weight of 1100 to 1200: 0.09 to 0.11 parts by weight.

[2] The interior / exterior member for an automobile according to [1], wherein the refractive index of diphenyl dimethicone of the component (B) is 1.49 to 1.51.
[3] The interior / exterior member for an automobile according to [1] or [2], wherein the component (C) is a hindered amine light stabilizer having a plurality of piperidine structures.
[4] The interior and exterior member for an automobile according to [3], wherein a plurality of piperidine structures possessed by the hindered amine light stabilizer of the component (C) are linked to one alkane chain by an ester bond.

  According to the present invention, since a specific polycarbonate resin composition is used, an automobile interior and exterior article having excellent impact resistance, heat resistance, scratch resistance and light resistance can be provided.

  Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention. Further, in the present invention, "wt%" and "mass%", "weight ppm" and "mass ppm", and "parts by weight" and "parts by weight" are respectively synonymous.

The present invention relates to an interior / exterior member for an automobile comprising a polycarbonate resin composition containing a predetermined amount of a specific component.
[Polycarbonate resin composition]
The polycarbonate resin composition is a specific polycarbonate resin, butadiene-methyl methacrylate-styrene rubber (hereinafter may be referred to as "butadiene rubber"), dibutyl hydroxytoluene (component (A)), 23 ° C. Diphenyldimethicone (component (B)) having a kinematic viscosity of 4000 to 5500 cSt, hindered amine light stabilizer (component (C)) having a melting point of 125 to 130 ° C., benzotriazole having a melting point of 102 to 106 ° C. Light stabilizers ((D) component), tris (2,4-di-t-butylphenyl) phosphite ((E) component) and hindered phenolic antioxidants having a molecular weight of 1100 to 1200 ((F) component) In a predetermined amount.

[Polycarbonate resin]
The polycarbonate resin of the present invention is a melt mixture in which a plurality of carbonate copolymers are melt mixed.
The carbonate copolymer is a carbonate copolymer obtained by polymerizing at least using a dihydroxy compound represented by the following general formula (1) and cyclohexane dimethanol as a dihydroxy compound, and When the structural unit derived from the dihydroxy compound represented by 1) (hereinafter, may be referred to as "structural unit (1)"), and the structural unit derived from cyclohexane dimethanol (hereinafter referred to as "CHDM unit" And a carbonate copolymer having at least
The polycarbonate resin is a mixture obtained by melt-mixing a plurality of carbonate copolymers different in the copolymerization ratio of the polyol component, specifically, the copolymerization ratio of the structural unit (1) and the CHDM unit. is there.

<Dihydroxy Compound Represented by Formula (1)>
Examples of the dihydroxy compound represented by the above formula (1) include isosorbide, isomannide and isoidet which are in a stereoisomer relationship.
The dihydroxy compounds represented by the formula (1) may be used alone or in combination of two or more.
Among the dihydroxy compounds represented by the formula (1), isosorbide which is abundantly available as a resource, is readily available, and is obtained by dehydration condensation of sorbitol produced from various starches is obtained and produced. Most preferred from the viewpoints of ease of application, optical properties and moldability.

<Cyclohexane dimethanol>
Specifically as said cyclohexane dimethanol, a 1, 2- cyclohexane dimethanol, a 1, 3- cyclohexane dimethanol, 1, 4- cyclohexane dimethanol etc. are mentioned.

<Carbon diester>
The above polycarbonate resin can be produced by a commonly used polymerization method, and the polymerization method may be any of an interfacial polymerization method using phosgene, and a melt polymerization method in which ester exchange reaction with carbonic acid diester is carried out. Preference is given to melt polymerization processes in which the dihydroxy compound is reacted with a less toxic carbonate diester in the presence of a catalyst.

  In this case, the polycarbonate resin can be obtained by a melt polymerization method in which a dihydroxy compound at least containing a dihydroxy compound represented by the general formula (1) and cyclohexanedimethanol and a carbonic diester are transesterified.

  As a carbonic acid diester to be used, what is normally represented by following formula (2) is mentioned. One of these carbonic acid diesters may be used alone, or two or more thereof may be mixed and used.

In Formula (2) above, A ¹ and A ² are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic group.

  Examples of the carbonic acid diester represented by the above formula (2) include, for example, substituted diphenyl carbonate such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate and di-t-butyl carbonate, but preferably diphenyl It is a substituted diphenyl carbonate such as carbonate, particularly preferably diphenyl carbonate. The carbonic acid diester may contain impurities such as chloride ions, and these impurities may inhibit the polymerization reaction or may deteriorate the color of the obtained polycarbonate resin. It is preferable to use one purified by distillation or the like.

  The carbonic diester is preferably used in a molar ratio of 0.90 to 1.20, more preferably 0.95 to 1.10, with respect to the total dihydroxy compound used in the melt polymerization, and 0 It is even more preferred to use a molar ratio of .96 to 1.10, particularly preferably a molar ratio of 0.98 to 1.04.

  When this molar ratio is less than 0.90, the terminal hydroxyl group of the produced polycarbonate resin is increased, the thermal stability of the polymer is deteriorated, coloration is caused when molding the polycarbonate resin composition, and transesterification is caused. The reaction rate may be reduced or the desired high molecular weight product may not be obtained.

  In addition, when this molar ratio is greater than 1.20, the rate of transesterification reaction is reduced under the same conditions, which makes it difficult to produce a polycarbonate resin having a desired molecular weight, and residual in the produced polycarbonate resin. The amount of carbonic acid diester increases, and this residual carbonic acid diester may cause undesirable odor during molding or molding, and may increase the heat history during polymerization reaction, resulting in the hue of the polycarbonate resin obtained. And may deteriorate the light resistance.

  Furthermore, when the molar ratio of carbonic diester to the total dihydroxy compound increases, the amount of residual carbonic diester in the obtained polycarbonate resin may increase, and these may absorb ultraviolet rays to deteriorate the light resistance of the polycarbonate resin. Not desirable. The concentration of carbonic diester remaining in the polycarbonate resin of the present invention is preferably 200 ppm by weight or less, more preferably 100 ppm by weight or less, particularly preferably 60 ppm by weight or less, and particularly preferably 30 ppm by weight or less. However, the polycarbonate resin may actually contain unreacted carbonic acid diester, and the lower limit value of the unreacted carbonic acid diester concentration in the polycarbonate resin is usually 1 ppm by weight.

<Transesterification catalyst>
The polycarbonate resin of the present invention is produced by transesterification between a dihydroxy compound represented by the above formula (1) and a dihydroxy compound containing cyclohexanedimethanol as described above and a carbonic acid diester represented by the above formula (2) be able to. More specifically, it is obtained by transesterification reaction and removal of by-produced monohydroxy compounds etc. out of the system. In this case, melt polymerization is usually carried out by transesterification in the presence of a transesterification catalyst.

  Examples of the transesterification reaction catalyst (hereinafter sometimes referred to as “catalyst”) that can be used in the production of the polycarbonate resin of the present invention include Group 1 or 2 in the long period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005) And basic compounds such as metal compounds of basic groups (hereinafter simply referred to as “group 1” and “group 2”), basic boron compounds, basic phosphorus compounds, basic ammonium compounds, amine compounds and the like. Among these, preferably Group 1 metal compounds and / or Group 2 metal compounds are used.

  In addition to the Group 1 metal compound and / or the Group 2 metal compound, it is also possible to jointly use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound. It is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.

  The group 1 metal compound and / or group 2 metal compound is usually used in the form of a hydroxide or a salt such as a carbonate, carboxylate or phenol salt, but it is easy to obtain and handle From the viewpoint of ease, hydroxides, carbonates and acetates are preferred, and from the viewpoint of hue and polymerization activity, acetates are preferred.

  Examples of Group 1 metal compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, lithium hydrogencarbonate, cesium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium carbonate, Cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, sodium stearate, lithium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, lithium borohydride , Sodium phenylated boron, potassium potassium phenylated, lithium lithium phenylated, cesium cesium phenylated, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, hydrogen phosphate 2 sodium Hydrogen potassium diphosphate, dilithium hydrogen phosphate disodium hydrogen phosphate disodium phenyl phosphate dipotassium phenyl phosphate dilithium phenyl phosphate dilithium cesium phosphate phenyl cesium disodium sodium potassium lithium Examples thereof include alcoholate of cesium, phenolate, disodium salt of bisphenol A, dipotassium salt of dipotassium, dilithium salt and disodium cesium salt, and among them, cesium compounds and lithium compounds are preferable.

  Examples of Group 2 metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogencarbonate, barium hydrogencarbonate, magnesium hydrogencarbonate, magnesium hydrogencarbonate, strontium hydrogencarbonate, calcium carbonate, barium carbonate, magnesium carbonate, Strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like can be mentioned. Among them, magnesium compounds, calcium compounds, barium compounds are preferable, magnesium compounds and Or calcium compounds are more preferred.

  As a basic boron compound, for example, tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzyl Sodium salts such as boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, strontium salts, etc. Be

  Examples of the basic phosphorus compound include triethyl phosphine, tri-n-propyl phosphine, triisopropyl phosphine, tri-n-butyl phosphine, triphenyl phosphine, tributyl phosphine, and quaternary phosphonium salts.

  As the basic ammonium compound, for example, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethylethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, trimethyl phenyl ammonium hydroxide, Triethylmethyl ammonium hydroxide, triethyl benzyl ammonium hydroxide, triethyl phenyl ammonium hydroxide, tributyl benzyl ammonium hydroxide, tributyl phenyl ammonium hydroxide, tetraphenyl ammonium hydroxide, benzyl triphenyl ammonium hydroxide, methyl triphenyl ammonium hydroxide Sid, butyl triphenyl ammonium hydroxide, and the like.

  Examples of amine compounds include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, and the like. -Dimethylamino imidazole, 2-methoxy imidazole, imidazole, 2-mercapto imidazole, 2-methyl imidazole, amino quinoline etc. are mentioned.

  Among the above, using at least one metal compound selected from the group consisting of a group 2 metal compound and a lithium compound as a catalyst is excellent in various physical properties such as transparency, hue and light resistance of the obtained polycarbonate resin. It is preferable to assume.

  Also, in order to make the transparency, hue and light resistance of the polycarbonate resin particularly excellent, the catalyst is at least one metal compound selected from the group consisting of a magnesium compound, a calcium compound and a barium compound. Preferably, at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds is preferable.

  In the case of Group 1 metal compounds and / or Group 2 metal compounds, the amount of the catalyst used is preferably 0.1 to 300 μmol, and more preferably 0.1 to 300 μmol, in terms of metal per 1 mol of all dihydroxy compounds to be subjected to the reaction. It is in the range of 0.1 to 100 μmol, more preferably 0.5 to 50 μmol, still more preferably 1 to 25 μmol.

  Among the above, when a compound containing at least one metal selected from the group consisting of Group 2 metals is used, the amount of metal conversion is preferably 0.1 μmol or more, more preferably 0.1 mol or more per mol of all dihydroxy compounds to be subjected to the reaction. Is preferably 0.5 μmol or more, particularly preferably 0.7 μmol or more. The upper limit is preferably 20 μmol, more preferably 10 μmol, particularly preferably 3 μmol, and most preferably 2.0 μmol.

  If the amount of the catalyst used is too small, the polymerization activity necessary for producing a polycarbonate resin having a desired molecular weight can not be obtained, and sufficient fracture energy may not be obtained. On the other hand, when the amount of the catalyst used is too large, not only the hue of the obtained polycarbonate resin is deteriorated, but also by-products are generated to cause a decrease in fluidity and generation of gel, resulting in brittle fracture. In some cases, it may be difficult to produce the polycarbonate resin of the target quality.

<Method for Producing Carbonate Copolymer>
The above-mentioned carbonate copolymer is obtained by melt-polymerizing a dihydroxy compound containing a dihydroxy compound represented by the above general formula (1) and cyclohexanedimethanol and a diester of carbon dioxide by a transesterification reaction. Preferably, the compound and the carbonic diester are uniformly mixed prior to the transesterification reaction.

  The mixing temperature is usually 80 ° C. or more, preferably 90 ° C. or more, and the upper limit is usually 250 ° C. or less, preferably 200 ° C. or less, and more preferably 150 ° C. or less. Among them, 100 ° C. or more and 120 ° C. or less are preferable. If the temperature of mixing is too low, the dissolution rate may be slow or the solubility may be insufficient, often causing problems such as solidification, and if the temperature of mixing is too high, thermal degradation of the dihydroxy compound may be caused, resulting in The color of the polycarbonate resin obtained may be deteriorated, which may adversely affect the light resistance.

The carbonate copolymer is preferably produced by melt polymerization in multiple stages using a plurality of reactors using a catalyst.
The type of reaction may be batch type, continuous type, or any combination of batch type and continuous type.
Furthermore, it is effective to use a reflux condenser in the polymerization reactor in order to suppress the amount of monomers to be distilled out, and the effect is particularly large in a reactor at the initial stage of polymerization where there are many unreacted monomer components.
In order to maintain the polymerization rate appropriately and to suppress the distillation of the monomer, the hue, thermal stability, light resistance and the like of the finally obtained polycarbonate resin (mixture of carbonate copolymer) are not impaired It is important to select the type and amount of catalyst mentioned above.

  In the production of the above-mentioned carbonate copolymer, if the number of the above-mentioned reactors is two or more, a plurality of reaction stages having different conditions are further provided in the reactor, temperature / pressure is continuously changed, etc. You may

  In the production of the above-mentioned carbonate copolymer, the catalyst can be added to the raw material preparation tank and the raw material storage tank, or directly to the reactor, but from the viewpoint of supply stability and control of melt polymerization, A catalyst feed line is installed in the middle of the feed line before being fed to the reactor, preferably fed as an aqueous solution.

  As polymerization conditions, it is preferable to obtain the prepolymer at relatively low temperature and low vacuum at the initial stage of polymerization, and to raise the molecular weight to a predetermined value at relatively high temperature and high vacuum at the latter stage of polymerization. Proper selection of the jacket temperature and the internal temperature at the stage and the pressure in the reaction system is important from the viewpoint of the color and light resistance of the obtained polycarbonate resin. For example, if the temperature or pressure is changed too quickly before the polymerization reaction reaches a predetermined value, unreacted monomers will distill, causing the molar ratio of the dihydroxy compound to the carbonic acid diester to fall, and the polymerization rate to decrease. As a result, it may not be possible to achieve the object of the present invention as a result of not obtaining a polymer having a predetermined molecular weight or end group.

  If the temperature of the transesterification reaction is too low, it causes a decrease in productivity and an increase in the heat history to the product, and when it is too high, it may not only cause the volatilization of the monomer but also promote the decomposition and coloring of the carbonate copolymer. There is.

  In the production of the above-mentioned carbonate copolymer, the method of transesterification reaction between the dihydroxy compound represented by the above general formula (1) and the dihydroxy compound containing cyclohexanedimethanol and the carbonic diester in the presence of a catalyst is generally two steps. It is implemented by the above multistage process.

  When the transesterification temperature is excessively high, the hue may be deteriorated when it is formed into a molded article, and brittle fracture may easily occur. If the transesterification temperature is excessively low, the target molecular weight may not increase, and the molecular weight distribution may be broad, and the impact strength may be poor. In addition, when the residence time of the transesterification reaction is excessively long, brittle fracture may easily occur. If the residence time is too short, the target molecular weight may not increase and the impact strength may be poor.

  In addition, Group 1 metals, in particular lithium, sodium, potassium, cesium, especially sodium, potassium and cesium may be mixed not only from the catalyst used but also from raw materials and reactors, but these metals may be polycarbonate resin The total content of these compounds in the polycarbonate resin of the present invention is preferably as small as possible because if it is contained in a large amount, the total amount of these compounds in the polycarbonate resin of the present invention is usually 1 weight It is at most ppm, preferably at most 0.8 ppm by weight, more preferably at most 0.7 ppm by weight.

  The amount of metal in the polycarbonate resin (carbonate copolymer mixture) can be measured by various methods known in the prior art, but after the metal in the polycarbonate resin is recovered by a method such as wet ashing, atomic emission is obtained. , Atomic absorption, inductively coupled plasma (ICP), and the like.

The carbonate copolymer of the present invention is generally solidified by cooling after melt polymerization as described above, and is pelletized by a rotary cutter or the like.
Although the method of pelletization is not limited, for example, a method of extracting polycarbonate resin in a molten state from a final polymerization reactor, cooling and solidifying it in the form of a strand and pelletizing it, uniaxial polymerization in a molten state from a final polymerization reactor Alternatively, the resin is supplied to a twin-screw extruder, melted and extruded, and then solidified by cooling and pelletized, or it is extracted from the final polymerization reactor in the molten state, cooled and solidified in the form of strands and pelletized once After that, the resin is again supplied to a single-screw or twin-screw extruder, and after melt extrusion, it is cooled and solidified to pelletize it.

  At that time, in the extruder, degassing the remaining monomer under reduced pressure, a heat stabilizer, a neutralizing agent, an ultraviolet absorber, a mold release agent, a colorant, an antistatic agent, a lubricant, a lubricant, which are generally known. It is also possible to add and knead plasticizers, compatibilizers, flame retardants and the like.

  Moreover, in order to prevent the deterioration of the molecular weight in shaping | molding etc. and the deterioration of a hue, 1 type (s) or 2 or more types of thermal stabilizers may be mix | blended with the carbonate copolymer manufactured in this way.

Such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid.
Such a heat stabilizer can be additionally blended in addition to the addition amount added at the time of melt polymerization. That is, after blending an appropriate amount of a phosphorous acid compound or a phosphoric acid compound to obtain a polycarbonate resin, if a phosphorous acid compound is further blended by a blending method described later, the transparency during polymerization is reduced, and coloring is caused. And heat resistance can be avoided, and more heat stabilizers can be blended to prevent the deterioration of the hue.

  The content of these heat stabilizers is preferably 0.0001 to 1 parts by weight, more preferably 0.0005 to 0.5 parts by weight, per 0.001 parts by weight of the carbonate copolymer, and 0.001 to 0. 2 parts by weight is more preferred.

<Physical Properties of Polycarbonate Resin (or Carbonate Copolymer)>
About the preferable physical property of polycarbonate resin (or carbonate copolymer) of this invention, it shows below.

(Glass-transition temperature)
The glass transition temperature (Tg) of the polycarbonate resin (or carbonate copolymer) of the present invention is less than 145 ° C. If the glass transition temperature of the polycarbonate resin (or carbonate copolymer) is too high beyond this range, it tends to be colored, which may make it difficult to improve the impact strength. In this case, when the shape of the mold surface is transferred to the molded product at the time of molding, it is necessary to set the mold temperature high. Therefore, there is a possibility that the selectable temperature control device may be limited or the transferability of the mold surface may be deteriorated.

The glass transition temperature of the polycarbonate resin (or carbonate copolymer) of the present invention is more preferably less than 140 ° C., still more preferably less than 135 ° C.
The glass transition temperature of the polycarbonate resin (or carbonate copolymer) of the present invention is usually 90 ° C. or higher, preferably 95 ° C. or higher.

As a method of setting the glass transition temperature of the polycarbonate resin (or carbonate copolymer) of the present invention to less than 145 ° C., the proportion of the structural unit (1) in the polycarbonate resin (or carbonate copolymer) may be reduced As a dihydroxy compound to be used for the production of a resin (or carbonate copolymer), an alicyclic dihydroxy compound such as a bisphenol compound in polycarbonate resin (or carbonate copolymer) is selected, or an alicyclic dihydroxy compound having low heat resistance is selected. And the like, and the like.
In addition, the glass transition temperature of the polycarbonate resin (or carbonate copolymer) of this invention is measured by the method as described in the below-mentioned Example.

(Reduced viscosity)
The degree of polymerization of the polycarbonate resin (or carbonate copolymer) of the present invention is as follows: using a mixed solvent of phenol and 1,1,2,2-tetrachloroethane in a weight ratio of 1: 1 as a solvent, the polycarbonate resin concentration is 1. The viscosity is precisely adjusted to 00 g / dl, and is preferably 0.40 dl / g or more as a reduced viscosity (hereinafter sometimes referred to simply as “reduced viscosity”) measured at a temperature of 30.0 ° C. ± 0.1 ° C. More preferably, it is 0.42 dl / g or more, particularly preferably 0.45 dl / g or more, but depending on the use of the polycarbonate resin composition of the present invention, it is 0.60 dl / g or more, more preferably 0.85 dl / g or more There are cases where the ones of is preferably used. The reduced viscosity of the polycarbonate resin (or carbonate copolymer) of the present invention is preferably 2.0 dl / g or less, more preferably 1.7 dl / g or less, and particularly preferably 1.4 dl / g or less. If the reduced viscosity of the polycarbonate resin (or carbonate copolymer) is excessively low, the mechanical strength may be weakened, and if the reduced viscosity of the polycarbonate resin (or carbonate copolymer) is excessively high, molding may be performed. The flowability is lowered, the cycle characteristics are lowered, and the distortion of the molded article tends to be large and the deformation tends to be caused by heat.

[Production of polycarbonate resin (mixture of carbonate copolymer)]
The polycarbonate resin of the present invention is obtained by melt-mixing a plurality of carbonate copolymers having different copolymerization ratios. The temperature of the melt mixing is preferably 235 ° C. to 245 ° C., and preferably 238 ° C. to 242 ° C., as the resin temperature of the melt extrusion port. By setting the content in this range, it is possible to suppress coloring of the polycarbonate resin, heat deterioration or burn and obtain a good polycarbonate resin mixture having high impact strength.

  The range of the copolymerization ratio of each of the plurality of carbonate copolymers different in copolymerization ratio, and the mixing ratio of the plurality of carbonate copolymers, the copolymerization ratio of the polycarbonate resin mixture obtained after mixing has a predetermined range It chooses suitably on the conditions to satisfy. The copolymerization ratio of the polycarbonate resin mixture obtained after this mixing is the amount (mol) of the structural unit (1) relative to the total amount (mol number) of the structural unit (1) and the structural unit (CHDM unit) derived from cyclohexanedimethanol The number) is at least 61 mol%, preferably at least 61.5 mol%. Furthermore, the upper limit is 63 mol% or less, preferably 62.5 mol% or less. The amount (number of moles) of the structural unit (CHDM unit) derived from cyclohexanedimethanol relative to the total amount (number of moles) is 37 mol% or more, preferably 37.5 mol% or more. Furthermore, the upper limit is 39 mol% or less and 38.5 mol% or less.

  When the amount of the structural unit (1) to the total amount (number of moles) is less than 61 mol% (the amount of CHDM units to the total amount (number of moles is more than 39 mol%)), the heat resistance decreases May cause points. On the other hand, when the amount of the structural unit (1) is more than 63 mol% to the total amount (mol number) (the amount of CHDM units to the total amount (mol number) is less than 37 mol%), the impact resistance is lowered. Problems may occur.

[Butadiene-methyl methacrylate-styrene-based rubber (butadiene-based rubber)]
In the polycarbonate resin composition of the present invention, butadiene-methyl methacrylate-styrene rubber (butadiene rubber) is contained in the above-mentioned polycarbonate resin.
In addition, as the butadiene rubber, a core / shell type graft copolymer obtained by graft copolymerizing a polymer component called a rubber component as a core layer and a monomer component copolymerizable therewith as a shell layer is preferable. .

  The core-shell type graft copolymer may be produced by any method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization, and the method of copolymerization is single-stage grafting or multistage grafting. It may be. However, in the present invention, generally, commercially available butadiene-based rubber can be used as it is. Examples of commercially available butadiene-based rubbers include Dow Chemical Japan Ltd .: Paraloid EXL-2690, Mitsubishi Rayon Co., Ltd .: Metabrene E-901, Kaneka Co .: Kaneace M-711, etc. Can be mentioned.

The polymer component of the core layer and the monomer component that can be graft-copolymerized with the core layer, which constitute the shell layer, are (meth) acrylic acid ester compounds.
As a specific example of a (meth) acrylic acid ester compound, methyl methacrylate and butyl methacrylate are mentioned.

  In the core-shell type graft copolymer, one containing 40% by weight or more of a butadiene-styrene copolymer component is preferable, and one containing 60% by weight or more is more preferable. Moreover, what contains 10 weight% or more of (meth) acrylic acid ester components is preferable.

Here, in the core-shell type graft copolymer, the "butadiene-styrene" portion corresponds to the core layer.
These butadiene based rubbers such as core-shell type graft copolymers may be used alone or in combination of two or more.

  The amount of the butadiene-methyl methacrylate-styrene rubber compounded is preferably 4.0 parts by weight or more, more preferably 4.5 parts by weight or more, of the butadiene-methyl methacrylate-styrene rubber in the polycarbonate resin composition. When it is blended in 4.0 parts by weight or more, it is preferable because the impact resistance improvement effect can be easily improved. On the other hand, the upper limit of the compounding amount is preferably 6 parts by weight or less, and more preferably 5.5 parts by weight or less. If it is 6 parts by weight or less, it is preferable from the viewpoints of light resistance and heat resistance of a molded article which is an interior and exterior member for a motor vehicle according to the present invention.

[Method of producing polycarbonate resin composition]
The polycarbonate resin composition of the present invention can be produced by melt-mixing the above-mentioned specific polycarbonate resin, the above-mentioned butadiene rubber and the later-described additives.

  Specifically, for example, a pellet-like plurality of the above-mentioned plural kinds of carbonate copolymers (polycarbonate resin), butadiene rubber and various additives are mixed using an extruder, and extruded into strands, which are pelletized by a rotary cutter or the like. The polycarbonate resin composition of the present invention can be obtained by cutting into a shape of a circle.

<Additives>
At the time of mixing with the specific polycarbonate resin mixture and the butadiene rubber, the following additives can be added and mixed.

((A) component (dibutylhydroxytoluene))
In the polycarbonate resin composition of the present invention, dibutyl hydroxytoluene is blended as the component (A). By blending this, it is possible to exhibit the feature of suppressing the molecular weight reduction at the time of the light resistance test, that is, improving the light resistance.

  In the polycarbonate resin composition of the present invention, the content of the component (A) is preferably 0.001 parts by weight or more, with respect to a total of 100 parts by weight of the polycarbonate resin and butadiene-methyl methacrylate-styrene rubber. .005 parts by weight or more is preferable. If the amount is less than 0.001 part by weight, there may be a problem that the molecular weight reduction suppressing effect in the light resistance test is not sufficient. On the other hand, the upper limit of the content of the component (A) is preferably 0.015 parts by weight, and preferably 0.012 parts by weight. If the amount is more than 0.015 parts by weight, there may be a problem that mold deposit increases.

((B) component (diphenyldimethicone having a kinematic viscosity of 4000 to 5500 cSt at 23 ° C.))
In the polycarbonate resin composition of the present invention, diphenyldimethicone having a kinematic viscosity of 4000 to 5500 cSt at 23 ° C. is blended as the component (B). By blending this, scratch resistance is improved, and abrasion that may occur when using the molded article can be prevented. In addition, since the difference in refractive index with the resin can be made small by the phenyl group contained in diphenyldimethicone, the color developability becomes high, and thus it is possible to obtain a molded article with high quality appearance. Diphenyl dimethicone having a kinematic viscosity of 4000 to 5500 cSt at 23 ° C. has an effect of improving releasability during molding. Therefore, it becomes possible to manufacture a molded article having a complicated shape.

  The diphenyl dimethicone having a kinematic viscosity of 4000 to 5500 cSt at 23 ° C. preferably has a high refractive index from the viewpoint of enhancing the color developability of the molded article of the polycarbonate resin composition. Specifically, the refractive index of diphenyl dimethicone having a kinematic viscosity of 4000 to 5500 cSt at 23 ° C. is preferably 1.49 or more, and more preferably 1.495 or more. When the refractive index is greater than 1.49, the feature of improving the transparency can be exhibited more. On the other hand, the upper limit of the refractive index is preferably 1.51, preferably 1.505. When the refractive index is less than 1.51, the feature of improving the transparency can be exhibited more.

  The difference in refractive index between the polycarbonate resin composition of the present invention and diphenyl dimethicone having a kinematic viscosity of 4000 to 5500 cSt at 23 ° C. is preferably within ± 0.1, and more preferably within ± 0.05. Preferably, it is more preferably ± 0.01 or less. By adjusting the difference in refractive index within the above range, the transparency can be further improved, and the image sharpness at the time of coloring can be further improved.

  In the polycarbonate resin composition of the present invention, the content of the component (B) is preferably 0.05 parts by weight or more, with respect to a total of 100 parts by weight of the above polycarbonate resin and butadiene-methyl methacrylate-styrene rubber. .06 parts by weight or more is preferable. If the amount is less than 0.05 parts by weight, there may be a problem that the molecular weight reduction inhibitory effect in the light resistance test is not sufficient. On the other hand, the upper limit of the content of the component (B) is preferably 0.31 parts by weight, preferably 0.30 parts by weight. If the amount is more than 0.31 parts by weight, there may be a problem that mold deposit increases.

((C) component (a hindered amine light stabilizer having a melting point of 125 ° C. to 130 ° C.))
In the polycarbonate resin composition of the present invention, as the component (C), a hindered amine light stabilizer having a predetermined melting point is blended. By blending this, the feature of molecular weight reduction suppression at the time of light resistance test can be exhibited.

  The melting point of the above-mentioned hindered amine light stabilizers is essentially 125 ° C. or more, preferably 127 ° C. or more. If the temperature is lower than 125 ° C., the light resistance performance may be deteriorated. On the other hand, the upper limit of the melting point is preferably 130 ° C. or less, and preferably 129 ° C. or less. If the temperature is higher than 130 ° C., the compatibility as a resin composition may be deteriorated.

  As the hindered amine light stabilizer having a melting point of 125 ° C. to 130 ° C., one having a structure in which nitrogen is a part of a cyclic structure is preferable, and one having a piperidine structure is more preferable. The piperidine structure specified here may be any structure as long as it is a saturated 6-membered cyclic amine structure, and includes those in which a part of the piperidine structure is substituted by a substituent. Examples of the substituent which the piperidine structure may have include an alkyl group having 4 or less carbon atoms, and a methyl group is particularly preferable. As the amine compound, further, a compound having a plurality of piperidine structures is preferable, and in the case of having a plurality of piperidine structures, a compound in which those piperidine structures are linked to one alkane chain by an ester structure is preferable. As a specific example of such a hindered amine light stabilizer, a compound particularly represented by the following formula (3) can be mentioned.

  In the polycarbonate resin composition of the present invention, the content of the component (C) is preferably 0.05 parts by weight or more, with respect to 100 parts by weight in total of the above polycarbonate resin and butadiene-methyl methacrylate-styrene rubber. .056 parts by weight or more is preferable. If the amount is less than 0.05 parts by weight, there may be a problem that the molecular weight reduction inhibitory effect in the light resistance test is not sufficient. On the other hand, the upper limit of the content of the component (C) is preferably 0.21 parts by weight or less, and more preferably 0.20 parts by weight or less. If the amount is more than 0.21 parts by weight, there may be a problem that mold deposit increases.

((D) Component (benzotriazole-based light stabilizer having a melting point of 102 ° C. to 106 ° C.))
In the polycarbonate resin composition of the present invention, a benzotriazole light stabilizer having a predetermined melting point is blended as the component (D). By blending this, the feature of molecular weight reduction suppression at the time of light resistance test can be exhibited.

  The melting point of the above benzotriazole-based light stabilizers is essentially 102 ° C. or more, preferably 103 ° C. or more. If the temperature is lower than 102 ° C., the light resistance performance may be lowered. On the other hand, the upper limit of the melting point is preferably 106 ° C. or less, and preferably 104 ° C. or less. When the temperature is higher than 106 ° C., there is a case that the light resistance performance at the time of actual exposure becomes difficult to be exhibited.

  More specific examples of benzotriazole-based light stabilizers having a melting point of 102 to 106 ° C. include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) A phenol etc. are mentioned.

  In the polycarbonate resin composition of the present invention, the content of the component (D) is preferably 0.05 parts by weight or more, with respect to 100 parts by weight in total of the polycarbonate resin and butadiene-methyl methacrylate-styrene rubber. .10 parts by weight or more is preferable. If the amount is less than 0.05 parts by weight, there may be a problem that the molecular weight reduction inhibitory effect in the light resistance test is not sufficient. On the other hand, the upper limit of the content of the component (D) is preferably 0.31 parts by weight or less, and more preferably 0.30 parts by weight or less. If the amount is more than 0.31 parts by weight, there may be a problem that mold deposit increases.

((E) component (tris (2,4-di-t-butylphenyl) phosphite))
In the polycarbonate resin composition of the present invention, tris (2,4-di-t-butylphenyl) phosphite is blended as the component (E).
The content of the component (E) in the polycarbonate resin composition of the present invention is preferably 0.049 parts by weight or more, with respect to 100 parts by weight in total of the polycarbonate resin and butadiene-methyl methacrylate-styrene-based rubber. More than a weight part is preferable. When it is blended in the above range or more, it is preferable because the improvement effect of surface impact resistance and impact resistance is easily improved. On the other hand, the upper limit of the blending amount of the component (E) is preferably 0.051 parts by weight or less, and more preferably 0.050 parts by weight or less. If it is the said range or less, it is preferable in the external appearance and heat resistance viewpoint of the molded article which is the interior-exterior member for motor vehicles based on this invention.

(F component (hindered phenolic antioxidant having a molecular weight of 1100 to 1200))
The polycarbonate resin composition of the present invention contains, as the component (F), a hindered phenolic antioxidant having a molecular weight of 1100 to 1200.

  As for the molecular weight of said hindered phenolic antioxidant, 1100 or more is essential, and 1120 or more is preferable. If it is smaller than 1,100, it may have a problem that the oxidation deterioration preventing effect is low. On the other hand, the upper limit of the molecular weight is preferably 1200, preferably 1180. If it is more than 1200, the compatibility as a resin composition may be poor.

  Examples of hindered phenol-based antioxidants having a molecular weight of 1100 to 1200 include compounds such as pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

  In the polycarbonate resin composition of the present invention, the content of the component (F) is preferably at least 0.09 parts by weight with respect to a total of 100 parts by weight of the above polycarbonate resin and butadiene-methyl methacrylate-styrene rubber. .094 parts by weight or more is preferable, and 0.096 parts by weight or more is more preferable. When it is blended in the above range or more, it is preferable because the improvement effect of surface impact resistance and impact resistance is easily improved. On the other hand, the upper limit of the compounding amount of the component (F) is preferably 0.11 parts by weight or less, preferably 0.108 parts by weight or less, and more preferably 0.106 parts by weight or less. If it is the said range or less, it is preferable in the viewpoint of the external appearance of the molded article which is an interior-exterior member for motor vehicles concerning this invention.

<Formulation method>
The compounding method of the polycarbonate resin composition of the present invention, that is, the mixing method of the plurality of types of carbonate copolymer (polycarbonate resin), the butadiene rubber and the additive described above includes, for example, tumbler, V-type blender, There are a method of mixing and kneading with a super mixer, a Nauta mixer, a Banbury mixer, a kneading roll, an extruder or the like, or a solution blending method of mixing in a state dissolved in a common good solvent such as methylene chloride. This is not particularly limited, and any commonly used blending method may be used.

  Specifically, for example, the above-mentioned pellet-like carbonate copolymer and various components are mixed using an extruder, extruded into strands, and cut into pellets with a rotary cutter or the like to obtain the polycarbonate resin composition of the present invention You can get things.

  The components of the polycarbonate resin composition of the present invention thus obtained are mixed and directly or after being pelletized by a melt extruder, they are generally known by extrusion molding method, injection molding method, compression molding method, etc. It can be molded into a desired shape by any molding method.

[Polycarbonate resin molded article]
By molding the polycarbonate resin composition of the present invention, the interior and exterior members for automobiles of the present invention can be obtained.
Preferably, the interior and exterior members for automobiles of the present invention are molded by an injection molding method.
In this case, the interior and exterior members of the present invention of complicated shape can be prepared.

  The invention will now be described in more detail by way of examples. The present invention is not limited at all by these examples. First, the evaluation method will be described.

<Evaluation method>
(1) Measurement of deflection temperature under load The pellets of the polycarbonate resin composition were dried at 90 ° C. for 6 hours using a hot air drier. Next, an ISO test piece for mechanical properties was molded from the dried polycarbonate resin composition using an injection molding machine (EC-75SX manufactured by Toshiba Machine Co., Ltd.). The deflection temperature under load at 1.80 MPa was measured using the obtained ISO test pieces for mechanical properties by the method described in ISO 75-1: 2: 2013.

(2) Measurement of Charpy Impact Strength The notched Charpy impact test was carried out by the method described in ISO 179-1: 2010, ISO 179-2: 1997, using the ISO test pieces for mechanical properties obtained above. The higher the value, the higher the impact resistance.

(3) Light fastness test (ΔE ^* )
A sheet of 100 mm × 100 mm × 2 mmt was molded from the dried polycarbonate resin composition using an injection molding machine (EC-75SX manufactured by Toshiba Machine Co., Ltd.). Using a xenon light resistance tester Ci4000 manufactured by Atlas, in accordance with JIS D 0205, using a xenon arc lamp under conditions of black panel temperature 89 ° C. and relative humidity 50%, a wavelength range of 300 to 400 nm, sample surface radiation intensity The test was conducted at an integrated irradiation intensity of 100 MJ / m ² through an outer glass filter of soda lime glass and an inner filter of borosilicate glass at 100 W / m ² . L ^* a ^* b ^* after irradiation treatment was measured using SE-2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. according to the method described in JIS Z 8722, and ΔE ^* was determined from the value before the test.

(4) Abrasion resistance test Using a surface property measuring machine (manufactured by Shinto Scientific Co., Ltd., type: Tribogear TYPE-14), fold the tissue (Nippon Paper Cresia Co., Ltd. flower box) three folds, and then wear the abrasive element (projecting the bottom Attached to an area of 20 mm x 20 mm) and after making 200 reciprocations at a speed of 9.8 N, stroke 50 mm, 3000 mm / minute on the surface of a sheet (100 mm x 100 mm x 2 mm t) formed in the same manner as in (3), JIS According to the method described in Z 8722, using CM-5 manufactured by Konica Minolta Japan Co., Ltd., measure the L ^* of the wound surface by the D65 / 10 ° light source reflection method, and evaluate the L ^* change rate before and after the abrasion test did. The smaller the value, the better the scratch resistance.

(5) Comprehensive judgment When load deflection temperature is 90 ° C or more, ΔE ^* after light resistance test is less than 2.0, L ^* change ratio before and after abrasion resistance test is 50 or less, and Charpy impact strength is 60 kJ / m ² or more ○, and other than x.

<Raw materials>
<Material for polycarbonate resin>
D7340 R: Isosorbide polycarbonate (ISB / CHDM = 70/30 (molar ratio)), manufactured by Mitsubishi Chemical Corporation.
D5360R: isosorbide polycarbonate (ISB / CHDM = 50/50 (molar ratio)), manufactured by Mitsubishi Chemical Corporation.

<Butadiene rubber>
-EXL-2690 ... butadiene-methyl methacrylate-styrene rubber (Dow Chemical Japan Ltd., Paraloid EXL 2690).
<BA-MA-S rubber>
M-590: butyl acrylate-methyl methacrylate-styrene-based rubber, manufactured by Kaneka Corporation.

<(A) component>
BHT: Dibutylhydroxytoluene, manufactured by API Corporation.
<(B) component>
· KF 54-HV: silicone oil (diphenyl dimethicone), manufactured by Shin-Etsu Chemical Co., Ltd., refractive index 1.503, dynamic viscosity 5000 cSt at 23 ° C
<(C) component>
-(C) -1: LA-57 ... HALS (hindered amine light stabilizer) represented by the following formula (3), manufactured by ADEKA Co., Ltd., melting point: 130 ° C.

-(C) -2: Tinuvin 770DF ... HALS (hindered amine light stabilizer) represented by the following formula (4), manufactured by Ciba Geigy KK, melting point: 84 ° C.

<(D) component>
Seesorb 709: 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, manufactured by Cipro Chemical Industries, Ltd., melting point: 104 ° C.

<(E) component>
AS2112 ... tris (2,4-di-t-butylphenyl) phosphite, manufactured by ADEKA Corporation.
<(F) component>
Irganox 1010 ... pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF, molecular weight: 1176.

Example 1
Each component is compounded by the polycarbonate resin composition combination shown in Table 1 using pellets of D7340R and D5360R, and further, Solvent Red 179, Solvent Green 3 and Solvent Blue 97 are mixed, and L ^* value of the polycarbonate resin composition is It was set to be 1.0. Thereafter, it was pelletized with a rotary cutter using a twin-screw extruder. The load deflection temperature (1.80 MPa), notched Charpy impact strength, ΔE ^* after the light resistance test, and the L ^* change rate before and after the abrasion resistance test were measured and evaluated for the obtained polycarbonate resin composition by the above method. . The results are shown in Table 1.

(Example 2, Comparative Example 1)
Production and evaluation of a polycarbonate resin composition were performed in the same manner as in Example 1 except that pellets of D7340R and D5360R and various additives were made to have the compositions shown in Table 1. The results are shown in Table 1.

(Comparative example 2)
The pellets of D7340R and D5360R and various additives are made to have the compositions shown in Table 1, and Mitsubishi carbon black (MCF # 960) is mixed to obtain an L ^* value of 2.1 for the polycarbonate resin composition. The process was performed in the same manner as in Example 1 except for the above, and production and evaluation of a polycarbonate resin composition were performed. The results are shown in Table 1.

Claims (4)

An interior and exterior member for an automobile comprising a polycarbonate resin composition comprising a polycarbonate resin and butadiene-methyl methacrylate-styrene rubber,
The polycarbonate resin has a structural unit (structural unit (1)) derived from a dihydroxy compound represented by the following general formula (1) and a structural unit (CHDM unit) derived from cyclohexanedimethanol, and is copolymerizable A melt mixture of carbonate copolymers of different proportions,
The content ratio of the molar ratio of the structural unit (1) to the CHDM unit in the polycarbonate resin is 61/39 to 63/37 (molar ratio),
In the above polycarbonate resin composition, 4.0 to 6.0 parts by weight of butadiene / methyl methacrylate / styrene based rubber is contained with respect to a total of 100 parts by weight of the above polycarbonate resin and butadiene / methyl methacrylate / styrene based rubber ,
Furthermore, the interior-exterior member for motor vehicles which contains the following (A) component-(F) component with respect to the total of 100 weight part of said polycarbonate resin and butadiene- methyl methacrylate- styrene-type rubber, respectively as follows.
Component (A): Dibutylhydroxytoluene: 0.001 to 0.015 parts by weight.
Component (B): diphenyl dimethicone having a kinematic viscosity at 25 ° C. of 4000 to 5500 cSt: 0.05 to 0.31 parts by weight.
Component (C): A hindered amine light stabilizer having a melting point of 125 ° C. to 130 ° C .: 0.05 to 0.21 parts by weight.
Component (D): a benzotriazole light stabilizer having a melting point of 102 ° C. to 106 ° C .: 0.05 to 0.31 parts by weight.
Component (E): tris (2,4-di-t-butylphenyl) phosphite: 0.049 to 0.051 parts by weight.
Component (F): A hindered phenolic antioxidant having a molecular weight of 1100 to 1200: 0.09 to 0.11 parts by weight.

  The interior / exterior member for an automobile according to claim 1, wherein the refractive index of diphenyl dimethicone of the component (B) is 1.49 to 1.51.   The interior / exterior member for an automobile according to claim 1 or 2, wherein the component (C) is a hindered amine light stabilizer having a plurality of piperidine structures.   The interior and exterior member for an automobile according to claim 3, wherein a plurality of piperidine structures possessed by the hindered amine light stabilizer of the component (C) are linked to one alkane chain by an ester bond.