JP2018154826A - Polycarbonate resin composition and molding containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition that makes it possible to obtain a high-quality molding that has an improved appearance by suppressing white haze at a molding terminal part while maintaining high wear resistance, and a molding containing the same.SOLUTION: The present invention provides a polycarbonate resin composition that contains a polycarbonate resin (A) containing a constitutional unit represented by the following formula (1), derived from an isosorbide-based dihydroxy compound, and a specific phenyl group-containing organopolysiloxane (B), and a molding containing the same.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition containing a polycarbonate resin and a phenyl group-containing organopolysiloxane, and a molded article comprising the same.

  In recent years, polycarbonate resins using ether group-containing diols typified by isosorbide, which is a plant-derived raw material, have been developed in consideration of the environment (for example, see Patent Documents 1 and 2). Polycarbonate resins using isosorbide are known to be excellent in heat resistance, weather resistance and impact resistance, and are also known to be applied to automobile interior and exterior parts (see, for example, Patent Document 3).

  On the other hand, a resin composition containing a polycarbonate resin containing a structural unit derived from isosorbide and a silicone compound is also known (see, for example, Patent Document 4). Patent Document 4 describes that the scratch resistance is improved by containing a silicone compound. Furthermore, in Patent Document 5, by containing a polycarbonate resin containing a structural unit derived from isosorbide and a silicone compound having a diorganosiloxane structure or a specific organosilsesquioxane structure, the scratch resistance is improved and molding is performed. It is described that it has good transparency when made into a product and is excellent in initial appearance, mechanical properties and the like.

International Publication WO2004 / 111106 Pamphlet International Publication WO2007 / 063823 Pamphlet JP 2013-209585 A Japanese Patent Laying-Open No. 2015-199954 Japanese Patent Laid-Open No. 2017-8140

  In recent years, it has been studied that a molded article using a polycarbonate resin having a structural unit derived from isosorbide is used for interior and exterior parts for vehicles such as automobiles. Such molded articles are required to have increased wear resistance in order to prevent scratches that occur during use. Furthermore, it has been desired to further enhance the appearance of the molded product by suppressing white haze at the end of the molded product that occurs during molding while maintaining high wear resistance.

  However, the molded products of the conventional polycarbonate resin compositions such as Patent Document 4 and Patent Document 5 are still in view of enhancing the aesthetics by suppressing the white haze at the end of the molded product while maintaining high wear resistance. There is room for improvement. Furthermore, the transparency is insufficient.

  The object of the present invention is to solve the above-mentioned problems in the conventional product, and to obtain a high-quality molded product with improved aesthetics by suppressing white haze at the end of the molded product while maintaining high wear resistance. The object is to provide a polycarbonate resin composition and a molded article comprising the same.

As a result of intensive studies to solve the above problems, the present inventors have found that a polycarbonate resin composition containing a specific polycarbonate resin (A) and a specific phenyl group-containing organopolysiloxane (B) has an abrasion resistance. The present inventors have found that it is possible to realize a high-quality molded product that suppresses the white haze at the end of the molded product while maintaining high properties, thereby improving the appearance of the molded product. That is, the gist of the present invention is as follows.
[1] A polycarbonate resin (A) containing a structural unit derived from a dihydroxy compound represented by the following formula (1);
A phenyl group-containing organopolysiloxane (B) having a silyl group represented by the following formula (2) at the end;
A polycarbonate resin composition in which R ^{1 to} R ³ in the following formula (2) comprise an alkyl group or an aryl group.

[2] The polycarbonate resin (A) is represented by a structural unit derived from the dihydroxy compound represented by the formula (1), an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and the formula (1). The polycarbonate resin composition according to [1], comprising a copolymer containing a structural unit derived from at least one dihydroxy compound selected from the group consisting of ether group-containing dihydroxy compounds other than dihydroxy compounds.

[3] The content of the phenyl group-containing organopolysiloxane (B) with respect to 100 parts by mass of the polycarbonate resin (A) is 0.01 part by mass or more and 5 parts by mass or less, according to [1] or [2]. Polycarbonate resin composition.

[4] The polycarbonate resin composition according to any one of [1] to [3], wherein R ^{1 to} R ³ in the formula (2) are methyl groups.

[5] The polycarbonate resin composition according to any one of [1] to [4], wherein the phenyl group-containing organopolysiloxane (B) has a kinematic viscosity at 25 ° C. of 500 mm ² / s or more.

[6] Further, at least one selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid, phosphonic acid ester, acidic phosphoric acid ester, and aliphatic cyclic phosphite ester The polycarbonate resin composition according to any one of [1] to [5], which contains a phosphorus compound.

[7] A molded product formed by molding the polycarbonate resin composition according to any one of [1] to [6].

[8] The molded article according to [7], which is an interior part or exterior part for automobiles.

  According to the polycarbonate resin composition, a molded product having high wear resistance can be obtained. Therefore, it is possible to prevent scratches that occur during use of the molded product. That is, the molded article has excellent scratch resistance with few scratches generated when wiped with a dust cloth or tissue. Therefore, for example, in applications where visibility is required, a reduction in visibility can be suppressed. Furthermore, the molded product can suppress white haze at the end of the molded product that may occur during molding while maintaining high wear resistance. Therefore, a high-quality molded product with improved aesthetics can be obtained.

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents. In addition, when the expression “to” is used in the present specification, it is used in a sense including numerical values or physical values described before and after the expression. In addition, numerical values or physical values described as the upper limit and the lower limit are used in a sense including the values.

[Polycarbonate resin (A)]
The polycarbonate resin composition contains a polycarbonate resin (A). The polycarbonate resin (A) includes at least a structural unit derived from a dihydroxy compound represented by the following formula (1) (hereinafter referred to as “structural unit (a1)” as appropriate). The polycarbonate resin (A) may be a homopolymer of the structural unit (a1) or a copolymer containing the structural unit (a1) and another structural unit (a2). From the viewpoint of increasing the molecular weight and further improving the impact resistance, the polycarbonate resin (A) is preferably a copolymer.

  Examples of the dihydroxy compound represented by the formula (1) include isosorbide (that is, ISB), isomannide, and isoidet having a stereoisomeric relationship, and these may be used alone or in combination of two or more. May be used in combination. Among these, ISB is most preferable from the viewpoints of availability and production, weather resistance, optical properties, moldability, heat resistance, and carbon neutral. ISB is obtained by dehydrating and condensing sorbitol produced from various starches that are abundant as plant-derived resources and are readily available.

  In addition, the dihydroxy compound represented by Formula (1) tends to be gradually oxidized with oxygen. Therefore, during storage or handling during production, it is preferable to prevent moisture from entering in order to prevent decomposition by oxygen, and to use an oxygen scavenger or in a nitrogen atmosphere. For example, when isosorbide is oxidized, decomposition products such as formic acid may be generated. When isosorbide containing these decomposition products is used as a raw material for the production of polycarbonate resin, there is a risk that the resulting polycarbonate resin and polycarbonate resin composition will be colored. Furthermore, there is a possibility that not only the physical properties may be remarkably deteriorated, but also the polymerization reaction is affected and a high molecular weight polymer may not be obtained.

  The polycarbonate resin (A) is a kind selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and an ether group-containing dihydroxy compound other than the dihydroxy compound represented by the formula (1) as the structural unit (a2). It is preferably made of a copolymer containing the structural unit (a2-1) derived from the above dihydroxy compound (hereinafter, these may be referred to as “other dihydroxy compounds”). That is, the polycarbonate resin (A) is preferably made of a copolymer containing the structural unit (a1) and the structural unit (a2-1). In this case, the impact resistance of the polycarbonate resin (A) can be improved.

  The aliphatic dihydroxy compound may be a linear aliphatic dihydroxy compound or a branched aliphatic dihydroxy compound. For example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1 , 4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1, Examples include 9-nonanediol, 1,10-decanediol, 1,11-dodecanediol, 1,12-undecanediol, and the like.

  Examples of the alicyclic dihydroxy compound include 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, Tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane di Examples thereof include methanol and 1,3-adamantane dimethanol.

  Examples of the ether group-containing dihydroxy compound include diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight 150 to 2000), poly-1,3-propylene glycol, and polytetramethylene glycol.

  From the viewpoint of increasing the heat resistance of the polycarbonate resin (A), the other dihydroxy compounds are more preferably aliphatic dihydroxy compounds and alicyclic dihydroxy compounds, and even more preferably alicyclic dihydroxy compounds. Of the alicyclic dihydroxy compounds, cyclobutanediol, cyclohexanedimethanol, and tricyclodecanedimethanol are even more preferable from the viewpoint of further improving heat resistance and impact resistance.

  In the polycarbonate resin (A), the content ratio of the structural unit (a2) such as the structural unit (a2-1) is preferably 10 mol% or more with respect to 100 mol% of the structural unit derived from all dihydroxy compounds, and 20 mol. % Or more is more preferable, and 30 mol% or more is particularly preferable. Moreover, 60 mol% or less is preferable, 50 mol% or less is more preferable, and 45 mol% or less is especially preferable. By adjusting the content ratio of the structural unit (a2) within this range, both impact resistance and heat resistance of the polycarbonate resin can be improved in a well-balanced manner.

  The polycarbonate resin (A) can be produced by a generally used method for producing a polycarbonate resin. The polycarbonate resin (A) can be produced, for example, by any of a solution polymerization method using phosgene and a melt polymerization method in which a carbonic acid diester and a dihydroxy compound are reacted. Preferably, a melt polymerization method in which a dihydroxy compound containing the dihydroxy compound represented by the formula (1) is reacted with a carbonic diester having a lower environmental toxicity in the presence of a polymerization catalyst is preferable.

  As the polymerization catalyst (transesterification reaction catalyst) in the melt polymerization, at least one selected from the group consisting of alkali metal compounds and alkaline earth metal compounds is used. For example, known ones can be used. A basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound can be used in combination with the alkali metal compound and the alkaline earth metal compound.

  The polycarbonate resin (A) can be produced by a transesterification reaction between a dihydroxy compound and a carbonic acid diester. Examples of the dihydroxy compound include a compound represented by the above formula (1), and examples of the carbonic acid diester include diphenyl carbonate. Specifically, a polycarbonate resin can be obtained by subjecting a dihydroxy compound and a carbonic acid diester to an ester exchange reaction and removing a monohydroxy compound and the like as a by-product from the system. In this case, melt polymerization is usually carried out by a transesterification reaction in the presence of a polymerization catalyst.

  Examples of the transesterification reaction catalyst (hereinafter, sometimes referred to as “catalyst”) include, for example, Group 1 or Group 2 (hereinafter simply referred to as “Group 1”, “No. 1”, “Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005”). And a basic compound such as a metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound. Among these, Group 1 metal compounds and / or Group 2 metal compounds are preferably used, and Group 2 metal compounds are particularly preferably used from the viewpoint of weather resistance.

  The group 1 metal compound and / or the group 2 metal compound are usually used in the form of a hydroxide or a salt such as a carbonate, carboxylate or phenol salt. Hydroxides, carbonates and acetates are preferable from the viewpoint of easy availability and handling, and acetates are preferable from the viewpoint of hue and polymerization activity.

  Examples of the Group 1 metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, Cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride , Sodium borohydride, potassium borohydride, lithium phenide boron, cesium phenide boron, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, 2 sodium hydrogen phosphate Arm, potassium hydrogen phosphate, lithium hydrogen phosphate, hydrogen phosphate 2 cesium, disodium phenyl phosphate, dipotassium phenyl phosphate, phenyl phosphate lithium, and 2 cesium phenyl phosphate. Moreover, sodium, potassium, lithium, cesium alcoholate, phenolate, etc. are mentioned. Furthermore, disodium salt, bispotassium salt, dilithium salt, cesium salt, etc. of bisphenol A are mentioned. Among these examples, a cesium compound and a lithium compound are preferable.

  Examples of the Group 2 metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, Examples include strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate. Among these examples, a magnesium compound, a calcium compound, and a barium compound are preferable, and at least one of a magnesium compound and a calcium compound is more preferable.

  It is possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound in combination with the Group 1 metal compound and / or the Group 2 metal compound. It is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.

  Examples of basic boron compounds include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzyl. Boron, tributylphenyl boron, tetraphenyl boron, benzyltriphenyl boron, methyltriphenyl boron and the like can be mentioned. Moreover, sodium salts, such as a butyl triphenyl boron, potassium salt, lithium salt, calcium salt, barium salt, magnesium salt, or strontium salt are mentioned.

  Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

  Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide Sid, butyl triphenyl ammonium hydroxide, and the like.

  Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.

  Among these, at least one metal compound selected from the group consisting of Group 2 metal compounds is preferably used as the catalyst. In this case, various physical properties such as transparency, hue and weather resistance of the polycarbonate resin (A) can be further improved. From the viewpoint of further enhancing this effect, the catalyst is more preferably composed of at least one metal compound selected from the group consisting of magnesium compounds, calcium compounds, and barium compounds, and is selected from the group consisting of magnesium compounds and calcium compounds. More preferably, it comprises at least one metal compound.

  When a catalyst consists of at least 1 sort (s) chosen from a group 1 metal compound and a group 2 metal compound, the usage-amount of a catalyst is 0.1-as a metal conversion amount with respect to 1 mol of all the dihydroxy compounds with which it uses for reaction. It is preferably 300 μmol. More preferably, it is 0.1-100 micromol, More preferably, it is 0.5-50 micromol, Most preferably, it exists in the range of 1-25 micromol.

  When a compound containing at least one metal selected from the group consisting of group 2 metals is used as the catalyst, the amount of group 2 metal compound used is, as a metal equivalent, per mole of all dihydroxy compounds subjected to the reaction, The amount is preferably 0.1 μmol or more. More preferably, it is 0.5 μmol or more, and particularly preferably 0.7 μmol or more. Further, the upper limit is preferably 20 μmol, more preferably 10 μmol, particularly preferably 3 μmol, and most preferably 2 μmol.

  By adjusting the amount of the catalyst used within the above range, a polycarbonate resin having a desired molecular weight with sufficient polymerization activity and sufficient breaking energy can be obtained, and the hue becomes better. That is, the quality of the polycarbonate resin (A) can be further improved.

  As the polymerization reaction, a known method can be used, and any method of a batch method, a continuous method, or a combination of a batch method and a continuous method may be used.

  When producing the polycarbonate resin (A), it is desirable to install a filter in order to prevent foreign matter from entering. The filter installation position is preferably on the downstream side of the extruder, and the filter foreign matter removal size (opening) is usually preferably 100 μm or less as 99% removal filtration accuracy. In particular, in the case of disagreeing with the entry of minute foreign matters for film applications, the thickness is more preferably 40 μm or less, and further preferably 10 μm or less.

  From the viewpoint of preventing foreign matter from being mixed after extrusion, the extrusion of the polycarbonate resin (A) is preferably carried out in a clean room having higher cleanliness than class 7 defined in JIS B 9920 (2002). More preferably, it is good to carry out in a clean room with higher cleanliness than class 6.

  Moreover, when cooling the extruded polycarbonate resin (A) to form chips, it is preferable to use a cooling method such as air cooling or water cooling. The air used for air cooling is preferably air that has been previously removed with a hepa filter or the like to prevent reattachment of foreign matter in the air. It is preferable to use water used for water cooling after removing metal by an ion exchange resin or the like and further removing foreign substances with a filter. The opening of the filter is preferably 10 μm to 0.45 μm as 99% removal filtration accuracy.

  The molecular weight of the polycarbonate resin (A) can be represented by a reduced viscosity, and the higher the reduced viscosity, the higher the molecular weight. The reduced viscosity is preferably 0.30 dL / g or more, and more preferably 0.35 dL / g or more. On the other hand, the reduced viscosity is preferably 1.20 dL / g or less, more preferably 1.00 dL / g or less, and still more preferably 0.80 dL / g or less. By adjusting the reduced viscosity within the above range, fluidity during molding can be improved, and productivity and moldability can be further improved. Therefore, a molded product having a complicated shape can be manufactured with high productivity, which is suitable for electrical / electronic device parts, automobile interior / exterior parts, and the like. The reduced viscosity of the polycarbonate resin (A) was precisely adjusted to 0.6 g / dL using methylene chloride as a solvent, and Ubellode under a temperature of 20.0 ° C. ± 0.1 ° C. Measure using a viscosity tube.

  The glass transition temperature of the polycarbonate resin (A) is preferably 90 ° C. or higher. In this case, the heat resistance of the polycarbonate resin composition is further improved. From the same viewpoint, the glass transition temperature of the polycarbonate resin (A) is more preferably 100 ° C. or higher, and further preferably 110 ° C. or higher. On the other hand, the glass transition temperature of the polycarbonate resin (A) is preferably 145 ° C. or lower. In this case, the fluidity at the time of molding is improved, and even if the molded product has a complicated shape, the resin composition easily reaches the end of the molding die at the time of molding, and a desired molded product can be obtained. In addition, a decrease in strength at the weld portion can be suppressed. From the viewpoint of further enhancing these effects, the glass transition temperature of the polycarbonate resin (A) is more preferably 135 ° C. or lower, and further preferably 125 ° C. or lower.

  The polycarbonate resin composition may contain one type of resin alone as the polycarbonate resin (A), but the type, copolymerization ratio, physical properties, etc. of the structural unit (a2) derived from other dihydroxy compounds. Two or more different resins may be mixed.

[Phenyl group-containing organopolysiloxane (B)]
The polycarbonate resin composition contains a phenyl group-containing organopolysiloxane (B). Therefore, the wear resistance is improved, and scratches that can occur during use of the molded product can be prevented. Furthermore, while maintaining high wear resistance, it is possible to obtain a high-quality molded product that suppresses white haze at the end of the molded product and enhances the appearance of the molded product. In addition, the white haze at the end of the molded product can occur during molding of the resin composition. In addition, the phenyl group-containing organopolysiloxane (B) has an effect of improving releasability during molding. Therefore, it becomes possible to manufacture a molded product having a complicated shape.

The phenyl group-containing organopolysiloxane (B) preferably contains a diorganosiloxane structure represented by the following formula (3). In formula (3), at least one of R ⁴ and R ⁵ is an aryl group, and the other represents an alkyl group or an aryl group. R ⁴ and R ⁵ may be the same or different.

In the case of containing an alkyl group as R ⁴ and R ⁵ , the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 10 from the viewpoint of improving the compatibility. More preferably, it is 1-5.

In the case of containing an aryl group as R ⁴ and R ⁵ , it is preferably 6 to 30, more preferably 6 to 15, and more preferably 6 to 10 from the viewpoint of improving compatibility. Further preferred.

Examples of the phenyl group-containing organopolysiloxane (B) include phenyl-modified silicone in which at least one of R ⁴ and R ⁵ bonded to Si in the above formula (3) is a phenyl group. Specific examples of the phenyl group-containing organopolysiloxane (B) such as phenyl-modified silicone include methylphenyl silicone oil, diphenyldimethicone, phenyltrimethicone, trimethylpentaphenyltrisiloxane, tetraphenyltetramethyltrisiloxane, and the like. It is done.

  Among these examples, phenyl trimethicone and diphenyl dimethicone are preferable as the phenyl group-containing organopolysiloxane (B). From the viewpoint that slipperiness can be further imparted to the resin composition, diphenyldimethicone is more preferable. Moreover, you may use the mixture containing the structure which bridge | crosslinked dimethyl silicone oil and methylphenyl silicone oil to diphenyl dimethicone. Furthermore, when using a crosslinked structure, it is preferable that a silicate structure and a silsesquioxane structure are included.

The phenyl group-containing organopolysiloxane (B) has a silyl group represented by the following formula (2) at the end of the polymer chain. That is, the phenyl group-containing organopolysiloxane has a silyl group represented by the formula (2) as a terminal functional group. R ^{1 to} R ³ in the formula (2) may be the same as or different from each other.

From the viewpoint of enhancing the compatibility between the polycarbonate resin (A) and the phenyl group-containing organopolysiloxane (B), it is preferable that R ^{1 to} R ³ contain an alkyl group or an aryl group. Further, all of R ^{1 to} R ³ may be composed of an alkyl group or an aryl group, and both of them are contained such that a part of R ^{1 to} R ³ is an alkyl group and the rest is an aryl group. It may be.

When R ^{1 to} R ³ contain an alkyl group, the alkyl group has 1 to 6 carbon atoms, for example. As R ¹ to R ^3, when it contains an aryl group has a carbon number of the aryl group is, for example, 6 to 20.

From the viewpoint that the reactivity during production of the phenyl group-containing organopolysiloxane (B) becomes better, R ^{1 to} R ³ are preferably alkyl groups. From the viewpoint of further improving the compatibility described above, the number of carbon atoms of the alkyl group represented by R ^{1 to} R ³ is preferably 1 to 4, more preferably 1 to 3, and further preferably 1 to 2. Preferably 1 is most preferred.

  From the viewpoint of enhancing the transparency of the molded article of the polycarbonate resin composition, the phenyl group-containing organopolysiloxane (B) preferably has a high refractive index. Specifically, the refractive index of the phenyl group-containing organopolysiloxane (B) is preferably 1.450 or more, and more preferably 1.500 or more. 1 type (s) or 2 or more types can be used for a phenyl group containing organopolysiloxane, The mixing | blending etc. can be suitably prepared according to a desired refractive index.

  The difference in refractive index between the polycarbonate resin (A) and the phenyl group-containing organopolysiloxane (B) is preferably within ± 0.1, more preferably within ± 0.05, and ± 0.01. More preferably, it is within. By adjusting the difference in refractive index within the above range, the transparency can be further improved, and the sharpness at the time of coloring can be further improved.

As the phenyl group-containing organopolysiloxane (B), those having high viscosity are preferable from the viewpoint of wear resistance. The kinematic viscosity of the phenyl group-containing organopolysiloxane (B) at a temperature of 25 ° C. is preferably 15 mm ² / s or more, more preferably 500 mm ² / s or more, and 1000 mm ² / s or more. More preferably, it is still more preferably 3000 mm ² / s or more. The phenyl group-containing organopolysiloxane may be used alone or in combination of two or more, and adjusted to the desired kinematic viscosity. On the other hand, the upper limit of the kinematic viscosity, from the viewpoint of kneading or the like of the handling and the polycarbonate resin (A) and phenyl-containing organopolysiloxane (B), is preferably from 15000 ² / s, at 7000 mm ² / s More preferably.

As the phenyl group-containing organopolysiloxane (B), for example, a commercially available product can be used. As a commercial item of phenyl group-containing organopolysiloxane (B), for example, Shin-Etsu Chemical Co., Ltd .: KF-54HV (diphenyl dimethicone, refractive index: 1.503, kinematic viscosity: 4800 mm ² / s (25 ° C.) ), Manufactured by Momentive: TSF437 (diphenyldimethicone, refractive index: 1.499, kinematic viscosity: 22 mm ² / s (25 ° C.)), manufactured by Shin-Etsu Chemical Co., Ltd .: KF54-SS (diphenyldimethicone, refractive index: 1) 504, kinematic viscosity: 500 mm ² / s (25 ° C.), manufactured by Momentive: TSF433 (methylphenyl oil, refractive index: 1.505, kinematic viscosity: 450 mm ² / s (25 ° C.)), manufactured by Momentive: TSF4300 (methylphenyl oil, refractive index: 1.498, kinematic viscosity: 140 mm ² / s (25 ° C.)), Shin-Etsu Chemical Co., Ltd.: K 56 (phenyl trimethicone, refractive index: 1.500, kinematic viscosity: 15 mm ² / s (25 ° C.)), manufactured by Dow Corning Toray Co., Ltd.: SH556 (phenyl trimethicone, refractive index: 1.459, kinematic viscosity : 23 mm ² / s (25 ° C.))) and the like.

  The content of the phenyl group-containing organopolysiloxane (B) in the polycarbonate resin composition is preferably 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A). More preferably, it is at least 3 parts by mass and more preferably at least 0.1 part by mass and at most 2 parts by mass. When the content of the phenyl group-containing organopolysiloxane (B) is within the above range, it is possible to further improve the wear resistance and to further suppress white mist during molding of the molded product. A polycarbonate resin composition can contain 1 or more types as a phenyl group containing organopolysiloxane (B). In the case of containing a plurality of phenyl group-containing polysiloxanes (B), the total content of the phenyl group-containing polysiloxanes (B) is preferably within the above range.

[Additive]
Various additives can be further added to the polycarbonate resin composition as long as the above-mentioned desired effects are not impaired. Additives include catalyst deactivators, antioxidants, UV absorbers, light stabilizers, release agents, colorants, neutralizers, antistatic agents, lubricants, lubricants, plasticizers, flame retardants, fillers Etc.

(Catalyst deactivator)
The catalyst deactivator has a property of deactivating the polymerization catalyst of the polycarbonate resin (A). The effect of improving the color tone of the polycarbonate resin and improving the thermal stability can be exhibited. As the catalyst deactivator, for example, an acidic compound can be used. As such an acidic compound, a compound having a carboxylic acid group, a phosphoric acid group or a sulfonic acid group, or an ester thereof can be used. Preferably, a phosphorus compound containing a partial structure represented by the following formula (4) or (5) is used.

  Examples of the phosphorus compound having a partial structure represented by the formula (4) or (5) include phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid ester, and acidic phosphoric acid ester. Can be mentioned. Among these, phosphorous acid, phosphonic acid, and phosphonic acid ester are preferable, and phosphorous acid is more preferable, from the viewpoint that the catalyst deactivation and coloring suppression effects are further excellent.

  Examples of phosphonic acid include phosphonic acid (phosphorous acid), methylphosphonic acid, ethylphosphonic acid, vinylphosphonic acid, decylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, aminomethylphosphonic acid, methylenediphosphonic acid, 1-hydroxyethane- Examples include 1,1-diphosphonic acid, 4-methoxyphenylphosphonic acid, nitrilotris (methylenephosphonic acid), and propylphosphonic anhydride.

  Examples of phosphonic acid esters include dimethyl phosphonate, diethyl phosphonate, bis (2-ethylhexyl) phosphonate, dilauryl phosphonate, dioleyl phosphonate, diphenyl phosphonate, dibenzyl phosphonate, dimethyl methylphosphonate, diphenyl methylphosphonate, and ethylphosphonic acid. Diethyl, diethyl benzylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, diethyl (methoxymethyl) phosphonate, diethyl vinylphosphonate, diethyl hydroxymethylphosphonate, dimethyl (2-hydroxyethyl) phosphonate, p-methylbenzylphosphonate diethyl, diethylphosphonoacetic acid, diethylphosphonoacetic acid ethyl, diethylphosphonoacetic acid tert-butyl, (Robenzyl) diethyl phosphonate, diethyl cyanophosphonate, diethyl cyanomethylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethylphosphonoacetaldehyde diethyl acetal, diethyl (methylthiomethyl) phosphonate Can be mentioned.

  Acid phosphate esters include dimethyl phosphate, diethyl phosphate, divinyl phosphate, dipropyl phosphate, dibutyl phosphate, bis (butoxyethyl) phosphate, bis (2-ethylhexyl) phosphate, diisotridecyl phosphate, phosphate Examples include phosphoric acid diesters such as dioleyl, distearyl phosphate, diphenyl phosphate and dibenzyl phosphate, mixtures of diesters and monoesters, diethyl chlorophosphate, and zinc stearyl phosphate.

  These phosphorus compounds may be used alone or in a combination of two or more in any combination and ratio.

  The addition amount of the phosphorus compound can be adjusted according to the amount of catalyst used in the polymerization reaction. If the amount of phosphorus compound added to the resin is too small, the effects of catalyst deactivation and coloring suppression will be insufficient, and if too much, the resin will be colored, especially in durability tests at high temperatures and high humidity. The resin is likely to be colored. From this point of view, the phosphorus compound is preferably 0.5 times mol or more and 5 times mol or less, and 0.7 times mol or more and 4 times mol or more of the phosphorus compound relative to 1 mol of the catalyst metal used in the polymerization reaction. The molar ratio is more preferably 2 times mol or less, more preferably 0.8 times mol or more and 3 times mol or less.

(Antioxidant)
As antioxidant, the general antioxidant used for resin can be used. From the viewpoints of oxidation stability, thermal stability, good jetness at the time of coloring, phosphite antioxidants, sulfur antioxidants and phenolic antioxidants are preferred. As the antioxidant, one type of compound may be used, or two or more types of compounds may be used in combination.

  From the standpoint of sufficiently obtaining an additive effect such as a weather resistance improving effect, the content of the antioxidant in the polycarbonate resin composition is preferably 0.001 part by mass or more with respect to 100 parts by mass of the polycarbonate resin (A). 0.002 parts by mass or more is more preferable, and 0.005 parts by mass or more is still more preferable. From the viewpoints of improving moldability, suppressing mold contamination, and improving the surface appearance of the molded product, the content of the antioxidant is preferably 5 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A). 3 parts by mass or less is more preferable, and 2 parts by mass or less is more preferable.

<Phosphite antioxidant>
Phosphite antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl Phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert- Butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol Diphosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like.
Among these, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferably used.

<Sulfur-based antioxidant>
Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, diester Stearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate) ), Glycerol-3-stearylthiopropionate, bis [2-methyl-4- (3-laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6 -Methylbenzui Imidazole, 1,1'-thiobis (2-naphthol), and the like.
Among these, pentaerythritol tetrakis (3-lauryl thiopropionate) is preferable.

<Phenolic antioxidant>
Examples of the phenolic antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3, 5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris ( , 5-Di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl 2-[[beta]-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane, 2,6- Examples of the compound include di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4-ethylphenol.
Among these compounds, an aromatic monohydroxy compound substituted with one or more alkyl groups having 5 or more carbon atoms is preferable. Specifically, octadecyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and the like, preferably pentaerythritol- Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] More preferable.

(Ultraviolet absorber (C))
The polycarbonate resin composition can contain an ultraviolet absorber as long as the object of the present invention is not impaired. Examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole and 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzo. Triazole, 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2H -Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2,2'-p-phenylenebis (1,3-benzoxazin-4-one), and the like It is done. 0.01-2 mass parts is preferable with respect to 100 mass parts of polycarbonate resin, and, as for content of a ultraviolet absorber, 0.05-1 mass part is more preferable.

(Light stabilizer (D))
The polycarbonate resin composition can contain a light stabilizer as long as the object of the present invention is not impaired. As the light stabilizer, for example, a compound derived from an amine compound can be used. A compound having a secondary amine structure with a melting point of 85 ° C. or higher is preferable. A compound having a secondary amine structure is more basic than a primary amine. The higher the basicity of the light stabilizer composed of an amine compound or the like, the more stable the polycarbonate is with respect to light, and the deterioration due to hydrolysis or the like is suppressed.

  From the viewpoint that the rate of change of the maximum height after the light resistance test of the molded product can be reduced, the secondary amine structure is preferably one in which nitrogen is part of the cyclic structure, and has a piperidine structure. What has is more preferable. The piperidine structure defined here may be any structure as long as it is a saturated 6-membered cyclic amine structure, and includes a structure in which a part of the piperidine structure is substituted with a substituent. Examples of the substituent that the piperidine structure may have include an alkyl group having 4 or less carbon atoms, and a methyl group is particularly preferable.

  As a compound having a melting point of 85 ° C. or higher and a secondary amine structure, those having a plurality of secondary amine structures are preferable. A compound having a plurality of secondary amine structures having a piperidine structure is more preferable. More preferably, a compound in which a plurality of piperidine structures are linked by an ester structure is preferable.

  From the viewpoint of improving the bleed-out resistance, the absolute value of the difference in solubility parameter (that is, SP value) between the polycarbonate resin (A) and the amine compound is preferably 0.0 or more and 15.0 or less. The SP value is calculated by the Hoy method. From the viewpoint of further improving the bleed-out resistance, the absolute value of the difference in SP value is more preferably 0.0 or more and 12.0 or less, further preferably 0.0 or more and 8.0 or less, As described above, 6.0 or less is even more preferable.

  The melting point of the light stabilizer composed of an amine compound or the like is preferably 85 ° C. or higher. In this case, smoothness and bleed-out resistance after the light resistance test can be improved. From the viewpoint of enhancing this improvement effect, the melting point of the light stabilizer is more preferably 90 ° C. or higher and 300 ° C. or lower, more preferably 100 ° C. or higher and 250 ° C. or lower, and even more preferably 110 ° C. or higher and 200 ° C. or lower. .

  Moreover, from a viewpoint that a weather resistance improves more with a small amount, the terminal functional group equivalent of a light stabilizer has preferable 100 g / eq or more and 500 g / eq or less. From the viewpoint that the effect of improving the weather resistance can be obtained with a smaller amount, the terminal functional group equivalent of the light stabilizer is preferably 100 g / eq or more and 350 g / eq or less, more preferably 100 g / eq or more and 300 g / eq or less. 100 g / eq or more and 300 g / eq or less is even more preferable.

  From the viewpoint of further improving the weather resistance of the molded article, the molecular weight of the light stabilizer is preferably 5000 or less, and more preferably 3000 or less. The molecular weight of the light stabilizer is preferably 300 or more, and more preferably 400 or more, from the viewpoint of suppressing a decrease in heat resistance and further suppressing mold contamination and surface appearance deterioration during molding.

  Examples of such a light stabilizer (D) include 2,2,6,6-tetramethyl-4-piperidinol, tetrakis (2,2,6,6-tetramethyl-4-piperidyl-butane-1,2, 3,4-tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid tetrakis (2,2,6,6-tetramethyl-4-piperidinyl), 1,2,3,4-butanetetracarboxylic acid Tetrakis (2,2,6,6-tetramethyl-4-piperidinyl), tetrakis (2,2,6,6-tetramethyl-4-piperidyl-butane-1,2,3,4-tetracarboxylate, bis (1,2,3,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, 1,2,3 4-butanetetra Rubonic acid, 2,2,6,6-tetramethyl-4-piperidinol and β, β, β, β-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] Condensates with undecane-diethanol, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1- (Dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, etc. Among them, tetrakis (2,2,6,6) from the viewpoint of high melting point. Tetramethyl-4-piperidyl-butane-1,2,3,4-tetracarboxylate (SP value 19.2, melting point 130 ° C.), 1,2,3,4-butanetetracarboxylic acid and 2,2, 6,6-tetramethyl-4 Mixed esterified product of piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (SP value 18.5, melting point) 95 ° C.) As the light stabilizer (D), one type of amine compound may be used alone, or two or more types may be mixed and used.

  The content of the light stabilizer (D) such as an amine compound in the polycarbonate resin composition is preferably 0.001 part by mass or more and 5 parts by mass or less, and 0.005 part by mass or more and 3 parts by mass with respect to 100 parts by mass of the polycarbonate resin. The amount is more preferably equal to or less than part by weight, and still more preferably equal to or greater than 0.01 part by weight and equal to or less than 1 part by weight. Coloring can be prevented by adjusting the content of the light stabilizer within the above range. In addition, when a colorant is added, for example, a jet black with depth and clarity can be obtained. Furthermore, the effect of light resistance is sufficiently obtained, and for example, a molded product suitable for an automobile interior / exterior product is obtained.

  As the light stabilizer (D), for example, an amine compound having a secondary amine structure is preferable as described above, but an amine compound different from these preferable forms may be used in combination. As the amine compound that can be used in combination, an amine compound having a tertiary amine structure is preferred. In this case, the effect of light stability can be exhibited over a longer period. From the viewpoint of further enhancing this effect, the light stabilizer is more preferably a combination of a secondary amine having a piperidine structure and a tertiary amine having a piperidine structure.

(Coloring agent)
Examples of the colorant include organic dyes such as inorganic pigments, organic pigments, and organic dyes. A coloring agent may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  Examples of inorganic pigments include carbon black and oxide pigments. Examples of the oxide pigment include titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, copper-iron black, and the like.

  Examples of organic dyes include phthalocyanine dyes, condensed polycyclic dyes, dyes and the like. Examples of the condensed polycyclic dye include azo, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, and quinophthalone. Examples of dyes and pigments include anthraquinone, perinone, perylene, methine, quinoline, heterocyclic, and methyl.

  As the colorant, an inorganic pigment is preferable. In this case, even when the molded product is used outdoors, the vividness and the like can be maintained for a long time.

  The content of the colorant in the polycarbonate resin composition is preferably 0.05 parts by mass or more and 5 parts by mass or less, and more preferably 0.05 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A). Preferably, it is 0.1 to 2 parts by mass. By adjusting the content of the colorant to the above range, an original molded product with high definition can be obtained, and an increase in the surface roughness of the molded product can be further prevented.

When the polycarbonate resin composition is toned in jet black, the lightness L ^* is preferably from 0.1 to 10, more preferably from 0.1 to 6. Further, the glossiness is preferably 85% or more, and more preferably 88% or more.

(filler)
The polycarbonate resin composition can contain a filler such as an inorganic filler and an organic filler as long as the design properties can be maintained. Examples of inorganic fillers include glass fibers, glass milled fibers, glass flakes, glass beads, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whiskers, barium sulfate, talc, mica, wollastonite, and other calcium silicates. Carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, potassium titanate fiber, whiskers thereof and the like. Organic fillers include powdered organic fillers such as wood powder, bamboo powder, coconut starch, cork powder, and pulp powder; balun and spherical organic fillers such as crosslinked polyester, polystyrene, styrene / acrylic copolymer, urea resin, etc. Agents: Fibrous organic fillers such as carbon fibers, synthetic fibers and natural fibers.

(Lubricant)
The polycarbonate resin composition can contain a lubricant as long as the object of the present invention is not impaired. The lubricant is also called a fluidity modifier. Examples of the lubricant include oils composed of hydrocarbon compounds such as fatty acid amide and paraffin oil, silicone oils, ester compounds such as carboxylic acid esters, and fluorine waxes. From the viewpoint of enhancing transparency and maintaining physical properties, fatty acid amide is preferred.

  Examples of the fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, hydroxystearic acid amide, N-stearyl stearic acid amide and the like; N-oleylpaltimine Unsaturated fatty acid monoamides such as acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bis hydroxy Stearic acid amide, ethylene bisbehenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbehenic acid amide, N, N'-dis Saturated fatty acid bisamides such as allyl adipic acid amide, N, N′-distearyl sebacic acid amide; ethylene bisoleic acid amide, ethylene bis erucic acid amide, hexamethylene bis oleic acid amide, N, N′-dioleyl adipic acid amide And unsaturated fatty acid bisamides such as N, N′-dioleyl sebacic acid amide; aroma such as m-xylylene bisstearic acid amide, m-xylylene bishydroxystearic acid amide, N, N′-cysteallyl isophthalic acid amide Aliphatic bisamides; fatty acid ester amides such as stearamide ethyl stearate. From the viewpoint of compatibility with the polycarbonate resin (A), a saturated fatty acid bisamide, an unsaturated fatty acid bisamide, and an aromatic bisamide are preferable.

  From the viewpoint of obtaining a sufficient effect of addition, the content of the lubricant in the composition is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more. From the viewpoint of suppressing bleed-out and reduction in transparency, the content of the lubricant is preferably 5% by mass or less, more preferably 1% by mass or less, and further preferably 0.5% by mass or less.

[Production Method of Polycarbonate Resin Composition]
The polycarbonate resin composition is produced by mixing the above components at a predetermined ratio at the same timing or in any order with a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading roll, or extruder. can do. That is, a polycarbonate resin composition can be produced by mixing at least the polycarbonate resin (A) and the phenyl group-containing organopolysiloxane (B). At the time of mixing, an ultraviolet absorber, a light stabilizer and the like which are added as necessary can be used in combination.

[Molding]
The molded product is obtained by molding a polycarbonate resin composition. Molding can be performed by any molding method. For example, injection molding, injection compression molding, and injection press molding are preferably used. As a runner used for molding, either a cold runner method or a hot runner method can be used. Further, molding by insert molding, in-mold coating molding, two-color molding, sandwich molding, or the like is also possible. From the viewpoint of enhancing the design properties, it is also possible to use heat insulating mold forming and rapid heating / cooling mold forming.

(Use)
For example, the molded article can exhibit excellent abrasion resistance such that it is excellent in abrasion resistance and has few abrasion scratches when wiped with a dust cloth or tissue even if it is not coated by painting. Therefore, the process and cost for painting can be reduced. Since it has such an effect, the molded product can be applied to various parts. In addition, since the molded product is excellent in smoothness and can be further improved in transparency by selecting further materials, for example, sharpness and the like can be improved. Furthermore, it is considered that by adding a light stabilizer, an ultraviolet ray preventing agent, etc., effects such as excellent transparency can be maintained over a long period even in an environment exposed to light. Moreover, it is possible to prevent the occurrence of white haze at the end of the product. From the viewpoint that generation of this white haze can be suppressed, the transparency of the entire molded product can be improved. However, the molded product includes not only a transparent product but also a product colored with the above-described colorant.
Since the effects as described above can be exhibited, the molded product can provide high-quality parts with a high-class feeling and profound feeling. Although there is no restriction | limiting in particular as an application use of a molded article, It is suitable for interior parts and exterior parts for interior goods, exterior goods, vehicles, such as a car.

  As exterior parts for automobiles to which molded products are applied, for example, fender, bumper, facer, door panel, side garnish, pillar, radiator grill, side protector, side molding, rear protector, rear molding, various spoilers, bonnet, roof panel, Examples include trunk lids, detachable tops, wind reflectors, mirror housings, outer door handles, and the like. Examples of automobile interior parts include instrument panels, center console panels, meter parts, various switches, car navigation parts, car audio visual parts, and the like. Also, it can be applied to auto mobile computer parts. Although the said use is suitable for a molded article, it is not limited to these uses at all.

<Reason why the present invention is effective>
The reason why the present invention is effective is not yet clear, but is presumed as follows. That is, by using the phenyl group-containing organopolysiloxane, the abrasion resistance is improved, and scratches that may occur when the molded product is used can be prevented. Furthermore, by using a phenyl group-containing polyorganosiloxane that is modified with a weakly polar alkyl group or aryl group at the terminal, in places such as the end of the molded product where the molding pressure does not act much during molding such as injection molding, Since surface segregation of the phenyl group-containing polyorganosiloxane is likely to occur, it is considered that the white haze that occurs at the time of molding a molded product can be suppressed while maintaining the above-mentioned abrasion resistance high. As a result, the polycarbonate resin composition enables the production of a high-quality molded product with an enhanced aesthetic appearance. In contrast, when a silicone oil having a terminal group with a high polarity such as an alkoxy group or a carboxyl group is used, the silicone oil is sufficiently on the surface because it has a high polarity at a location where the molding pressure is low. It is considered that white turbidity (that is, white haze) occurs at the end of the molded product without bleeding out.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[Evaluation method]
In the following, the physical properties or characteristics of the polycarbonate resin and the polycarbonate resin composition were evaluated by the following methods.

(1) Test piece preparation method The pellet of polycarbonate resin composition was dried at 100 degreeC under nitrogen atmosphere for 8 hours. Next, the dried pellets are supplied to an injection molding machine (EC-75SX manufactured by TOSHIBA MACHINE CO., LTD.), And at a resin temperature of 240 ° C. and a mold temperature of 60 ° C., an injection molded plate (width 100 mm × length 100 mm × thickness 2 mm). ). This injection-molded plate is used as a test piece.

(2) Coefficient of dynamic friction For the test piece obtained in (1) above, a surface property measuring machine (manufactured by Shinto Kagaku, model: HEIDON-) is used with a ball indenter (material: SUS, size: φ3 mm) manufactured by Shinto Kagaku. 14D), and obtained from the load when moving at a load of 200 gf and a moving speed of 100 mm / min. As the dynamic friction coefficient μk, an average value of loads from 4 seconds to 10 seconds after the start of movement was adopted.

(3) Abrasion resistance test The abrasion resistance test was performed using a surface property measuring machine (manufactured by Shinto Kagaku Co., Ltd., model: Tribogear TYPE-14D). First, tissue (a flower box made by Nippon Paper Crecia Co., Ltd.) was folded three times and attached to a steel wool holder made by Shinto Kagaku of φ28 mm. Next, the surface of the test piece obtained in the above (1) was attached to a steel wool holder and the other tissue was reciprocated 200 times. The reciprocating motion was performed under the conditions of a load of 9.8 N, a stroke of 50 mm, and a speed of 3000 mm / min. Then, the haze of the surface which reciprocated was measured and the haze change rate before and behind an abrasion test was evaluated. That is, the amount of scratches that could occur on the surface was measured as the haze change rate. The haze measurement was performed using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.) and a D65 light source in accordance with JIS K7105.

(4) White haze evaluation method The terminal part of the test piece obtained by said (1) was visually observed, and the presence or absence of cloudiness was evaluated.

[Polycarbonate resin (A)]
The following PC1 and PC2 were used as the polycarbonate resin to be blended in the polycarbonate resin composition.
PC1: D7340R (Mitsubishi Chemical Corporation), refractive index 1.500
PC2: D5380R (Mitsubishi Chemical Corporation), refractive index 1.499

[Phenyl group-containing organopolysiloxane (B)]
In Examples 1 to 4 described later, the following silicone oils 1 to 4 were used as the phenyl group-containing organopolysiloxane (B) to be blended in the polycarbonate resin composition.
Silicone oil 1: KF54-HV (manufactured by Shin-Etsu Chemical Co., Ltd., trimethylsilyl-terminated diphenyldimethicone, refractive index: 1.503, kinematic viscosity: 4800 mm ² / s (25 ° C.))
Silicone oil 2: TSF437 (manufactured by Shin-Etsu Chemical Co., Ltd., trimethylsilyl-terminated diphenyldimethicone, refractive index: 1.499, kinematic viscosity: 22 mm ² / s (25 ° C.))
Silicone oil 3: KF54-SS (manufactured by Shin-Etsu Chemical Co., Ltd., trimethylsilyl-terminated diphenyldimethicone, refractive index: 1.504, kinematic viscosity: 500 mm ² / s (25 ° C.))
Silicone oil 4: 2-2078 (manufactured by Toray Dow Corning Co., Ltd., a mixture of aminopropylphenyltrimethicone and phenyltrimethylsilyloxy-terminated silsesquioxane, refractive index: 1.500, kinematic viscosity: 2000 mm ² / s ( 25 ° C))
In Comparative Examples 1 and 2 described later, the following silicone oils 5 and 6 were used.
Silicone oil 5: KR-510 (manufactured by Shin-Etsu Chemical Co., Ltd., alkoxy-terminal-modified methylphenyl silicone, refractive index: 1.509, kinematic viscosity: 100 mm ² / s (25 ° C.))
Silicone oil 6: BY16-201 (manufactured by Toray Dow Corning, carbinol-end-modified dimethylsiloxane, kinematic viscosity: 45 mm ² / s (25 ° C.))

[Benzotriazole UV absorber (C)]
The following benzotriazole type was used as the ultraviolet absorber (C) to be blended in the polycarbonate resin composition.
Benzotriazole-based ultraviolet absorber: LA-29 (manufactured by ADEKA, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, melting point 104 ° C.)

[Hindered amine light stabilizer (D)]
The following were used as the hindered amine light stabilizer (D) to be blended in the polycarbonate resin composition.
Hindered amine light stabilizer: LA-57 (manufactured by ADEKA, tetrakis (2,2,6,6-tetramethyl-4-piperidyl-butane-1,2,3,4-tetracarboxylate, SP value 19.2) The melting point is the average value of the lowest temperature and the highest temperature for those having a temperature range between the melting points.

[Example 1]
PC1 and PC2 are used as the polycarbonate resin (A), silicone oil 1 is used as the phenyl group-containing organopolysiloxane (B), and LA-29 manufactured by ADEKA is used as the ultraviolet absorber (C). LA-57 manufactured by ADEKA was used as a stabilizer. Specifically, first, 90 parts by mass of PC1, 10 parts by mass of PC2, 0.3 parts by mass of silicone oil 1, 0.1 parts by mass of LA-29, and 0.1 parts by mass of LA. -57 was previously blended and charged into a twin-screw kneader (manufactured by Nippon Steel Works, TEX30SST42BW: screw diameter 30 mm) and kneaded. Using a strand cutter, extrude the kneaded material into a strand at a cylinder temperature of 230 ° C., a screw rotation speed of 100 rpm, and a discharge rate of 15 kg / hr, while adjusting the pressure from 10 to 20 kPa with a vacuum pump from one place in the kneader. Thus, a pellet-shaped polycarbonate resin composition was obtained. This is a pellet-like sample. The pellet-like sample was dried at 100 ° C. for 5 hours with a hot air dryer, and then evaluated according to the evaluation methods (1) to (4) described above. The results are shown in Table 1.

[Examples 2 to 4]
A pellet-like sample was obtained in the same manner as in Example 1 except that the formulation was changed as shown in Table 1. Next, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Examples 1-3]
A pellet-like sample was obtained in the same manner as in Example 1 except that the formulation was changed as shown in Table 1. Next, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

  As is known from Table 1, in Comparative Example 3 containing no silicone silicone oil, the wear resistance was insufficient. That is, the molded product of Comparative Example 3 is likely to be scratched. Further, Comparative Example 1 containing a silicone oil having a polar alkoxy terminal, and Comparative Example 2 containing a silicone oil having a carbinol terminal and not containing a phenyl group both have white haze at the end of the molded part. Observed. On the other hand, in Examples using the polycarbonate resin composition containing the specific polycarbonate resin (A) and the specific phenyl group-containing organopolysiloxane (B) as in Examples 1 to 4, the abrasion resistance It can be seen that a high-quality molded product with an improved aesthetic appearance can be obtained by suppressing the white haze at the end of the molded product while maintaining a high value.

Claims (8)

A polycarbonate resin (A) containing a structural unit derived from a dihydroxy compound represented by the following formula (1);
A phenyl group-containing organopolysiloxane (B) having a silyl group represented by the following formula (2) at the end;
A polycarbonate resin composition in which R ^{1 to} R ³ in the following formula (2) comprise an alkyl group or an aryl group.

  The polycarbonate resin (A) is a structural unit derived from the dihydroxy compound represented by the formula (1), an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a dihydroxy compound represented by the formula (1). The polycarbonate resin composition of Claim 1 which consists of a copolymer containing the structural unit derived from the at least 1 sort (s) of dihydroxy compound chosen from the group which consists of these ether group containing dihydroxy compounds.   The polycarbonate resin composition of Claim 1 or 2 whose content of the said phenyl group containing organopolysiloxane (B) with respect to 100 mass parts of said polycarbonate resins (A) is 0.01 mass part or more and 5 mass parts or less. The polycarbonate resin composition according to any one of claims 1 to 3, wherein R ^{1 to} R ³ in the formula (2) are composed of a methyl group. The polycarbonate resin composition of any one of Claims 1-4 whose kinematic viscosity in 25 degreeC of the said phenyl group containing organopolysiloxane (B) is 15 mm < ² > / s or more.   Further, at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid, phosphonic acid ester, acidic phosphoric acid ester, and aliphatic cyclic phosphite ester The polycarbonate resin composition according to any one of claims 1 to 5, comprising:   The molded article formed by shape | molding the polycarbonate resin composition of any one of Claims 1-6.   The molded article according to claim 7, which is an interior part or exterior part for an automobile.