JP6642093B2 - Polycarbonate resin composition and molded article comprising the same - Google Patents

Description

  The present invention is a polycarbonate resin composition using isosorbide, which is a plant-derived raw material, and when formed into a molded article, a polycarbonate resin composition having excellent abrasion resistance with less abrasion caused when wiped with a rag or tissue or the like. The present invention relates to an article and a molded article made thereof.

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, 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 interior and exterior parts of automobiles (Patent Document 3).

On the other hand, a resin composition containing a polycarbonate resin containing a structural unit derived from isosorbide and a specific impact modifier is also known (Patent Document 4). Patent Document 4 discloses a core-shell type in which a polymer of a diene-based monomer and a vinyl-based monomer is used in the core and a vinyl-based monomer is used in the shell as the impact modifier. A core-shell type polymer having at least one of butyl acrylate and butadiene as a core and methyl methacrylate as a shell is used as an impact modifier.
In addition, a resin composition containing a polycarbonate compound containing a structural unit derived from isosorbide and a silicone compound is also known (Patent Document 5). Patent Document 5 describes that the inclusion of a silicone compound improves scratch resistance.

International Publication WO2004 / 111106 pamphlet International Publication WO2007 / 063823 pamphlet JP 2013-209585 A International Publication WO2014 / 021475 pamphlet JP 2015-199954 A

In recent years, there has been a problem that automotive interior and exterior parts using a polycarbonate resin using isosorbide have insufficient scratch resistance. In addition, when applied to interior and exterior parts of automobiles, there is a demand for a high-quality, profound and high-quality part that is excellent in sharpness and the like and is exposed to light for a long period of time.
However, although Patent Document 4 describes the impact resistance modification of this polycarbonate resin composition, it is excellent in sharpness and the like, and has a more luxurious and profound feeling for a long time under an environment exposed to light. In terms of obtaining high quality parts, further improvement in characteristics was expected.
Patent Literature 5 describes improving scratch resistance. However, further improvement in characteristics has been expected from the viewpoint of obtaining a high-quality and profound feeling of high quality parts over a long period of time in an environment that is excellent in sharpness and the like and is exposed to light.

  An object of the present invention is to solve the above-mentioned conventional problems, to provide a high-quality part having a superior feeling and a profound feeling for a long time in an environment exposed to light, having excellent scratch resistance, sharpness, and the like. An object of the present invention is to provide a polycarbonate resin composition from which a molded article can be obtained and a molded article made of the same.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have produced a high-quality, solid feeling high-quality part with excellent sharpness and the like for a long time in an environment exposed to light. In order to achieve this, it has been found that a material capable of obtaining a molded article having high smoothness even after the light resistance test is suitable. That is, they have found that the following polycarbonate resin composition has excellent scratch resistance when formed into a molded article, and has high smoothness even after a light resistance test, and has reached the present invention.
"Containing a polycarbonate resin (A) containing a structural unit (a) derived from a dihydroxy compound represented by the following formula (1), a silicone-based compound (B), and an amine compound (C),
The amine compound (C) is a polycarbonate resin composition which is a compound having a secondary amine structure of 85 ° C. or higher.

」

"

That is, the gist of the present invention resides in the following.
[1] A polycarbonate resin (A) containing a structural unit (a) derived from a dihydroxy compound represented by the following formula (1), a silicone-based compound (B), and an amine compound (C),
The amine compound (C) is a polycarbonate resin composition which is a compound having a secondary amine structure of 85 ° C. or higher.

[2] The polycarbonate resin (A) includes a structural unit (a) derived from the dihydroxy compound represented by the formula (1), an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a compound represented by the formula (1). The polycarbonate resin composition according to [1], which is a copolymerized polycarbonate resin containing a structural unit (b) derived from at least one dihydroxy compound selected from the group consisting of ether group-containing dihydroxy compounds other than the dihydroxy compound represented. object. [3] In the above polycarbonate resin composition, when the total of the components (A) and (B) is 100 parts by weight, the silicone compound (B) is contained in an amount of 0.01 to 5 parts by mass [1] or The polycarbonate resin composition according to [2].
[4] The silicone compound (B) contains a diorganosiloxane structure represented by the following formula (4) and / or an organosilsesquioxane structure represented by the following formula (5) [1] to [3] ] The polycarbonate resin composition of any one of the above.

(In the formulas (4) and (5), R ¹ , R ² and R ³ are each independently substituted with a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. Represents an aryl group having 6 to 13 carbon atoms which may be substituted.)
[5] The polycarbonate resin composition according to any one of [1] to [4], wherein the silicone compound (B) is a copolymer of a dialkylsiloxane and an alkyl (meth) acrylate.
[6] The polycarbonate resin composition further contains 0.001 to 5 parts by mass of the amine compound (C) based on 100 parts by weight of the total of the components (A) and (B). 5] The polycarbonate resin composition according to any one of the above.
[7] At least one phosphorous 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 [6], containing a compound.
[8] A molded article containing the polycarbonate resin composition according to any one of [1] to [7].
[9] The molded article according to [8], which is an automobile interior part or exterior part.

  ADVANTAGE OF THE INVENTION According to this invention, when it is made into a molded article, the polycarbonate resin composition which is excellent in abrasion resistance and has high smoothness even after a light resistance test, and a molded article comprising the same can be obtained. Further, according to the present invention, for example, even for a component whose surface is conventionally coated, by using the polycarbonate resin composition of the present invention, without applying a coating, a scratch resistance equivalent to that of a coated product is obtained. It is possible to easily supply the component with the property.

  Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent requirements described below is an example (representative example) of the embodiment of the present invention, and the present invention is described below unless it exceeds the gist thereof. It is not limited to the content of.

<Polycarbonate resin (A)>
The resin composition of the present invention is characterized by containing a polycarbonate resin (A).
The polycarbonate resin (A) used in the present invention is a polycarbonate resin containing a structural unit (a) derived from a dihydroxy compound represented by the following formula (1).

  Examples of the dihydroxy compound represented by the above formula (1) include isosorbide, isomannide, and isoidet, which are in a stereoisomeric relationship. These may be used alone or in combination of two or more. You may. Above all, isosorbide obtained by dehydrating and condensing sorbitol, which is abundant as a plant-derived resource and is produced from various readily available starches, is easy to obtain and produce, moldability, heat resistance, impact resistance It is most preferable in terms of properties, surface hardness, and carbon neutrality.

  Since the dihydroxy compound represented by the above formula (1) has a cyclic ether structure, it is easily oxidized by oxygen. Therefore, at the time of storage or production, in order to prevent decomposition by oxygen, moisture is prevented from being mixed. It is important to use an oxygen scavenger or the like or to handle in a nitrogen atmosphere. For example, when isosorbide is oxidized, a decomposition product such as formic acid may be generated. When isosorbide containing these decomposed products is used as a raw material for producing a polycarbonate resin, there is a possibility that the obtained polycarbonate resin and the polycarbonate resin composition may be colored, and that not only may the physical properties be significantly deteriorated, but also the polymerization may occur. In some cases, the reaction is affected and a high molecular weight polymer cannot be obtained.

  The polycarbonate resin (A) used in the present invention includes, in addition to the structural unit (a) derived from the dihydroxy compound represented by the formula (1), an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a compound represented by the formula (1). A compound containing a structural unit (b) derived from one or more dihydroxy compounds (hereinafter, sometimes referred to as “other dihydroxy compounds”) selected from the group consisting of ether group-containing dihydroxy compounds other than the represented dihydroxy compound. A polymerized polycarbonate resin is preferable in terms of the impact resistance of the polycarbonate resin (A).

  The aliphatic dihydroxy compound may be a straight-chain aliphatic dihydroxy compound or a branched-chain aliphatic dihydroxy compound, for example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, Examples thereof include 9-nonanediol, 1,10-decanediol, 1,11-dodecanediol, and 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-norbornanedi Methanol and 1,3-adamantane dimethanol are included.

Examples of the ether group-containing dihydroxy compound include diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight: 150 to 2,000), poly-1,3-propylene glycol, polytetramethylene glycol, and the like.
Considering the heat resistance of the polycarbonate resin (A), the other dihydroxy compound is preferably an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, more preferably an alicyclic dihydroxy compound, Cyclobutanediol, cyclohexane dimethanol, and tricyclodecane dimethanol are preferred from the viewpoints of properties and impact resistance.

  The content ratio of the structural unit (b) derived from another dihydroxy compound in the polycarbonate resin (A) used in the present invention is 10 mol% or more in all the structural units derived from the dihydroxy compound in the polycarbonate resin (A). It is preferably at least 20 mol%, more preferably at least 30 mol%. Further, it is preferably at most 50 mol%, more preferably at most 45 mol%. If the structural unit (b) derived from another dihydroxy compound in the polycarbonate resin (A) is too small, the impact resistance may be insufficient, and if it is too large, the heat resistance may be insufficient.

  The polycarbonate resin (A) used in the present invention can be produced by a generally used method for producing a polycarbonate resin. The method for producing the resin is a solution polymerization method using phosgene, a melt polymerization method for reacting a diester carbonate and a dihydroxy compound. Any method of the polymerization method may be used, but a melt polymerization method in which a dihydroxy compound containing the dihydroxy compound represented by the formula (1) is reacted with a carbonic acid diester having lower environmental toxicity in the presence of a polymerization catalyst is preferable. . As a polymerization catalyst (ester exchange catalyst) in the melt polymerization, a known alkali metal compound and / or alkaline earth metal compound is used. A basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, an amine compound or the like can be used together with the alkali metal compound and / or the alkaline earth metal compound.

  As described above, the polycarbonate resin (A) used in the present invention can be produced by subjecting a dihydroxy compound containing the dihydroxy compound represented by the formula (1) to a transesterification reaction of a carbonic acid diester such as diphenyl carbonate. More specifically, it can be obtained by subjecting a transesterification reaction to remove a by-product monohydroxy compound or the like out of the system. In this case, usually, melt polymerization is carried out by a transesterification reaction in the presence of a transesterification catalyst.

  Examples of the transesterification catalyst (hereinafter sometimes referred to as “catalyst”) that can be used in the production of the polycarbonate resin (A) used in the present invention include, for example, a long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). , Such as a metal compound of Group 1 or Group 2 (hereinafter simply referred to as "Group 1" or "Group 2"), a basic boron compound, a basic phosphorus compound, a basic ammonium compound, an amine compound, or the like. Compounds. Of 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.

It is also possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound together 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.
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, a carboxylate, or a phenol. Hydroxides, carbonates, and acetates are preferred from the viewpoint of easiness, and acetates are preferred 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 borohydride, cesium borohydride, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, sodium hydrogen phosphate System, 2 potassium hydrogen phosphate, 2 lithium lithium phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, lithium, Cesium alcoholate, phenolate, bisphenol A disodium salt, dipotassium salt, dilithium salt, dicesium salt, and the like, among which cesium compounds and lithium compounds 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, strontium stearate, among which magnesium compounds, calcium compounds, barium compounds are preferable, and magnesium compounds and / or Or a calcium compound is more preferred.

  Examples of the basic boron compound include, for example, tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl Examples include sodium, potassium, lithium, calcium, barium, magnesium, and strontium salts of boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, and the like. Can be

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, for example, 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, -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.

Among the above, the use of at least one metal compound selected from the group consisting of Group 2 metal compounds as a catalyst is excellent in various physical properties such as transparency, hue, and weather resistance of the obtained polycarbonate resin (A). It is preferable to use
In order to make the polycarbonate resin (A) particularly excellent in transparency, hue, and weather resistance, the catalyst is at least one metal compound selected from the group consisting of a magnesium compound, a calcium compound, and a barium compound. Is preferable, and at least one metal compound selected from the group consisting of a magnesium compound and a calcium compound is particularly preferable.

In the case of a Group 1 metal compound and / or a Group 2 metal compound, the amount of the catalyst to be used is preferably 0.1 to 300 μmol, more preferably 0.1 to 300 μmol, in terms of metal, based on 1 mol of all dihydroxy compounds to be subjected to the reaction. It is in the range of 0.1-100 mol, more preferably 0.5-50 mol, particularly preferably 1-25 mol.
When a compound containing at least one metal selected from the group consisting of Group 2 metals is used, a metal conversion amount is preferably 0.1 μmol or more, more preferably 1 mol or more, per 1 mol of all dihydroxy compounds subjected to the reaction. Is 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 is too small, the polymerization activity required for producing the polycarbonate resin (A) having a desired molecular weight cannot be obtained, and sufficient breaking energy may not be obtained. On the other hand, if the amount of the catalyst is too large, not only the hue of the obtained polycarbonate resin (A) is deteriorated, but also by-products are generated and the flowability is reduced and gels are generated. And the production of the target quality polycarbonate resin (A) may be difficult.

As the type of the polymerization reaction, a known type can be used, and any method of a batch type, a continuous type, or a combination of a batch type and a continuous type may be used.
When the polycarbonate resin (A) used in the present invention is produced, it is desirable to install a filter in order to prevent foreign substances from being mixed. The installation position of the filter is preferably on the downstream side of the extruder, and the size (opening) of foreign matter removal of the filter is usually preferably 100 μm or less as a filtration accuracy of 99% removal. In particular, in the case where it is not desired to mix a minute foreign substance in a film application or the like, the thickness is preferably 40 μm or less, and more preferably 10 μm or less.

The extrusion of the polycarbonate resin (A) used in the present invention is preferably a class 7 defined in JIS B 9920 (2002), more preferably a higher cleanness than class 6, in order to prevent foreign matter from being mixed in after extrusion. It is desirable to carry out in a clean room.
When the extruded polycarbonate resin (A) is cooled and formed into chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance using a hepa filter or the like to prevent foreign substances in the air from re-adhering. When using water cooling, it is desirable to use water from which metal components in the water have been removed with an ion exchange resin or the like, and further, foreign matter in the water has been removed with a filter. The aperture of the filter used is preferably 10 μm to 0.45 μm as a filtration accuracy of 99% removal.

The molecular weight of the polycarbonate resin (A) used in the present invention can be represented by a reduced viscosity, and the reduced viscosity is usually preferably at least 0.30 dL / g, more preferably at least 0.35 dL / g. The upper limit of the reduced viscosity is usually 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.
If the reduced viscosity of the polycarbonate resin (A) is too low, the toughness of the resin composition may be low, and if the reduced viscosity is too large, the flow during molding of electric / electronic device parts and automobile interior / exterior parts is reduced. This tends to decrease the productivity and the productivity and moldability. In addition, the molding temperature must be higher than appropriate, and the color tone may deteriorate.
The reduced viscosity of the polycarbonate resin is measured using a Ubbelohde viscosity tube at a temperature of 20.0 ° C. ± 0.1 ° C., using methylene chloride as a solvent, precisely adjusting the polycarbonate resin concentration to 0.6 g / dL. .

The glass transition temperature of the polycarbonate resin (A) used in the present invention is preferably from 90 ° C to 145 ° C, more preferably from 100 ° C to 135 ° C, particularly preferably from 110 ° C to 125 ° C. If the glass transition temperature is less than 90 ° C., the heat resistance is insufficient, and if the glass transition temperature is 145 ° C. or more, the fluidity is insufficient at the time of molding, and the resin composition is not filled to the end of the product or the strength at the weld portion is reduced. There is.
In the polycarbonate resin composition of the present invention, one type may be used alone as the polycarbonate resin (A), and the types of structural units derived from other dihydroxy compounds, copolymerization ratios, physical properties and the like are different. May be used as a mixture of two or more.

<Silicone compound (B)>
The resin composition of the present invention is characterized by containing a silicone compound (B). By containing the silicone compound (B), scratch resistance can be improved, and in addition, slidability and squeak noise can be improved.
The silicone compound (B) used in the present invention preferably contains a diorganosiloxane structure represented by the following formula (4) and / or an organosilsesquioxane structure represented by the following formula (5).

(In the formulas (4) and (5), R ¹ , R ² and R ³ are each independently substituted with a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. Represents an aryl group having 6 to 13 carbon atoms which may be substituted.)
In the above formulas (4) and (5), examples of the aryl group having 6 to 13 carbon atoms which may be substituted with an alkyl group having 1 to ³ carbon atoms of R ^{1 to} R ³ include a phenyl group, a naphthyl group and a tolyl group And the like. It is preferable that R ^{1 to} R ³ are each independently a methyl group or a phenyl group from the viewpoint of industrial availability.

As the silicone compound (B), an oligomer or polymer containing a diorganosiloxane structure represented by the above formula (4) and / or an organosilsesquioxane structure represented by the above formula (5) is preferable. The oligomer or polymer may be a homopolymer comprising a diorganosiloxane structural unit represented by the formula (4) or an organosilsesquioxane structural unit represented by the formula (5), or may be another polymerizable polymer. It may be copolymerized with a monomer. The other polymerizable monomer is, for example, an acrylate, a methacrylate, a (meth) acrylate having another functional group such as an epoxy group or a hydroxyl group (here, “(meth) acrylic acid” "One or both of" acrylic acid "and" methacrylic acid "). As the (meth) acrylic acid ester as another polymerizable polymer, an alkyl ester of (meth) acrylic acid is preferable, and the alkyl group of the alkyl ester preferably has 1 to 4 carbon atoms.

  Commercially available products can be used as the silicone compound (B). For example, a homopolymer comprising a diorganosiloxane structural unit represented by the formula (4) or an organosilsesquioxane structural unit represented by the formula (5) Konishi Chemical, such as silicone powder KSP-100 and KSP-300 manufactured by Shin-Etsu Silicone Co., Ltd., Tospearl 120, 130, 145 manufactured by Momentive Performance Materials Japan GK, GENIOPLAST pellets S manufactured by Asahi Kasei Wacker Silicone Co., Ltd. It can be obtained as PSQ SR-13, SR-20, SR-21, SR-33, etc. manufactured by Kogyo.

Examples of the copolymer of a dialkylsiloxane having a diorganosiloxane structure represented by the formula (4) and an alkyl (meth) acrylate include Metablen S2001, SRK200A, and SX-005 manufactured by Mitsubishi Rayon Co., Ltd. It can be obtained as Charine R-170, R-170S, etc., manufactured by Shin Chemical Industry Co., Ltd.
As the silicone compound (B), a copolymer of dialkylsiloxane and alkyl (meth) acrylate, polymethylsilsesquioxane, and polymethylphenylsilsesquioxane are particularly preferable in terms of jet-blackness.

The average particle size of the silicone compound (B) is preferably 0.05 μm or more and 500 μm or less, more preferably 0.1 μm or more and 300 μm or less, and particularly preferably 0.1 μm or more and 200 μm or less. If the average particle diameter is less than 0.05 μm, depending on the amount added, the melt viscosity of the polycarbonate resin composition may be too high, and molding may be difficult. It tends to decrease, and the original clarity (for example, jet blackness) tends to decrease.
Here, the average particle diameter of the silicone compound (B) is a value of D50 measured by a laser diffraction particle size distribution analyzer, but a catalog value can be adopted for a commercially available product.

In the polycarbonate resin composition of the present invention, the compounding amount of the silicone compound (B) is 0.01 parts by mass or more when the total of the components (A) and (B) is 100 parts by weight in the polycarbonate resin composition. It is preferably 5 parts by mass or less, more preferably 0.05 parts by mass or more and 3 parts by mass or less, particularly preferably 0.1 part by mass or more and 2 parts by mass or less. When the amount of the silicone compound (B) is less than 0.01 parts by mass, the dynamic friction coefficient μk of the polycarbonate resin composition does not become less than 0.22. It is in.
In the polycarbonate resin composition of the present invention, one of the above-mentioned silicone compounds (B) may be used alone, or two or more thereof may be used in combination.

<Amine compound (C)>
The resin composition of the present invention contains an amine compound (C), and the amine compound (C) is a compound having a melting point of 85 ° C. or higher and having a secondary amine structure. By including a compound having a melting point of 85 ° C. or higher and having a secondary amine structure, the rate of change of the maximum height after the light resistance test can be reduced.
The compound having a secondary amine structure has higher basicity than the primary amine. As the amine compound (C) of the present invention, the higher the basicity, the higher the stability of polycarbonate against light and the more the deterioration such as hydrolysis is suppressed.
As the amine compound (C), for example, among the compounds available as light stabilizers, compounds having a melting point of 85 ° C. or higher and having a secondary amine structure can be used.
Among them, the secondary amine structure has a structure in which nitrogen is a part of the cyclic structure because the rate of change of the maximum height after the light resistance test can be reduced when a molded article is formed. Those having a piperidine structure are more preferable. The piperidine structure defined here may be any structure as long as it is a saturated 6-membered cyclic amine structure, including 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. The compound having a melting point of 85 ° C. or more and having a secondary amine structure preferably has a plurality of secondary amine structures, and further, the secondary amine structure is a piperidine structure, and the piperidine structure is A compound having a plurality of piperidine structures is preferable, and when having a plurality of piperidine structures, a compound in which the piperidine structures are linked by an ester structure is preferable.

Further, the absolute value of the difference between the SP value of the polycarbonate resin (A) and the amine compound (C) calculated by the Hoy method is preferably 0.0 or more and 15.0 or less, and since the bleed out resistance is more excellent, 0.0 or more and 12.0 or less are more preferable, 0.0 or more and 8.0 or less are still more preferable, and 0.0 or more and 6.0 or less are the most preferable.
Further, it is characterized in that its melting point is 85 ° C. or higher. 90 ° C. or higher and 300 ° C. or lower are preferable, 100 ° C. or higher and 250 ° C. or lower are more preferable, and 100 ° C. or higher and 250 ° C. or lower are preferable, and 110 ° C. or higher and 200 ° C. or lower are most preferable because the smoothness after the light resistance test is improved and the bleed-out resistance is excellent. preferable.

The terminal functional group equivalent is preferably 100 g / eq or more and 500 g / eq, and more preferably 100 g / eq or more and 350 g / eq or less, and more preferably 100 g / eq or more from the viewpoint that the effect of weather resistance can be imparted with a smaller amount. , 300 g / eq or less, more preferably 100 g / eq or more and 300 g / eq or less.
Moreover, the molecular weight is preferably 5,000 or less, more preferably 3,000 or less. If the molecular weight exceeds 5,000, it may not be possible to obtain sufficient weather resistance when a molded article is formed. The molecular weight is preferably 300 or more, more preferably 400 or more. When the molecular weight is less than 300, the heat resistance is poor, the mold is contaminated during molding, and a molded article having excellent surface appearance may not be obtained.

Examples of such an amine compound (C) include 2,2,6,6-tetramethyl-4-piperidinol, tetrakis (1,2,3,4-butanetetracarboxylic acid) (2,2,6,6-tetramethyl -4-piperidinyl), bis (1,2,3,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate , 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and β, β, β, β-tetramethyl-3,9- (2,4,8 And condensates with 10-tetraoxaspiro [5,5] undecane-diethanol, etc. Among these, tetrakis (1,2,3,4-butanetetracarboxylate is preferred due to its high melting point. 6,6-tetramethyl- -Piperidinyl) (SP value 19.2, melting point 130 ° C), 1,2,3,4-butanetetracarboxylic acid tetramethyl ester, 2,2,6,6-tetramethyl-4-piperidinol and β, β, A reaction product of β ′, β′-tetramethyl-2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol (SP value 18.5, melting point 95 ° C.) is preferred.

When the total amount of the component (A) and the component (B) is 100 parts by weight in the polycarbonate resin composition, the content of the amine compound (C) is preferably 0.001 to 5 parts by weight, more preferably 0 to 5 parts by weight. 0.005 to 3 parts by weight, particularly preferably 0.01 to 1 part by weight.
When the content of the amine compound (C) is more than 5 parts by weight, coloring tends to occur, and even if a coloring agent is added, it is difficult to obtain, for example, jet black having a deep and clear feeling. On the other hand, if the amount is less than 0.001 part by weight, sufficient light resistance may not be obtained when the product is used as an interior / exterior product for an automobile.

In the polycarbonate resin composition of the present invention, one of the above compounds may be used alone as the amine compound (C), or a mixture of two or more thereof may be used.
When an amine compound other than the amine compound (C) is used, it is preferable to combine the amine compound (C) with a compound having a tertiary amine structure from the viewpoint of long-term light stability as a combination of the amine compounds. Most preferably, the amine compound (C) is a compound having a piperidine structure of a secondary amine and a compound having a piperidine structure of a tertiary amine.

<Additives>
In the polycarbonate resin composition of the present invention, a catalyst deactivator, an antioxidant, an ultraviolet absorber, a release agent, a colorant, a neutralizing agent, and a charging agent as long as abrasion resistance and original image clarity can be maintained. Inhibitors, lubricants, lubricants, plasticizers, flame retardants, fillers and the like can also be added.

(Catalyst deactivator)
By adding an acidic compound to the polycarbonate resin of the present invention to neutralize and deactivate the catalyst used in the polymerization reaction, the color tone and the thermal stability can be improved. As the acidic compound used as the catalyst deactivator, a compound having a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, or an ester thereof can be used. In particular, the following formula (13) or (14) It is preferable to use a phosphorus compound having a partial structure represented by

  Examples of the phosphorus compound represented by the formula (13) or (14) include phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid ester, acidic phosphoric acid ester and the like. Can be Among the above, phosphorous acid, phosphonic acid, and phosphonic acid ester are more excellent in the effects of deactivating the catalyst and suppressing coloration, and phosphoric acid is particularly preferable.

  Examples of the 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 thereof include 1,1-diphosphonic acid, 4-methoxyphenylphosphonic acid, nitrilotris (methylenephosphonic acid), and propylphosphonic anhydride.

  Examples of phosphonate esters include dimethyl phosphonate, diethyl phosphonate, bis (2-ethylhexyl) phosphonate, dilauryl phosphonate, dioleyl phosphonate, diphenyl phosphonate, dibenzyl phosphonate, dimethyl methyl phosphonate, diphenyl methyl phosphonate, and diphenyl methyl phosphonate. Diethyl, diethyl benzyl phosphonate, dimethyl phenyl phosphonate, diethyl phenyl phosphonate, dipropyl phenyl phosphonate, diethyl (methoxymethyl) phosphonate, diethyl vinyl phosphonate, diethyl hydroxymethyl phosphonate, dimethyl (2-hydroxyethyl) phosphonate, Diethyl p-methylbenzylphosphonate, diethylphosphonoacetic acid, ethyl diethylphosphonoacetate, tert-butyl diethylphosphonoacetate, (4-k Robenzyl) diethyl phosphonate, diethyl cyanophosphonate, diethyl cyanomethylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethylphosphonoacetaldehyde diethyl acetal, diethyl (methylthiomethyl) phosphonate, etc. No.

  Examples of the acidic phosphate include dimethyl phosphate, diethyl phosphate, divinyl phosphate, dipropyl phosphate, dibutyl phosphate, bis (butoxyethyl) phosphate, bis (2-ethylhexyl) phosphate, diisotridecyl phosphate, and phosphoric acid. Examples thereof include diester phosphate such as dioleyl, distearyl phosphate, diphenyl phosphate, and dibenzyl phosphate, or a mixture of a diester and a monoester, diethyl chlorophosphate, and zinc stearyl phosphate.

One of these may be used alone, or two or more may be used as a mixture in any combination and in any ratio.
If the amount of the phosphorus-based compound added to the resin is too small, the effect of deactivating the catalyst and suppressing the coloring is insufficient, and if the amount is too large, the resin may be colored instead, or a durability test particularly under high temperature and high humidity. In the above, the resin is easily colored. The phosphorus-based compound is added in an amount corresponding to the amount of the catalyst used in the polymerization reaction. With respect to 1 mol of the metal of the catalyst used in the polymerization reaction, the amount of the phosphorus-based compound is preferably 0.5 mol or more and 5 mol or less, more preferably 0.7 mol or more and 4 mol or less as the amount of phosphorus atoms. It is preferably from 0.8 times mol to 3 times mol.

(Antioxidant)
As the antioxidant, general antioxidants used for resins can be used, but from the viewpoints of oxidation stability, heat stability, jet blackness, etc., phosphite antioxidants, sulfur antioxidants, and Phenolic antioxidants are preferred.
When an antioxidant is added to the polycarbonate resin composition of the present invention, the amount of the antioxidant is usually 0.1% when the total of the components (A) and (B) is 100 parts by weight in the polycarbonate resin composition. It is preferably at least 001 parts by weight, more preferably at least 0.002 parts by weight, even more preferably at least 0.005 parts by weight, usually at most 5 parts by weight, more preferably at most 3 parts by weight, even more preferably at most 2 parts by weight. Part or less.
If the amount of the antioxidant is more than 5 parts by weight, the mold may be contaminated during molding, and a molded article having excellent surface appearance may not be obtained. On the other hand, if the amount is less than 0.001 part by weight, there is a tendency that a sufficient improvement effect on the weather resistance test cannot be obtained.

<Phosphite antioxidant>
Examples of phosphite-based antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, and 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, distearylpentaerythritol diphosphite and the like.
Among these, trisnonylphenyl 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.
These compounds may be used alone or in combination of two or more.

<Sulfur antioxidant>
Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, 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, octadecyldisulfide, mercaptobenzimidazole, 2-mercapto-6 -Methylbenzy Imidazole, 1,1'-thiobis (2-naphthol), and the like.
Among these, pentaerythritol tetrakis (3-laurylthiopropionate) is preferred.
These compounds may be used alone or in combination of two or more.

<Phenolic antioxidant>
Examples of phenolic antioxidants include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and 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- (3,3 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, tetrakis (4,4′-biphenylenediphosphinic acid) (2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl -2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane, 2,6- Compounds such as di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4-ethylphenol are exemplified.

Among these compounds, an aromatic monohydroxy compound substituted by one or more alkyl groups having 5 or more carbon atoms is preferable, and 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, and pentaerythritol- Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] A further preferred.
These compounds may be used alone or in combination of two or more.

(UV absorber)
The polycarbonate resin composition of the present invention may contain an ultraviolet absorber as long as the object of the present invention is not impaired. Specifically, for example, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole , 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2'- p-phenylenebis (1,3-benzoxazin-4-one) and the like. The content of the ultraviolet absorber is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

(Colorant)
Examples of the colorant include organic dyes and pigments such as inorganic pigments, organic pigments, and organic dyes.
Examples of the inorganic pigment include carbon black; oxides such as titanium oxide, zinc oxide, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, and copper-iron black. Pigments and the like.

  Organic pigments such as organic pigments and organic dyes include, for example, phthalocyanine-based pigments; azo-based, thioindigo-based, perinone-based, perylene-based, quinacridone-based, dioxazine-based, isoindolinone-based, condensed polycycles such as quinophthalone-based Dyes and pigments; anthraquinone, perinone, perylene, methine, quinoline, heterocyclic and methyl dyes and the like.

These colorants may be used alone or in a combination of two or more.
Among the organic dyes such as inorganic pigments, organic pigments and organic dyes, inorganic pigments are preferred. By using an inorganic pigment as a colorant, sharpness and the like can be maintained for a long time even when the molded article is used outdoors or the like.
When a colorant is added to the polycarbonate resin composition of the present invention, the amount of the colorant is usually 0.05 mass when the total of the components (A) and (B) is 100 parts by weight in the polycarbonate resin composition. Or more, and preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass.

If the amount of the colorant is less than 0.05 parts by mass, it is difficult to obtain a moist original molded article. On the other hand, if the amount is more than 5 parts by mass, the surface roughness of the molded article becomes large, and it is difficult to obtain a moist original molded article.
When the colored polycarbonate resin composition of the present invention is toned to jet black, for example, the lightness L ^* is preferably 0.1 or more and 10 or less, particularly preferably 0.1 or more and 6 or less. is there. Further, the glossiness is preferably at least 85%, particularly preferably at least 88%.

(filler)
In the polycarbonate resin composition of the present invention, glass fibers, glass milled fibers, glass flakes, glass beads, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whisker, barium sulfate as long as the design can be maintained. , Calcium silicate such as talc, mica, wollastonite, carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, titanic acid Potassium fibers, inorganic fillers such as whiskers, and powdered organic fillers such as wood flour, bamboo flour, coconut starch, cork flour, pulp flour; crosslinked polyester, polystyrene, styrene / acrylic copolymer, urea resin, etc. Balun and spherical organic fillers; carbon fiber, synthetic fiber, natural fiber It can be added fibrous organic fillers such as.

<Production method of polycarbonate resin composition>
The polycarbonate resin composition of the present invention is manufactured by mixing the above components at a predetermined ratio simultaneously or in an arbitrary order by a mixer such as a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, an extruder, and the like. can do.

<Molded product>
When molding a molded article using the polycarbonate resin composition of the present invention, any molding method can be used, but injection molding, injection compression, and injection press molding are preferably used. The runner used at that time may be not only a normal cold runner system but also a hot runner system. Also, insert molding, in-mold coating molding, two-color molding, sandwich molding and the like are possible. Further, in order to obtain designability, it is also possible to use heat-insulating mold molding and rapid heating / cooling mold molding.

<Application>
The molded article of the present invention obtained by molding the polycarbonate resin composition of the present invention is excellent in abrasion resistance and has little abrasion generated when wiped with a rag or tissue, so that the coating is not applied, and therefore, The coating process and cost can be reduced, and the product can be applied to various parts. Moreover, since the molded article of the present invention is excellent in smoothness after the weather resistance test, for example, it is excellent in sharpness and the like, and it is possible to produce a high-quality, solid feeling high-quality part for a long time in an environment exposed to light. Can be provided.
The application of the molded article of the present invention is not particularly limited. However, the molded article of the present invention is suitable for interior or exterior products, automobile interior parts or exterior parts.

  The interior and exterior parts for automobiles to which the molded article of the present invention is applied include, for example, fenders, bumpers, fascias, door panels, side garnishes, pillars, radiator grills, side protectors, side moldings, rear moldings, rear moldings, various spoilers, bonnets, Automotive exterior parts such as roof panel, trunk lid, detachable top, wind reflector, mirror housing, outer door handle, instrument panel, center console panel, meter parts, various switches, car navigation parts, car audio visual parts, auto Examples include mobile computer components, but are not limited thereto.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist.

[Evaluation method]
In the following, the evaluation of the physical properties or properties of the polycarbonate resin and the polycarbonate resin composition was performed by the following methods.

(1) Measurement of reduced viscosity A polycarbonate resin sample was dissolved using methylene chloride as a solvent to prepare a polycarbonate solution having a concentration of 0.6 g / dL. Using Moritomo Rika Co. Ubbelohde viscometer tube was measured at a temperature of 20.0 ° C. ± 0.1 ° C., relative viscosity by the following equation (i) from the passing time t of the passing time t ₀ and a solution of solvent η _rel was determined, and the specific viscosity η _sp was determined from the relative viscosity η _rel by the following equation (ii).
η _rel = t / t ₀ (i)
η _sp = (η−η ₀ ) / η ₀ = η _rel −1 (ii)
The reduced viscosity η _sp / c was obtained by dividing the specific viscosity η _sp by the concentration c (g / dL). The higher the value, the higher the molecular weight.

(2) Jet-blackness 1 (lightness L ^* value)
A 100 mm × 100 mm × 2 mmt sheet was formed from the polycarbonate resin composition by an injection molding machine (EC-75SX manufactured by Toshiba Machine Co., Ltd.). JIS for the sheet
According to K 7105, L ^* value was measured by D65 / 10 light source reflection method using ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. It can be said that the smaller this value is, the higher the blackness is. In the present invention, 5 or less was regarded as acceptable.

(3) Jet-blackness 2 (glossiness)
The gloss value (Gs 60 °) of a sheet (100 mm × 100 mm × 2 mmt) formed in the same manner as in the above (2) is measured with a spectral color difference meter VG-2000 manufactured by Nippon Denshoku Industries, in accordance with JIS K 7105. did. It can be said that the larger this value is, the higher the glossiness is. In the present invention, 85 or less was regarded as acceptable.

(4) Scratch resistance Tissue (flower box made by Nippon Paper Crecia Co., Ltd.) was folded three times with a surface property measuring device (manufactured by Shinto Kagaku Co., Ltd., type: Tribogear TYPE-14FW), and the wear element (projected area of the bottom surface) was folded. 20 mm × 20 mm), and after reciprocating 500 times at a load of 9.8 N, a stroke of 50 mm, and a speed of 3000 mm / min on the surface of a sheet (100 mm × 100 mm × 2 mmt) formed in the same manner as (2) above, ), The glossiness of the scratched surface was measured, and the change in glossiness before and after the abrasion test was evaluated. In the present invention, 1 or less was regarded as acceptable.

(5) Weather resistance test A test piece composed of a sheet (100 mm × 100 mm × 2 mmt) formed in the same manner as in (2) above was cut in half, and a 7.5 kW super xenon weather meter SX75 manufactured by Suga Test Instruments Co., Ltd. was cut. According to JIS D0205, using a xenon arc lamp in an environment of a black panel temperature of 89 ° C. and a relative humidity of 50%, a wavelength range of 300 to 400 nm, a sample surface radiation intensity of 75 W / m 2, and a silicate glass The maximum height of the sample surface before and after irradiation treatment for 1200 hours through an outer glass filter and an inner filter of quartz glass was measured using a high-precision shape measurement system (manufactured by Keyence Corporation, model: KS-1100), The maximum height of the sample surface after the weather resistance test and the maximum height change rate of the sample surface before and after the weather resistance test were evaluated. In the present invention, 1% or less was regarded as acceptable.

[Silicone compound (B)]
As the silicone compound (B) to be added to the polycarbonate resin composition, Methrene SX-005 (manufactured by Mitsubishi Rayon Co., Ltd., alkyl methacrylate / alkyl acrylate / dimethylsiloxane copolymer, average particle diameter: 150 μm) was used.

[Amine compound (C)]
The following were used as the amine compound (C) to be blended in the polycarbonate resin composition.
(C-1): LA-57 (manufactured by ADEKA, tetrakis (1,2,3,4-butanetetracarboxylic acid) (2,2,6,6-tetramethyl-4-piperidinyl), SP value 19.2, (C-2): LA-68 (manufactured by ADEKA, 1,2,3,4-butanetetracarboxylic acid tetramethyl ester, 2,2,6,6-tetramethyl-4-piperidinol and β) , Β, β ′, β′-tetramethyl-2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol, SP value 18.5, melting point 95 ° C.)
(C-3): LA-52 (manufactured by ADEKA, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate, SP value 18)
. 0, melting point 65 ° C)
(C-4): LA-63P (manufactured by ADEKA, 1,2,3,4-butanetetracarboxylic acid, tetramethyl ester, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β , Β ', β'-tetramethyl-2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol, SP value 19.5, melting point 95 ° C)
(C-5): LA-81 (manufactured by ADEKA, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, SP value 18.3, liquid)
(C-6): Tinuvin 770 (manufactured by BASF Japan, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, SP value 18.8, melting point 83 ° C.)
* If the melting point has a range of temperature, the average of the minimum and maximum temperatures is taken as the melting point.

[Other additives]
The following were used as other additives of the polycarbonate resin composition.
Colorant: Mitsubishi Carbon Black # 960 (Mitsubishi Chemical Corporation)

[Production Example: Production of polycarbonate resin (A)]
Isosorbide (ISB) and 1,4-cyclohexane dimethanol (CHDM) were distilled and purified in a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C. to diphenyl having a chloride ion concentration of 10 ppb or less. The molar ratio of carbonate (DPC) and calcium acetate monohydrate is ISB / CHDM / DPC / calcium acetate monohydrate = 0.5 / 0.5 / 1.00 / 1.3 × 10 ⁻⁶ And sufficiently purged with nitrogen (oxygen concentration 0.0005% by volume to 0.001% by volume). Subsequently, the content was heated with a heating medium. Stirring was started when the internal temperature reached 100 ° C, and the contents were melted and made uniform while controlling the internal temperature to 100 ° C. Thereafter, the temperature was raised, and the internal temperature was raised to 210 ° C. in 40 minutes. When the internal temperature reaches 210 ° C., the temperature is controlled to be maintained at the same time. At the same time, pressure reduction is started, and 90 minutes after the temperature reaches 210 ° C., 13.3 kPa (absolute pressure, the same applies hereinafter). The pressure was maintained for an additional 60 minutes. Phenol vapor by-produced during the polymerization reaction was led to a reflux condenser. The components condensed in the reflux condenser were returned to the polymerization reactor, and the uncondensed phenol vapor was subsequently collected by introducing it to a condenser using hot water at 45 ° C. as a refrigerant.

After the content oligomerized in the polymerization reactor is once returned to atmospheric pressure, the content is transferred to another polymerization reactor equipped with a stirring blade and a reflux condenser controlled in the same manner as described above, and the temperature is raised and Decompression was started, and the internal temperature was set to 220 ° C. and the pressure to 200 Pa in 60 minutes. Thereafter, the internal temperature was lowered to 228 ° C. and the pressure to 133 Pa or lower over 20 minutes, and the pressure was restored when the predetermined stirring power was reached, to obtain a polycarbonate copolymer in a molten state from the polymerization reactor outlet. Further, the molten polycarbonate copolymer was continuously supplied to a twin-screw extruder provided with three vent ports and a water injection facility, and Irganox 1010 was used as an antioxidant with respect to 100 parts by mass of the polycarbonate copolymer. 0.1 parts by mass of pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (BASF Japan Co., Ltd.) and ADEKA STAB 2112 (Tris, manufactured by ADEKA Corporation) (2,4-di-tert-butylphenyl) phosphite) was 0.05 parts by mass, and phosphorous acid (manufactured by Taihei Chemical Industry Co., Ltd., molecular weight: 82.0) was 6.4 × 10 5 as a catalyst deactivator. ⁻⁵ parts by mass and 0.3 parts by mass of Unistar E-275 (manufactured by NOF CORPORATION) as a release agent were continuously added, and twin screw extrusion was performed. After low-molecular-weight substances such as phenol were devolatilized under reduced pressure at each vent portion provided in the machine, pelletization was performed with a pelletizer to obtain a polycarbonate resin (A) -1. The reduced viscosity η _sp / c of the polycarbonate resin (A) -1 was 0.61 dL / g.

[Example 1]
Using 98 parts by mass of the polycarbonate resin (A) -1 obtained in Production Example 1, 1 part by mass of (B) -1 as a silicone compound, and 0.1 part by mass of carbon black as a coloring agent, these were previously blended. In advance, using a twin-screw kneader (manufactured by Nippon Steel Works, TEX30SST42BW: screw diameter 30 mm), the absolute vacuum pressure is 10 to 20 with a vacuum pump from one place on the way.
The resin composition was extruded into a strand at a cylinder temperature of 230 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 30 kg / hr while adjusting the pressure to kPa, and a pellet-shaped resin composition sample was obtained using a strand cutter.
After the obtained pellet-shaped sample was dried at 100 ° C. for 5 hours using a hot air drier, evaluation was performed according to the above-described evaluation methods (2) to (5), and the results are shown in Table 1.

[Example 2]
Extrusion was performed in the same manner as in Example 1 except that the composition was as shown in Table 1, and a pellet sample was obtained. Evaluation was performed in the same manner, and the results are shown in Table 1.

[Comparative Examples 1 to 5]
Extrusion was performed in the same manner as in Example 1 except that the composition was as shown in Table 1, and a pellet sample was obtained. Evaluation was performed in the same manner, and the results are shown in Table 1.

  Table 1 shows that the polycarbonate resin composition of the present invention, which contains the polycarbonate resin (A) and the silicone compound (B), that is, the Example is superior in smoothness after the weather resistance test to the Comparative Example.

Claims (10)

It contains a polycarbonate resin (A) containing a structural unit (a) derived from a dihydroxy compound represented by the following formula (1), a silicone compound (B), and an amine compound (C),
The amine compound (C) is a polycarbonate resin composition having a secondary amine structure in which nitrogen is part of a cyclic structure and having a melting point of 85 ° C. or higher .

  The polycarbonate resin (A) is represented by the structural unit (a) 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 claim 1, wherein the polycarbonate resin composition is a copolymer polycarbonate resin containing at least one structural unit (b) derived from at least one dihydroxy compound selected from the group consisting of ether group-containing dihydroxy compounds other than the dihydroxy compound.   3. The polycarbonate resin composition according to claim 1, wherein the silicone compound (B) is contained in an amount of 0.01 to 5 parts by mass when the total of the components (A) and (B) is 100 parts by weight. Polycarbonate resin composition. The silicone compound (B) comprises a diorganosiloxane structure represented by the following formula (4) and / or an organosilsesquioxane structure represented by the following formula (5). Item 10. The polycarbonate resin composition according to item 1.

(In the above formulas (4) and (5), R1, R2 and R3 are each independently substituted with a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. Represents an aryl group having 6 to 13 carbon atoms.)   The polycarbonate resin composition according to any one of claims 1 to 4, wherein the silicone compound (B) is a copolymer of a dialkylsiloxane and an alkyl (meth) acrylate.   6. The polycarbonate resin composition according to claim 1, further comprising 0.001 to 5 parts by mass of the amine compound (C) based on 100 parts by weight of the total of the components (A) and (B). Item 2. The polycarbonate resin composition according to item 1.   Contains 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 6. The polycarbonate resin composition according to any one of claims 1 to 7, wherein the secondary amine structure has a piperidine structure. A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 8 . The molded article according to claim 9 , which is an automobile interior part or exterior part.