JP6866562B2 - Polycarbonate resin composition and molded products made of it - Google Patents

Description

The present invention is a polycarbonate resin composition using isosorbide, which is a plant-derived raw material, and has an excellent scratch resistance with less scratches generated when the molded product is wiped with a cloth or a tissue. It relates to an article and a molded article made of 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, Patent Documents 1 and 2).
Polycarbonate resin using isosorbide is known to be excellent in heat resistance, weather resistance and impact resistance, and is also known to be applied to automobile interior / exterior parts and the like (Patent Document 3).
However, there is a problem that automobile interior / exterior parts using a polycarbonate resin using isosorbide do not have sufficient scratch resistance.

On the other hand, a polycarbonate resin containing a structural unit typified by isosorbide, which comprises a polycarbonate resin having a double bond at the end thereof and a light diffusing agent having an average particle size of 0.01 to 50 μm. A thing is also known (Patent Document 4). Patent Document 4 includes organic fine particles typified by polymer fine particles and inorganic fine particles as the light diffusing agent. In the examples, bead-shaped crosslinked silicone particles, bead-shaped crosslinked acrylic resin and calcium carbonate particles are used. It is used. However, although Patent Document 4 describes the light diffusivity of this polycarbonate resin composition, it does not describe any improvement in scratch resistance. In addition, since it exhibits light diffusivity, it is not possible to obtain a molded product having excellent vividness when it is colored.

International Publication WO2004 / 111106 Pamphlet International Publication WO2007 / 063823 Pamphlet Japanese Unexamined Patent Publication No. 2013-209585 JP-A-2009-191226

An object of the present invention is to solve the above-mentioned conventional problems and to provide a polycarbonate resin composition having excellent scratch resistance and a molded product made of the same. Further, it is an object of the present invention to provide a polycarbonate resin composition having excellent visibility at the time of coloring and excellent weather resistance, and a molded product made of the same.

As a result of diligent studies to solve the above problems, the present inventors have added a specific silicone-based compound (B) to the polycarbonate resin (A), and molded the polycarbonate resin composition. A polycarbonate resin composition in which the coefficient of dynamic friction μk with respect to the steel plate of the plate is less than a specific value and the ratio of the coefficient of dynamic friction μk to the coefficient of static friction μs is equal to or more than a specific value is excellent in scratch resistance and also in the vividness at the time of coloring. We found it to be excellent and arrived at the present invention.

That is, the gist of the present invention lies in the following [1] to [10].

[1] A polycarbonate resin composition containing a polycarbonate resin (A) containing a structural unit (a) derived from a dihydroxy compound represented by the following formula (1) and a silicone-based compound (B), wherein the polycarbonate resin composition contains the following formula (1). A polycarbonate resin composition that satisfies 2) and (3).

μｋ＜０．２２ （２）
μｋ／μｓ≧０．７０ （３）

μk <0.22 (2)
μk / μs ≧ 0.70 (3)

(In the above formulas (2) and (3), μk indicates the dynamic friction coefficient measured by the following friction coefficient measurement test, and μs indicates the same static friction coefficient.
<Friction coefficient measurement test>
A steel plate (material: SK-5) whose surface has been polished in advance is superposed on a molded plate molded from the polycarbonate resin composition, and the surface pressure is 3.1 kPa and the moving speed is 100 mm / min on the molded plate. The steel plate is moved, and the maximum load at the start of movement is defined as the coefficient of static friction μs, and the average value of the loads 4 to 6 seconds after the start of movement is defined as the coefficient of dynamic friction μk. )

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

[3] The polycarbonate according to [1] or [2], which contains 0.01 part by mass or more and 5 parts by mass or less of the silicone compound (B) with respect to 100 parts by mass of the polycarbonate resin (A). Resin composition.

[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] The polycarbonate resin composition according to any one of [3].

(In the above formulas (4) and (5), R ¹ , R ² and R ³ are 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 used.)

[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 according to any one of [1] to [5], wherein the silicone compound (B) is polymethylphenylsilsesquioxane.

[7] Any of [1] to [6], which further contains 0.001 part by mass or more and 5 parts by mass or less of the light stabilizer (C) with respect to 100 parts by mass of the polycarbonate resin (A). The polycarbonate resin composition according to.

[8] A molded product obtained by molding the polycarbonate resin composition according to any one of the above [1] to [7].

[9] The molded product according to [8], which is an automobile interior part or an exterior part.

According to the present invention, a polycarbonate resin composition having excellent scratch resistance and a molded product made of the same can be obtained, and the polycarbonate resin composition of the present invention can be obtained even if the part is conventionally painted on the surface. By using the above, it is possible to easily supply a part having scratch resistance equivalent to that of a painted product without painting. Moreover, the polycarbonate resin composition of the present invention and a molded product made of the same are also excellent in weather resistance and excellent in vividness at the time of coloring, for example, providing a molded article having high jet blackness and excellent vividness. be able to.

Hereinafter, embodiments of the present invention will be described in detail, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is described below as long as the gist of the present invention is not exceeded. It is not limited to the contents of.

<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 having a stereoisomeric relationship, and these may be used alone or in combination of two or more. You may. Among them, isosorbide, which is abundantly abundant as a plant-derived resource and is obtained by dehydration condensation of sorbitol produced from various easily available starches, is easy to obtain and produce, moldability, heat resistance, and impact resistance. 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, in order to prevent decomposition by oxygen during storage and production, moisture should not be mixed in. , It is important to use an oxygen scavenger or handle it 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 producing a polycarbonate resin, it may cause coloring of the obtained polycarbonate resin and the polycarbonate resin composition, and not only may significantly deteriorate the physical properties, but also polymerize. It may affect the reaction and a high molecular weight polymer may not be obtained.

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

The aliphatic dihydroxy compound may be a linear aliphatic dihydroxy compound or a branched chain aliphatic dihydroxy compound, and may be, for example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1 , 4-Butandiol, 1,3-Butandiol, 1,2-Butandiol, 1,5-Heptanediol, 1,6-Hexanediol, 1,10-Decandiol and the like.

Examples of the alicyclic dihydroxy compound include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, and 2,6-decalingi. Examples thereof include methanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, and 1,3-adamantan 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, polytetramethylene glycol and the like.

Considering the heat resistance of the polycarbonate resin (A), the alicyclic dihydroxy compound is preferable as the other dihydroxy compound, and among the alicyclic dihydroxy compounds, cyclohexanedimethanol is preferable from the viewpoint of heat resistance 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 the structural unit derived from all the dihydroxy compounds in the polycarbonate resin (A). Preferably, 20 mol% or more is more preferable, and 30 mol% or more is particularly preferable. Further, 50 mol% or less is preferable, and 45 mol% or less is more preferable. If the structural unit (b) derived from the other 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, which is a solution polymerization method using phosgene, melting by reacting a carbonic acid diester with a dihydroxy compound. Any of the polymerization methods 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 a lower toxicity to the environment in the presence of a polymerization catalyst is preferable. .. Further, as a polymerization catalyst (ester exchange catalyst) in melt polymerization, known alkali metal compounds and / or alkaline earth metal compounds are used. It is also 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 an alkali metal compound and / or an alkaline earth metal compound.

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

Examples of the transesterification reaction 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 a long periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). Group 1 or Group 2 (hereinafter, simply referred to as "Group 1" or "Group 2") metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, amine-based compounds, etc. Examples include compounds. 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.

It is also 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 a group 1 metal compound and / or a group 2 metal compound. It is particularly preferable to use only Group 1 metal compounds and / or Group 2 metal compounds.
Further, as the form of the group 1 metal compound and / or the group 2 metal compound, it is usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt, but it is easy to obtain and can be handled. Hydroxides, carbonates and acetates are preferable from the viewpoint of ease, and acetates are preferable from the viewpoint of hue and polymerization activity.

Examples of Group 1 metal compounds 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 hydrogen carbonate, and the like. Cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium hydride, potassium hydride, lithium hydride, cesium hydride , Sodium phenylated, potassium boron phenylated, lithium boron phenylated, cesium phenylated, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, disodium hydrogen phosphate, phosphorus 2 lithium hydrogen acid, 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 Examples thereof include a disodium salt, a dipotassium salt, a dilithium salt, and a dicesium salt of A, and among them, 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 carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, and the like. Examples thereof include strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, etc. Among them, magnesium compounds, calcium compounds and barium compounds are preferable, and magnesium compounds and / Alternatively, a calcium compound is more preferable.

Examples of the basic boron compound include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron and tributylbenzyl. Sodium salts such as boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, potassium salt, lithium salt, calcium salt, barium salt, magnesium salt, strontium salt and the like. Be done.

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, and trimethylphenylammonium hydroxide. Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, Examples thereof include butyltriphenylammonium hydroxide.

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

Among the above, using at least one metal compound selected from the group consisting of Group 2 metal compounds and lithium compounds as a catalyst is used as a catalyst for various aspects such as transparency, hue, and light resistance of the obtained polycarbonate resin (A). It is preferable to make the physical properties excellent.

Further, in order to make the transparency, hue and light resistance of the polycarbonate resin (A) particularly excellent, at least one metal compound whose catalyst is selected from the group consisting of magnesium compounds, calcium compounds and barium compounds. It is particularly preferable that it is at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds.

In the case of a group 1 metal compound and / or a group 2 metal compound, the amount of the catalyst used is preferably 0.1 to 300 μmol, more preferably 0.1 to 300 μmol, as a metal equivalent amount with respect to 1 mol of the total dihydroxy compound to be subjected to the reaction. It is in the range of 0.1 to 100 μmol, more preferably 0.5 to 50 μmol, and particularly preferably 1 to 25 μmol.

Among the above, when a compound containing at least one metal selected from the group consisting of lithium and group 2 metals is used, the metal equivalent amount is preferably 0.1 μmol or more per 1 mol of the total dihydroxy compound to be subjected to the reaction. More preferably, it is 0.5 μmol or more, and particularly preferably 0.7 μmol or more. The upper limit is preferably 20 μmol, more preferably 10 μmol, particularly preferably 3 μmol, and most preferably 2.0 μmol.

If the amount of the catalyst used is too small, the polymerization activity required to produce the polycarbonate resin (A) having a desired molecular weight may not be obtained, and sufficient fracture energy may not be obtained. On the other hand, if the amount of the catalyst used is too large, not only the hue of the obtained polycarbonate resin (A) deteriorates, but also by-products are generated to reduce the fluidity and generate more gel, resulting in brittle fracture. May cause difficulty in producing the polycarbonate resin (A) of the target quality.

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

Further, when producing the polycarbonate resin (A) used in the present invention, it is desirable to install a filter in order to prevent foreign matter from being mixed. The installation position of the filter is preferably on the downstream side of the extruder, and the size (opening) of removing foreign matter on the filter is usually preferably 100 μm or less as the filtration accuracy for 99% removal. In particular, when it is disliked to mix a minute foreign substance in a film application or the like, it is preferably 40 μm or less, more preferably 10 μm or less.

The extrusion of the polycarbonate resin (A) used in the present invention preferably has a higher cleanliness than Class 7, preferably Class 6, defined in JIS B 9920 (2002) in order to prevent foreign matter from being mixed after extrusion. It is desirable to carry out in a clean room.

Further, 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 with a HEPA filter or the like to prevent reattachment of foreign substances in the air. When using water cooling, it is desirable to use water from which metals in the water have been removed with an ion exchange resin or the like and foreign substances in the water have been removed with a filter. The opening of the filter used is preferably 10 μm to 0.45 μm as the filtration accuracy for 99% removal.

The molecular weight of the polycarbonate resin (A) used in the present invention can be expressed by the reducing viscosity, and the reducing viscosity is usually preferably 0.30 dL / g or more, more preferably 0.35 dL / g or more. The upper limit of the reduction viscosity is usually preferably 1.20 dL / g or less, more preferably 1.00 dL / g or less, and further preferably 0.80 dL / g or less.
If the reducing viscosity of the polycarbonate resin (A) is too low, the toughness of the resin composition may be small, and if the reducing viscosity is too high, the flow during molding of electrical / electronic equipment parts and automobile interior / exterior parts The property tends to decrease, and the productivity and moldability tend to decrease. In addition, the molding temperature must be raised more than appropriate, and the color tone may deteriorate.
The reduced viscosity of the polycarbonate resin is measured by using methylene chloride as a solvent, precisely adjusting the polycarbonate resin concentration to 0.6 g / dL, and using an Ubbelohde viscous tube at a temperature of 20.0 ° C. ± 0.1 ° C. ..

The glass transition temperature of the polycarbonate resin (A) used in the present invention is preferably 90 ° C. or higher and 145 ° C. or lower, more preferably 100 ° C. or higher and 135 ° C. or lower, and particularly preferably 110 ° C. or higher and 125 ° C. or lower. If the glass transition temperature is less than 90 ° C, the heat resistance is insufficient, and if it is 145 ° C or higher, the fluidity is insufficient during molding, the resin composition is not filled to the end of the product, or the strength at the weld portion is lowered. There is.

In the polycarbonate resin composition of the present invention, one type of the polycarbonate resin (A) may be used alone, and the type of structural unit derived from another dihydroxy compound, the copolymerization ratio, the physical properties, and the like are different. 2 or more may be mixed and used.

<Silicone compound (B)>
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 above formulas (4) and (5), R ¹ , R ² and R ³ are 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 used.)

Examples of the aryl group having 6 to 13 carbon atoms which may be substituted with the alkyl group having 1 to ^{3 carbon atoms of R 1 to} R 3 in the above formulas (4) and (5) include a phenyl group, a naphthyl group and a tolyl group. And so on. R ^{1 to} R ³ are preferably methyl groups or phenyl groups independently of each other 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 formula (5) is preferable. The oligomer or polymer may be a homopolymer composed of a diorganosiloxane structural unit represented by the formula (4) or an organosilsesquioxane structural unit represented by (5), or another polymerizable. It may be copolymerized with a monomer. The other polymerizable monomer is, for example, an acrylic acid ester, a methacrylic acid ester, a (meth) acrylic acid ester having another functional group such as an epoxy group or a hydroxyl group (here, "(meth) acrylic acid" is It refers to one or both of "acrylic acid" and "methacrylic acid") and the like. 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.

A commercially available product can be used as the silicone compound (B), for example, a homopolymer composed of a diorganosiloxane structural unit represented by the formula (4) or an organosilsesquioxane structural unit represented by the formula (5). Asahi Kasei Wacker Silicone Co., Ltd. Silicone Powder KSP-100, KSP-300, etc., Momentive Performance Materials Japan GK Tospar 120, 130, 145, etc., Asahi Kasei Wacker Silicone Co., Ltd. It can be obtained as PSQ SR-13, SR-20, SR-21, SR-33, etc. manufactured by Kogyo Co., Ltd.

Examples of the copolymer of dialkylsiloxane having a diorganosiloxane structure represented by the above formula (4) and alkyl (meth) acrylate include Metabrene S2001, SRK200A, SX-005, manufactured by Mitsubishi Rayon Co., Ltd. It can be obtained as Charine R-170, R-170S, etc. manufactured by Shin Kagaku Kogyo 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 size is less than 0.05 μm, the melt viscosity of the polycarbonate resin composition becomes too high, depending on the amount added, and molding may become difficult. If the average particle size is larger than 500 μm, the glossiness of the obtained molded product becomes high. It tends to decrease, and the original freshness (for example, jet-blackness) tends to decrease.
Here, the average particle size of the silicone compound (B) is the value of D50 of the laser diffraction particle size distribution measuring device, but in the case of a commercially available product, the catalog value can be adopted.

In the polycarbonate resin composition of the present invention, the blending amount of the silicone compound (B) 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 0.05 parts by mass or more and 3 parts by mass or less, particularly preferably 0.1 parts by mass or more and 2 parts by mass or less. When the blending 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, and when it is more than 5 parts by mass, the original landing freshness tends to decrease. 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 mixed and used.

<Light stabilizer (C)>
The polycarbonate resin composition of the present invention may contain a light stabilizer (C), and the weather resistance can be improved by containing a predetermined amount of the light stabilizer (C).

Examples of the light stabilizer (C) include a hindered amine-based light stabilizer, and the molecular weight thereof is preferably 1000 or less, more preferably 900 or less. If the molecular weight exceeds 1000, sufficient weather resistance may not be obtained when the molded product is formed. The molecular weight is preferably 300 or more, more preferably 400 or more. If the molecular weight is less than 300, the heat resistance is poor, the mold is contaminated during molding, and a molded product having an excellent surface appearance may not be obtained.
Further, a compound having a piperidine structure is preferable. The piperidine structure defined here may be an amine structure having a saturated 6-membered ring, and includes a piperidine structure in which a part of the piperidine structure is substituted with a substituent. Examples of the substituent include an alkyl group having 4 or less carbon atoms, and a methyl group is particularly preferable.
As the hindered amine-based light stabilizer, a compound having a plurality of piperidine structures is particularly preferable, and a compound in which the plurality of piperidine structures are linked by an ester structure is particularly preferable.

Examples of such a light stabilizer (C) include 4-piperidinol, 2,2,6,6-tetramethyl-4-benzoate, bis (2,2,6,6-tetramethyl-piperidyl) sebacate, and bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethylpiperidine-4-carboxylic acid) 1,2,3,4-butanetetrayl, 2, , 2,6,6-tetramethyl-piperidinol, tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid condensate, 2,2,6,6-tetramethyl-pyrreridineol, methanol and 1,2 , 3,4-Butanetetracarboxylic acid condensate, bis (1,2,3,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxy Reaction formation of phenyl] methyl] butylmalonate, bisdecanoic acid (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethylhydroperoxide and octane , 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4, 4-Hydroxyphenyl) propionyloxy] ethyl] -2,2,6,6-tetramethylpiperidine, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane Tetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl) -4-Piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N'-bis (2,2,6,6-tetramethyl-4- A condensate of piperidine) -1,6-hexanediamine polymer with 2,4,6-trichloro-1,3,5-triazine, 1,2,3,4-butanetetracarboxylic acid and 2,2,6 Condensate of 6-tetramethyl-4-piperidinol with β, β, β, β-tetramethyl-3,9- (2,4,5,10-tetraoxaspiro [5,5] undecane-diethanol, N , N'-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1 , 3,5-with triazine Examples thereof include a condensate, a condensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine.

When the polycarbonate resin composition of the present invention contains the light stabilizer (C), the content thereof is usually 0.001 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A), which is preferable. Is 0.005 parts by mass or more and 3 parts by mass or less, more preferably 0.01 parts by mass or more and 1 part by mass or less.
If the content of the light stabilizer is more than 5 parts by mass, it tends to be colored, and even if a colorant is added, it is difficult to obtain jet black with a sense of depth and clarity, for example. On the other hand, if it is less than 0.001 part by mass, sufficient weather resistance may not be obtained when it is used as an automobile interior / exterior product.

In the polycarbonate resin composition of the present invention, one of the above-mentioned light stabilizers (C) may be used alone, or two or more thereof may be mixed and used.

<Additives>
The polycarbonate resin composition of the present invention contains an antioxidant, an ultraviolet absorber, a mold release agent, a colorant, a neutralizing agent, an antistatic agent, a lubricant, as long as the scratch resistance and the freshness of the original film can be maintained. Lubricants, plasticizers, flame retardants, fillers and the like can also be added.

(Antioxidant)
As the antioxidant, a general antioxidant used for resins can be used, but from the viewpoints of oxidation stability, thermal stability, jet blackness, etc., phosphite-based antioxidants, sulfur-based antioxidants, and sulfur-based 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 added is usually preferably 0.001 part by mass or more, more preferably 0.002 part by mass, based on 100 parts by mass of the polycarbonate resin (A). More than parts, more preferably 0.005 parts by mass or more, usually 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less.
If the amount of the antioxidant added is more than 5 parts by mass, the mold may be contaminated during molding, and a molded product having an excellent surface appearance may not be obtained. On the other hand, if it is less than 0.001 part by mass, a sufficient improvement effect on the weather resistance test tends not to be obtained.

<Phosphite-based antioxidant>
Examples of phosphite antioxidants include triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecylphosphite, trioctylphosphite, and trioctadecyl. Phenylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, bis (2,6-di-tert-) Butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4) -Di-tert-Butylphenyl) Pentaerythritol diphosphite, distearyl pentaerythritol diphosphite and the like can be mentioned.
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.
Only one of these compounds may be used, or two or more of these compounds may be used in combination.

<Sulfur-based antioxidant>
Examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodipropionic acid ester, and di-dipropionic acid ester. Stearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate) ), Glycon-3-stearylthiopropionate, bis [2-methyl-4- (3-laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyldisulfide, mercaptobenzimidazole, 2-mercapto-6 -Methylbenzimidazole, 1,1'-thiobis (2-naphthol) and the like can be mentioned.
Of these, pentaerythritol tetrakis (3-laurylthiopropionate) is preferred.
Only one of these compounds may be used, or two or more of these compounds may be used in combination.

<Phenolic antioxidant>
Examples of the phenolic antioxidant 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, 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 (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tetrakis 4,4'-biphenylenediphosphinate (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-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol and other compounds. Be done.
Among these compounds, an aromatic monohydroxy compound substituted with 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 are preferable, and pentaerythritol- Tetrax [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is more preferred.
Only one of these compounds may be used, or two or more of these compounds may be used in combination.

(Colorant)
Examples of the colorant include organic dyes such as inorganic pigments, organic pigments and organic dyes.

Examples of inorganic pigments include carbon black; oxide-based pigments such as titanium oxide, zinc flower, petals, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, and copper-iron black. Pigments; etc.

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

One of these colorants may be used alone, or two or more of these colorants may be mixed and used.

Among the organic dyes such as the inorganic pigments, organic pigments and organic dyes, inorganic pigments are preferable. By using the inorganic pigment as a colorant, it is possible to maintain the vividness and the like for a long period of time even when the molded product is used outdoors.

When a colorant is added to the polycarbonate resin composition of the present invention, the amount of the colorant added is usually 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A), preferably 0. It is 05 parts by mass or more and 3 parts by mass or less, more preferably 0.1 parts by mass or more and 2 parts by mass or less.
If the amount of the colorant added is less than 0.05 parts by mass, it is difficult to obtain a vivid molded product. On the other hand, if the amount is more than 5 parts by mass, the surface roughness of the molded product becomes large, and it is difficult to obtain a vivid molded product.

When the colored polycarbonate resin composition of the present invention is toned to a jet-black color, for example, the lightness L ^* is preferably 0.1 or more and 10 or less, and particularly preferably 0.1 or more and 6 or less. is there. The glossiness is preferably 85% or more, and particularly preferably 88% or more.

(filler)
The polycarbonate resin composition of the present invention contains 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. , Tarku, mica, wallastnite, etc. Calcium silicate, carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless fiber, titanic acid Inorganic fillers such as potassium fiber and these 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-like / spherical organic filler; fibrous organic fillers such as carbon fiber, synthetic fiber, and natural fiber can also be added.

<Manufacturing method of polycarbonate resin composition>
The polycarbonate resin composition of the present invention is produced by mixing the above components at a predetermined ratio at the same time 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, or an extruder. can do.

<Friction coefficient of polycarbonate resin composition>
The polycarbonate resin composition of the present invention is characterized by satisfying the following formulas (2) and (3).
μk <0.22 (2)
μk / μs ≧ 0.70 (3)
(In the above formulas (2) and (3), μk indicates the dynamic friction coefficient measured by the following friction coefficient measurement test, and μs indicates the same static friction coefficient.
<Friction coefficient measurement test>
A steel plate (material: SK-5) whose surface has been polished in advance is superposed on a molded plate molded from the polycarbonate resin composition, and the surface pressure is 3.1 kPa and the moving speed is 100 mm / min on the molded plate. The steel plate is moved, and the maximum load at the start of movement is defined as the coefficient of static friction μs, and the average value of the loads 4 to 6 seconds after the start of movement is defined as the coefficient of dynamic friction μk. )

That is, in the polycarbonate resin composition of the present invention, the above-mentioned dynamic friction coefficient μk with respect to the steel plate of the molded plate formed by molding the polycarbonate resin composition is less than 0.22, and the dynamic friction coefficient μk is preferably less than 0.20. When the dynamic friction coefficient μk is 0.22 or more, the scratch resistance is deteriorated. The dynamic friction coefficient μk of the polycarbonate resin composition of the present invention is preferably smaller from the viewpoint of scratch resistance, but the lower limit thereof is usually 0.10 or more.
The ratio of the coefficient of dynamic friction μk to the coefficient of static friction μs is 0.70 or more, and this ratio is preferably 0.75 or more. If the ratio of the coefficient of dynamic friction μk to the coefficient of static friction μs is less than 0.70, the scratch resistance deteriorates. The ratio of the coefficient of dynamic friction μk to the coefficient of static friction μs of the polycarbonate resin composition of the present invention is preferably larger from the viewpoint of scratch resistance, but the upper limit thereof is usually 0.99 or less.
In the present invention, the coefficient of dynamic friction μk and the coefficient of static friction μs of the polycarbonate resin composition are specifically measured by the methods described in the evaluation methods of Examples described later.

In order to obtain a polycarbonate resin composition satisfying the above formulas (2) and (3), for example, the above-mentioned polycarbonate resin (A) and silicone-based compound (B) are used, and the coefficient of dynamic friction μk and the coefficient of static friction μs are predetermined. Examples thereof include a method of adjusting the blending amount of the polycarbonate resin (A) according to the copolymerization composition ratio of the polycarbonate resin (A) and the type of the silicone-based compound (B) in the resin composition.

<Molded product>
When molding a molded product 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. As the runner used at that time, not only the normal cold runner method but also the hot runner method can be used. In addition, insert molding, in-mold coating molding, two-color molding, sandwich molding and the like are also possible. Further, in order to obtain designability, it is also possible to use heat insulating mold molding and rapid heating and cooling mold molding.

<Use>
The molded product of the present invention, which is obtained by molding the polycarbonate resin composition of the present invention, has excellent scratch resistance and is less likely to be scratched when wiped with a cloth or tissue. It can be applied to various parts as a product by reducing the process and cost for painting. Moreover, the molded product of the present invention is excellent in vividness at the time of coloring, for example, excellent in jet-blackness and the like, and can provide high-quality parts having a high-class feeling and a profound feeling.
The application of the molded product of the present invention is not particularly limited, but it is suitable for automobile interior parts or exterior parts.

Examples of automobile interior / exterior parts to which the molded product of the present invention is applied include fenders, bumpers, facers, door panels, side garnishes, pillars, radiator grilles, side protectors, side moldings, rear protectors, rear moldings, various spoilers, and bonnets. Automotive exterior parts such as roof panels, trunk lids, detachable tops, wind reflectors, mirror housings, outer door handles, instrument panels, center console panels, meter parts, various switches, car navigation parts, car audio visual parts, autos. Examples include mobile computer parts, but the present invention is not limited to these.

Examples will be shown below and the present invention will be described in more detail, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

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

(1) Measurement of Reducing 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 _{The rel} was obtained, and the _{specific viscosity η sp} was obtained _{from the relative viscosity η ll} from the following equation (ii).
η _rel = t / t ₀ (i)
η _sp = (η − η ₀ ) / η ₀ = η _rel -1 (ii)
The specific viscosity η _sp was divided by the concentration c (g / dL) to obtain the reduced viscosity η _sp / c. The higher this value, the larger the molecular weight.

(2) Jet blackness 1 (brightness L ^* value)
A 100 mm × 100 mm × 2 mmt sheet was molded from the polycarbonate resin composition by an injection molding machine (EC-75SX manufactured by Toshiba Machine Co., Ltd.). ^{The L *} value of the sheet was measured by the D65 / 10 light source reflection method using JIS K 7105 and ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. It can be said that the smaller this value is, the higher the blackness is.

(3) Jet blackness 2 (glossiness)
For the sheet (100 mm × 100 mm × 2 mmt) molded in the same manner as in (2) above, the glossiness value (Gs60 °) was measured with a spectrocolor difference meter VG-2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS K 7105. did. It can be said that the larger this value is, the higher the glossiness is.

(4) Friction coefficient A steel plate whose surface is previously polished with # 1000 sandpaper on a test piece 1 made of a sheet (100 mm × 100 mm × 2 mmt) formed in the same manner as in (2) above (material: SK-5, Specimen 2 consisting of size: 40 mm × 40 mm × 1 mmt) is overlapped so that the polished surface is on the side of the test piece 1, and the test piece is used with a surface quality measuring machine (manufactured by Shinto Kagaku, model: HEIDON-14DR). The test piece 2 was obtained from the load when the test piece 2 was moved on 1 at a surface pressure of 3.1 kPa and a moving speed of 100 mm / min. For the coefficient of static friction μs, the maximum load at the start of movement of the test piece 2 was adopted, and for the coefficient of dynamic friction μk, the average value of the loads 4 to 6 seconds after the start of movement was adopted.

(5) Scratch resistance In a flat wear tester (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd., model: PA-300A), the tissue (manufacturer model number: 528896 manufactured by Nippon Paper Crecia Co., Ltd.) is folded three times and the wearer (bottom surface). The projected area is 20 mm x 20 mm, and the bottom surface is a curved surface of R45 mm.) A load of 9.8 N and a stroke are applied to the surface of a sheet (100 mm x 100 mm x 2 mmt) formed in the same manner as in (2) above. After 100 reciprocations at a speed of 100 mm and 30 reciprocations / minute, the surface was visually observed and evaluated according to the following criteria.
⊚: No scratches found ○: 2 or less scratches on the wearer width △: 3 or more and 10 or less scratches on the wearer width ×: The entire wearer width is white due to scratches appear

(6) Weather resistance test A test piece made of a sheet (100 mm × 100 mm × 2 mmt) formed in the same manner as in (2) above was cut in half, and black was used using an Atlas Weather Meter Ci4000 manufactured by Toyo Seiki Seisakusho Co., Ltd. Under the conditions of a panel temperature of 89 ° C. and a relative humidity of 50%, a xenon arclamp is attached as a light source, a type S porosilicate is attached as an inner filter, and a type S porosilicate is attached as an outer filter around the lamp to emit radiation having a wavelength of 300 nm to 400 nm. The illuminance was set to 100 w / m ^2, and the square surface of the test piece was irradiated with an irradiance exposure of 50 MJ / m ^2.
The obtained test piece was measured by the method (3) described above, and the gloss retention rate was calculated by the following formula.
Gloss retention rate = (gloss after irradiation treatment / gloss before irradiation treatment) x 100 (%)
The higher the value of the gloss retention rate, the better the weather resistance.
In addition, the appearance was visually observed, and if there were cracks or roughness (cloudiness) on the irradiated surface of the sample, it was marked with "x", and if there was no change, it was marked with "○".

[Silicone compound (B)]
As the silicone compound (B) to be blended in the polycarbonate resin composition, the following was used.
(B) -1: Metabrene SX-005 (manufactured by Mitsubishi Rayon, alkyl methacrylate, alkyl acrylate, dimethylsiloxane copolymer, average particle size: 150 μm)
(B) -2: PSQ SR-33 (Polymethylphenyl siloseskioxane manufactured by Konishi Chemical Industry Co., Ltd.)
(B) -3: Charine R-170S (manufactured by Nissin Chemical Industry Co., Ltd., dimethylsiloxane, alkyl methacrylate, hydroxyalkyl methacrylate copolymer, average particle size: 30 μm)
(B) -4: Metabrene SRK200A (manufactured by Mitsubishi Rayon, alkyl methacrylate, alkyl acrylate, dimethylsiloxane copolymer, average particle size: 0.15 μm)
(B) -5: Tospearl 120 (manufactured by Momentive Performance Materials Inc., polymethylsilsesquioxane, average particle size: 2 μm)

[Light stabilizer (C)]
As the light stabilizer (C) to be blended in the polycarbonate resin composition, bis (2,2,6,6-tetramethyl-piperidyl) sebacate (manufactured by BASF Japan, Tinubin 770, molecular weight 481) was used.

[Other additives]
The following were used as other additives for the polycarbonate resin composition.
other-1: Hi-Zex Million M240 (Mitsui Chemicals, ultra-high molecular weight polyethylene)
other-2: Metabrene L-1000 (manufactured by Mitsubishi Rayon, alkyl methacrylate / alkyl acrylate copolymer)
Colorant: Mitsubishi Carbon Black # 960 (manufactured by Mitsubishi Chemical Corporation)

[Manufacturing Example 1: Production of Polycarbonate Resin (A) -1]
Isosorbide (ISB) and 1,4-cyclohexanedimethanol (CHDM) were distilled and purified to a chloride ion concentration of 10 ppb or less in a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C. 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 . (Oxygen concentration 0.0005% by volume to 0.001% by volume). Subsequently, the contents were heated with a heat 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. Then, the temperature was raised, and the internal temperature was adjusted to 210 ° C. in 40 minutes. At the same time as controlling to maintain this temperature when the internal temperature reaches 210 ° C, decompression is started, and 90 minutes after reaching 210 ° C, the pressure is set to 13.3 kPa (absolute pressure, the same applies hereinafter). The pressure was retained for an additional 60 minutes. Phenol vapor produced as a by-product with the polymerization reaction was led to a reflux condenser. The components condensed by the reflux condenser were returned to the polymerization reactor, and the non-condensed phenol vapor was subsequently led to a condenser using hot water at 45 ° C. as a refrigerant and recovered.

The contents that were oligomerized in the above polymerization reactor were once repressurized to atmospheric pressure, and then transferred to another polymerization reactor equipped with a stirring blade and a similarly controlled reflux condenser to raise the temperature and raise the pressure. The depressurization was started, and the internal temperature was 220 ° C. and the pressure was 200 Pa in 60 minutes. Then, the internal temperature was lowered to 228 ° C. and the pressure to 133 Pa or less over 20 minutes, and the pressure was restored when the predetermined stirring power was reached, to obtain a molten polycarbonate copolymer from the outlet of the polymerization reactor.
Further, the molten polycarbonate copolymer is continuously supplied to a twin-screw extruder equipped with three vent ports and a water injection facility, and Irganox 1010 is used as an antioxidant for 100 parts by mass of the polycarbonate copolymer. (Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] manufactured by BASF Japan Co., Ltd.], 0.1 part by mass, Adecaster 2112 (manufactured by ADEKA Co., Ltd., Tris) (2,4-di-tert-butylphenyl) phosphite) was continuously added in an amount of 0.05 part by mass and Unistar E-275 (manufactured by Nichiyu Co., Ltd.) as a mold release agent in an amount of 0.3 part by mass. A low-molecular-weight substance such as phenol was devolatile under reduced pressure at each vent portion provided in the twin-screw extruder, and then pelletized 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.

[Manufacturing Example 2: Production of Polycarbonate Resin (A) -2]
In Production Example 1, except that the molar ratio of ISB / CHDM / DPC / calcium acetate monohydrate ^{was changed to 0.7 / 0.3 / 1.00 / 1.3 × 10-6} , the same as Production Example 1. The same procedure was carried out to obtain a polycarbonate resin (A) -2. _{The reduced viscosity η sp} / c of the polycarbonate resin (A) -2 was 0.44 dL / g.

[Example 1]
98 parts by mass of the polycarbonate resin (A) -1 obtained in Production Example 1, 1 part by mass of (B) -1 as the silicone compound, and 0.1 parts by mass of carbon black as the colorant are used and these are blended in advance. Then, using a twin-screw kneader (manufactured by Japan Steel Works, TEX30SST42BW: screw diameter 30 mm, L / D = 42), the cylinder is adjusted to an absolute vacuum pressure of 10 to 20 kPa with a vacuum pump from one place on the way. The resin composition was extruded into a strand shape at a temperature of 240 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 15 kg / hr, and a pellet-shaped resin composition sample was obtained using a strand cutter.
The obtained pellet-shaped sample was dried in a hot air dryer at 100 ° C. for 5 hours, evaluated according to the above-mentioned evaluation methods (2) to (6), and the results are shown in Table 1.

[Examples 2 to 8]
Except for the formulation shown in Table 1, extruded in the same manner as in Example 1, pellet-shaped samples were obtained, evaluated in the same manner, and the results are shown in Table 1.

[Comparative Examples 1 to 4]
Except for the formulation shown in Table 1, extruded in the same manner as in Example 1, pellet-shaped samples were obtained, evaluated in the same manner, and the results are shown in Table 1.

From Table 1, the polycarbonate resin composition of the present invention containing the polycarbonate resin (A) and the silicone compound (B) and satisfying the above formulas (2) and (3) has excellent scratch resistance and vividness at the time of coloring. It turns out to be excellent. Further, by containing the light stabilizer (C), the weather resistance is also good.

Claims (4)

A polycarbonate resin composition containing a polycarbonate resin (A) containing a structural unit (a) derived from a dihydroxy compound represented by the following formula (1) and a silicone-based compound (B).
The silicone compound (B) is contained in an amount of 0.01 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A).
The polycarbonate resin (A) is represented by a structural unit (a) derived from a dihydroxy compound represented by the following formula (1), an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and the above formula (1). A copolymerized polycarbonate resin containing a structural unit (b) derived from one or more dihydroxy compounds selected from the group consisting of ether group-containing dihydroxy compounds other than the dihydroxy compound, and the structural unit in the polycarbonate resin (A). The content ratio of (a) is 50 mol% or more and 70 mol% or less with respect to the structural unit derived from all the dihydroxy compounds in the polycarbonate resin (A), and the structural unit (b) in the polycarbonate resin (A). ) Is 10 mol% or more and 50 mol% or less with respect to the structural unit derived from the total dihydroxy compound in the polycarbonate resin (A).
The silicone compound (B) is a copolymer of dialkylsiloxane and alkyl (meth) acrylate, or polymethylphenylsilsesquioxane.
The glass transition temperature of the polycarbonate resin (A) is 90 ° C. or higher and 145 ° C. or lower.
Moreover, the polycarbonate resin composition is characterized by satisfying the following formulas (2) and (3).

μk <0.22 (2)
μk / μs ≧ 0.70 (3)
(In the above formulas (2) and (3), μk indicates the dynamic friction coefficient measured by the following friction coefficient measurement test, and μs indicates the same static friction coefficient.
<Friction coefficient measurement test>
A steel plate (material: SK-5) whose surface has been polished in advance is superposed on a molded plate molded from the polycarbonate resin composition, and the surface pressure is 3.1 kPa and the moving speed is 100 mm / min on the molded plate. The steel plate is moved, and the maximum load at the start of movement is defined as the coefficient of static friction μs, and the average value of the loads 4 to 6 seconds after the start of movement is defined as the coefficient of dynamic friction μk. ) The polycarbonate resin composition according to claim 1, further comprising 0.001 part by mass or more and 5 parts by mass or less of the light stabilizer (C) with respect to 100 parts by mass of the polycarbonate resin (A). A molded product obtained by molding the polycarbonate resin composition according to claim 1 or 2. The molded product according to claim 3, wherein the molded product is an automobile interior part or an exterior part.