JP6618239B2 - 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 is a polycarbonate resin composition having excellent scratch resistance with few scratches generated when wiped with a rag or tissue when formed into a molded product 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 to 4).
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 and exterior parts (Patent Document 3).
However, automotive interior / exterior parts using polycarbonate resin using isosorbide have a problem that the scratch resistance is not sufficient.

  Patent Documents 1 and 3 describe carbon fiber as an additive (filler) that may be blended in the polycarbonate resin composition. In addition, Patent Document 4 describes graphite (graphite) as an inorganic filler for reinforcement, and there is a description that conductivity, strength, and rigidity are imparted by addition of carbon fiber or milled fiber. There is also a description of polytetrafluoroethylene as an inhibitor. However, there is no specific example in which any of these patent documents is actually blended, and there is no description that the scratch resistance can be improved by blending milled carbon fiber, graphite, or polytetrafluoroethylene.

International Publication WO2004 / 111106 Pamphlet International Publication WO2007 / 063823 Pamphlet JP 2013-209585 A JP 2014-51558 A

  An object of the present invention is to solve the above-described conventional problems and provide a polycarbonate resin composition excellent in scratch resistance and a molded article comprising the same.

  As a result of intensive studies to solve the above problems, the present inventors have added a slidability modifier (B) to the polycarbonate resin (A), and are made of the polycarbonate resin composition. The present inventors have found that a polycarbonate resin composition having a dynamic friction coefficient μk and a static friction coefficient μs of a formed plate with respect to a steel plate are not more than specific values has excellent scratch resistance, and has reached the present invention.

  That is, the gist of the present invention resides in the following [1] to [8].

[1] see contains the following formula (1) derived from a dihydroxy compound represented by the structural units (a), a reduced viscosity of 0.35 dL / g or more, 0.80 dL / g or less is polycarbonate resin (A), the And a slidability modifier (B), which satisfies the following formulas (2) and (3):

μk ≦ 0.20 (2)
μs ≤ 0.25 (3)
(Μk in the above equation (2) indicates a dynamic friction coefficient measured by the following friction coefficient measurement test, and μs in the above equation (3) indicates a 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. The steel plate is moved, the maximum load at the start of movement is set as the static friction coefficient μs, and the average value of the load from 4 seconds to 6 seconds after the start of movement is set as the dynamic friction coefficient μk. )

[2] The polycarbonate resin (A) is a 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). [1] characterized in that it is a copolymer polycarbonate resin comprising 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 compounds. The polycarbonate resin composition as described.

[3] The slidability modifier (B) is contained in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A) [1] or [2] The polycarbonate resin composition described in 1.

[4] The sliding modifier (B) is one or more selected from the group consisting of graphite powder, pitch-based milled carbon fiber, and polytetrafluoroethylene powder. 3]. The polycarbonate resin composition according to any one of [3].

[5] The polycarbonate resin composition according to [4], wherein the slidability modifier (B) is a graphite powder.

[6] The polycarbonate resin composition according to [4], wherein the slidability modifier (B) is pitch-based milled carbon fiber.

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

[8] The molded article according to [7], 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 comprising the same can be obtained, and even a part that has been coated on the surface of the polycarbonate resin composition of the present invention can be obtained. By using, it becomes possible to easily supply a part imparted with scratch resistance equivalent to that of a coated product without coating.

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents.

<Polycarbonate resin (A)>
The polycarbonate resin (A) used for this invention is a polycarbonate resin characterized by including the structural unit (a) derived from the dihydroxy compound represented by 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, and these may be used alone or in combination of two or more. May be. Among them, isosorbide obtained by dehydrating and condensing sorbitol produced from various starches that are abundant as plant-derived resources is easy to obtain and manufacture, moldability, heat resistance, impact resistance Most preferable from the viewpoints of properties, surface hardness, and carbon neutral.

  Since the dihydroxy compound represented by the above formula (1) has a cyclic ether structure, it is likely to be gradually oxidized by oxygen. Therefore, during storage and production, in order to prevent decomposition by oxygen, water should not be mixed, It is important to use an oxygen scavenger and handle under a nitrogen atmosphere. For example, when isosorbide is oxidized, decomposition products such as formic acid may be generated. When isosorbide containing these decomposition products is used as a raw material for the production of polycarbonate resin, it may cause coloring of the obtained polycarbonate resin and polycarbonate resin composition, and may not only significantly deteriorate the physical properties, but also polymerize. The reaction may be affected and a high molecular weight polymer may not be obtained.

  The polycarbonate resin (A) used in the present invention is 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). Co-containing 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 compounds (hereinafter sometimes referred to as “other 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 aliphatic dihydroxy compound. For example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,10-decanediol and the like.

  Examples of alicyclic dihydroxy compounds include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, and 2,6-decalindi. Examples include methanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, and 1,3-adamantane dimethanol.

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

  Considering the heat resistance of the polycarbonate resin (A), the other dihydroxy compound is preferably an alicyclic 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 other dihydroxy compounds in the polycarbonate resin (A) used in the present invention is 10 mol% or more in the structural units derived from all dihydroxy compounds in the polycarbonate resin (A). Preferably, 20 mol% or more is more preferable, and 30 mol% or more is particularly preferable. Moreover, 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 production method of a polycarbonate resin, and the production method is a solution polymerization method using phosgene, a melt in which a carbonic acid diester and a dihydroxy compound are reacted. Although any polymerization method may be used, a melt polymerization method in which a dihydroxy compound is reacted with a carbon dioxide diester having lower toxicity to the environment in the presence of a polymerization catalyst is preferable. In addition, as a polymerization catalyst (transesterification catalyst) in melt polymerization, a known alkali metal compound and / or alkaline earth metal compound is 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 together with an alkali metal compound and / or an alkaline earth metal compound.
As the polymerization reaction, a known method can be used, and any method of a batch method, a continuous method, or a combination of a batch method and a continuous method may be used.

  Moreover, when manufacturing the polycarbonate resin (A) used for this invention, in order to prevent mixing of a foreign material, it is desirable to install a filter. The filter installation position is preferably on the downstream side of the extruder, and the filter foreign matter removal size (opening) is usually preferably 100 μm or less as a 99% removal filtration accuracy. In particular, in the case of disagreeing with the entry of minute foreign matters for film use etc., it is preferably 40 μm or less, more preferably 10 μm or less.

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

  Moreover, when cooling the extruded polycarbonate resin (A) 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 metal in water has been removed with an ion exchange resin or the like, and further, foreign matter in water has been removed with a filter. The opening of the filter to be used is preferably 10 μm to 0.45 μm as 99% removal filtration accuracy.

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 0.30 dL / g or more, and more preferably 0.35 dL / g or more. 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 small. If the reduced viscosity is too large, the flow when molding electrical / electronic equipment parts and automotive interior / exterior parts There is a tendency that the productivity is lowered and the productivity and moldability are lowered. 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 viscometer 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 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. When the glass transition temperature is less than 90 ° C, the heat resistance is insufficient, and when it 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 part is reduced. There is.

  In the polycarbonate resin composition of the present invention, one type of polycarbonate resin (A) may be used alone, and the types of structural units derived from other dihydroxy compounds, copolymerization ratios, physical properties, and the like are different. Two or more may be mixed and used.

<Slidability modifier (B)>
When the sliding property modifier (B) used in the present invention is added to the polycarbonate resin (A), the polycarbonate resin composition satisfies the following formulas (2) and (3). There is no particular limitation, and among these, one or more kinds of slides selected from the group consisting of graphite powder, pitch-based milled carbon fiber, and polytetrafluoroethylene powder (hereinafter abbreviated as “PTFE powder”). A mobility modifier is preferred. In particular, graphite powder and / or pitch-based milled carbon fibers are preferred.

<< (B) -1: Graphite powder >>
The graphite powder used in the present invention is preferably flaky graphite or exfoliated graphite.

Scaly graphite is refined natural graphite and processed into a scaly shape with increased purity.
The flaky graphite powder preferably has an average particle size of 5 to 30 μm, and more preferably 5 to 20 μm. Examples of commercially available scale-like graphite include CP series and special CP made by Nippon Graphite Industry.

Exfoliated graphite powder is ultra-thinned and highly purified by physical refining and chemical treatment that removes graphite and impurities in addition to the general manufacturing process. For example, ions such as nitrate ions between graphite layers It can be obtained by a chemical treatment method in which heat treatment is performed after insertion, a physical treatment method such as applying ultrasonic waves to graphite, or an electrochemical method in which electrolysis is performed using graphite as a working electrode.
The exfoliated graphite powder preferably has an average particle size of 5 to 600 μm, and more preferably 10 to 200 μm. Examples of commercially available exfoliated graphite include GR-15, UP-15N and UP-35 manufactured by Nippon Graphite Industries.

  The graphite powder may be subjected to surface modification treatment. Examples of the surface modification treatment include a treatment of grafting a resin on the surface of the graphite powder or introducing a hydrophilic functional group or a hydrophobic functional group onto the surface of the graphite powder. By subjecting the graphite powder to surface modification treatment, the affinity between the graphite powder and the polycarbonate resin (A) can be increased. When the affinity between the graphite powder and the polycarbonate resin (A) is increased, the mechanical strength of the obtained polycarbonate resin molded product is increased.

In addition, although the average particle diameter of said graphite powder is a value of D50 of a laser diffraction particle size distribution measuring apparatus, a catalog value can be employ | adopted about a commercial item.
If the average particle size of the graphite powder is too large, the appearance of the obtained polycarbonate resin molded product tends to deteriorate. On the other hand, if the average particle size is too small, the effect of improving the scratch resistance may not be sufficiently obtained. .

<< (B) -2: Pitch-based milled carbon fiber >>
The pitch-based milled carbon fiber used in the present invention is an isotropic pitch that is optically disordered and exhibits no deflection when the raw material pitch is observed with a polarizing microscope. For example, the density is 1.6 g / cm ³ and the diameter is 12 A powdery body obtained by finely pulverizing ˜18 μm short fibers is preferable. Further, the ratio (aspect ratio) between the average fiber length and the average fiber diameter of the pitch-based milled carbon fiber is preferably 3 to 150.
Such commercially available pitch-based milled carbon fibers can be obtained from Osaka Gas Chemical Company as Donakabo Milled S-2404, S-249, and the like.

<< (B) -3: PTFE powder >>
The PTFE constituting the PTFE powder used in the present invention preferably has a molecular weight of less than 1 million measured by a differential scanning calorimeter (DSC method). When the molecular weight measured by the DSC method is less than 1,000,000, the effect of improving the scratch resistance can be sufficiently exhibited.
The molecular weight of PTFE shown here is a value obtained by a DSC method obtained from a value measured by a differential scanning calorimeter. The number of heats of crystallization of PTFE measured by a differential scanning calorimeter is calculated based on the following formula: Average molecular weight (Mn).
Mn = 2.1 × 10 ¹⁰ × ΔHc− ^5.16
(ΔHc: DSC heat of crystallization (cal / g))

  In the PTFE, fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, perfluoroalkyl vinyl ether, perfluoroalkyl (meth) acrylate, etc. are used as copolymerization components as long as the properties of PTFE are not impaired. The copolymer component obtained by superposing | polymerizing in presence of fluorine-containing alkyl (meth) acrylate etc. may be contained. The content of the copolymer component is preferably 10% by mass or less with respect to PTFE.

The average particle diameter of the PTFE powder is preferably 0.05 to 10 μm, more preferably 0.1 to 8 μm. When the average particle diameter of PTFE is larger than 10 μm, the appearance of the obtained polycarbonate resin molded product tends to deteriorate. On the other hand, when the average particle size of the PTFE powder is less than 0.05 μm, the dispersion in the resin composition may not be sufficient, and the scratch resistance may not be sufficiently exhibited.
As such a commercial product of PTFE powder, for example, Lubron L-5, L-5F manufactured by Daikin Industries, Ltd. can be used.

  Here, although the average particle diameter of PTFE powder is the value of D50 of a laser diffraction particle size distribution measuring apparatus, a catalog value is employable about a commercial item.

  In the polycarbonate resin composition of the present invention, the blending amount of the slidability modifier (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 0.1 to 4 parts by mass, particularly preferably 0.5 to 3 parts by mass. When the blending amount of the slidability modifier (B) is less than 0.01 parts by mass, the dynamic friction coefficient μk and the static friction coefficient μs of the polycarbonate resin composition cannot be lowered, and the following formulas (2) and (3 ) May not be satisfied together, and when the amount is more than 5 parts by mass, the appearance of the obtained polycarbonate resin molded product tends to be inferior.

  In the polycarbonate resin composition of the present invention, one kind of the above-mentioned slidability modifier (B) may be used alone, or two or more kinds may be mixed and used.

<Additives>
The polycarbonate resin composition of the present invention has an antioxidant, a light stabilizer, an ultraviolet absorber, a release agent, a colorant, a neutralizer, and an antistatic material within a range that can maintain scratch resistance and original image clarity. Agents, lubricants, lubricants, plasticizers, flame retardants, fillers and the like can also be added.

(Antioxidant)
As the antioxidant, general antioxidants used for resins can be used, but from the viewpoint of oxidation stability, thermal stability, jet blackness, etc., phosphite antioxidants, sulfur antioxidants, and Phenol antioxidants are preferred.

When adding an antioxidant to the polycarbonate resin composition of the present invention, the addition amount is usually preferably 0.001 parts by mass or more, more preferably 0.002 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). Part or more, more preferably 0.005 part by weight or more, usually 5 parts by weight or less, more preferably 3 parts by weight or less, still more preferably 2 parts by weight or less.
When the addition amount of the antioxidant 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, when it is less than 0.001 part by mass, there is a tendency that a sufficient improvement effect for the weather resistance test cannot be obtained.

<Phosphite antioxidant>
Phosphite antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl Phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert- Butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol Diphosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like.
Among these, 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 use only 1 type and may use 2 or more types together.

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

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

(Light stabilizer)
Examples of the light stabilizer include hindered amine light stabilizers, and the molecular weight is preferably 1000 or less, and more preferably 900 or less. When the molecular weight exceeds 1000, there is a possibility that sufficient weather resistance cannot be obtained when formed into a molded product. 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 at the time of molding, and a molded product having an excellent surface appearance may not be obtained.
Furthermore, a compound having a piperidine structure is preferable. The piperidine structure defined here may be a saturated 6-membered amine structure, and includes a 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 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 preferable.

  Such light stabilizers include 4-piperidinol, 2,2,6,6-tetramethyl-4-benzoate, bis (2,2,6,6-tetramethyl-piperidyl) sebacate, 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, Condensate of 6,6-tetramethyl-pyridinol, tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-pyridinol and methanol, 1,2,3, 4-Butanetetracarboxylic acid condensate, bis (1,2,3,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphene [Lu] methyl] butyl malonate, decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide 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-teto Methyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N′-bis (2,2,6,6-tetramethyl-4 -Piperidyl) -1,6-hexanediamine polymer and 2,4,6-trichloro-1,3,5-triazine condensate, 1,2,3,4-butanetetracarboxylic acid and 2,2,6 , 6-tetramethyl-4-piperidinol and β, β, β, β-tetramethyl-3,9- (2,4,8,10-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- A condensate with 1,3,5-triazine, Condensates of Haq dimethyl and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethyl piperidine.

When the light stabilizer is added to the polycarbonate resin composition of the present invention, the addition amount is usually 0.001 part by mass or more and 5 parts by mass or less, preferably 0 with respect to 100 parts by mass of the polycarbonate resin (A). 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.
When the added amount of the light stabilizer is more than 5 parts by mass, it tends to be colored, and even if a colorant is added, for example, it is difficult to obtain a jet black with depth and clarity. On the other hand, when it is less than 0.001 part by mass, there is a possibility that sufficient weather resistance may not be obtained when an automobile interior / exterior product is obtained.

<Colorant>
Examples of the colorant include organic dyes such as inorganic pigments, organic pigments, and organic dyes.

  Inorganic pigments include, for example, carbon black; oxides such as titanium oxide, zinc white, dial, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, copper-iron black, etc. Pigments; and the like.

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

  These colorants may be used alone or in combination of two or more.

  Among organic dyes such as the inorganic pigment, organic pigment and organic dye, inorganic pigments are preferable. By using an inorganic pigment as a colorant, sharpness and the like can be maintained for a long time even when the molded product is used outdoors.

When a colorant is added to the polycarbonate resin composition of the present invention, the addition amount is usually 0.05 parts by mass or more and 5 parts by mass or less, preferably 0.005 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). 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 added amount of the colorant is less than 0.05 parts by mass, it is difficult to obtain a molded article with sharpness. On the other hand, when the amount is more than 5 parts by mass, the surface roughness of the molded product increases, and it is difficult to obtain an original molded product with sharpness.

(filler)
In the polycarbonate resin composition of the present invention, glass fiber, glass milled fiber, glass flake, glass bead, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whisker, barium sulfate can be used 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 powdery organic fillers such as wood powder, bamboo powder, coconut starch, cork powder, and pulp powder; 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.

<Method for producing polycarbonate resin composition>
The polycarbonate resin composition of the present invention is produced by mixing the above components simultaneously in a predetermined ratio or in an arbitrary order by a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading roll, or 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 ≦ 0.20 (2)
μs ≤ 0.25 (3)
(Μk in the above equation (2) indicates a dynamic friction coefficient measured by the following friction coefficient measurement test, and μs in the above equation (3) indicates a 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. The steel plate is moved, the maximum load at the start of movement is set as the static friction coefficient μs, and the average value of the load from 4 seconds to 6 seconds after the start of movement is set as the dynamic friction coefficient μk. )

That is, the polycarbonate resin composition of the present invention has a dynamic friction coefficient μk of 0.20 or less with respect to a steel sheet of a molded plate formed by molding the polycarbonate resin composition, and the dynamic friction coefficient μk is preferably 0.19 or less. When the dynamic friction coefficient μk is larger than 0.20, the scratch resistance is deteriorated. The dynamic friction coefficient μk of the polycarbonate resin composition of the present invention is preferably as small as possible from the viewpoint of scratch resistance, but its lower limit is usually 0.10 or more.
The polycarbonate resin composition of the present invention has a static friction coefficient μs of 0.25 or less with respect to a steel sheet of a molded plate formed by molding the polycarbonate resin composition, and the static friction coefficient μs is preferably 0.24 or less. When the static friction coefficient μs is larger than 0.25, the scratch resistance is deteriorated. The static friction coefficient μs of the polycarbonate resin composition of the present invention is preferably as small as possible from the viewpoint of scratch resistance, but its lower limit is usually 0.10 or more.
In the present invention, the dynamic friction coefficient μk and the static friction coefficient 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-described polycarbonate resin (A) and an appropriate slidability modifier (B) are used, and the slidability used. The method of adjusting the compounding quantity according to the kind of modifier (B) is mentioned.

<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 can use 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. Furthermore, in order to obtain a design property, it is also possible to use heat insulating mold forming and rapid heating / cooling mold forming.

<Application>
The molded product of the present invention formed by molding the polycarbonate resin composition of the present invention is excellent in scratch resistance and has few scratches generated when wiped with a dust cloth or tissue, etc. The process and cost for painting can be reduced and applied to various parts as products.
Although there is no restriction | limiting in particular as an application use of such a molded article of this invention, It is suitable for a motor vehicle interior component or an exterior component.

  Examples of automotive interior and exterior parts to which the molded article of the present invention is applied include fenders, bumpers, facers, door panels, side garnishes, pillars, radiator grills, side protectors, side moldings, rear protectors, rear moldings, various spoilers, 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, auto Examples include mobile computer parts, but are not limited thereto.

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

[Evaluation methods]
In the following, the physical properties or characteristics of the polycarbonate resin and the polycarbonate resin composition were evaluated 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. Measured at a temperature of 20.0 ° C. ± 0.1 ° C. using an Ubbelohde viscometer manufactured by Moriyu Rika Kogyo Co., Ltd. From the solvent passage time t ₀ and the solution passage time t, the relative viscosity 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 determined by dividing the specific viscosity η _sp by the concentration c (g / dL). The higher this value, the higher the molecular weight.

(2) Friction coefficient A test piece 1 in the form of a sheet (100 mm × 100 mm × 2 mmt) was prepared from a polycarbonate resin composition by an injection molding machine (EC-75SX manufactured by Toshiba Machine Co., Ltd.). A test piece 2 made of a steel plate (material: SK-5, size: 40 mm × 40 mm × 1 mmt) whose surface has been previously polished with # 1000 sandpaper is attached to the test piece 1 so that the polishing surface is on the test piece 1 side. When the test piece 2 is moved at a surface pressure of 3.1 kPa and a moving speed of 100 mm / min on the test piece 1 using a superposition and surface property measuring machine (manufactured by Shinto Kagaku, model: HEIDON-14DR). Obtained from the load. As the static friction coefficient μs, the maximum load at the start of movement of the test piece 2 was adopted, and as the dynamic friction coefficient μk, an average value of loads from 4 seconds to 6 seconds after the start of movement was adopted.

(3) Scratch resistance In a planar abrasion tester (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd., model: PA-300A), the tissue (manufactured by Nippon Paper Crecia Co., Ltd., manufacturer model number: 528896) is folded three times, and the wearer (on the bottom surface) The projected area is 20 mm × 20 mm and the bottom surface is a curved surface of R45 mm.) The load is 9.8 N on the surface of the sheet (100 mm × 100 mm × 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 △: 1 to 10 scratches are seen in the width of the wearer ×: The entire width of the wearer looks white due to scratches

[Sliding property modifier (B)]
As the slidability modifier (B) blended in the polycarbonate resin composition, the following was used.
(B) -1: exfoliated graphite powder (“UP-15N” manufactured by Nippon Graphite Industry Co., Ltd., average particle size: 15 μm)
(B) -2: Pitch milled carbon fiber (Osaka Gas Chemical Co., Ltd. “Donna Carbo Milled S-2404”, aspect ratio 3.1)
(B) -3: PTFE powder (“Lublon L-5” manufactured by Daikin Industries, Ltd., average particle size: 5 μm)
(B) -4: Montanate ester (“Lyco Wax E” manufactured by Clariant Japan)
(B) -5: Ultra high molecular weight polyethylene powder (“Hi-Zex Million 240M” manufactured by Mitsui Chemicals, Inc.)
(B) -6: Silicone particles (“Tospearl 120” manufactured by Momentive Performance Materials LLC, average particle size: 2 μm)

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

[Production Example 1: Production of polycarbonate resin (A) -1]
In a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C., isosorbide (ISB), 1,4-cyclohexanedimethanol (CHDM), diphenyl having a chloride ion concentration of 10 ppb or less by purification by distillation. Carbonate (DPC) and calcium acetate monohydrate have a molar ratio of ISB / CHDM / DPC / calcium acetate monohydrate = 0.7 / 0.3 / 1.00 / 1.3 × 10 ⁻⁶ Then, nitrogen was sufficiently substituted (oxygen concentration 0.0005 vol% to 0.001 vol%). Subsequently, the contents were 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 be 100 ° C. Thereafter, the temperature increase was started, and the internal temperature was brought to 210 ° C. in 40 minutes. When the internal temperature reaches 210 ° C., control is performed to maintain this temperature, and at the same time, pressure reduction is started, and after reaching 210 ° C., 13.3 kPa (absolute pressure, the same applies hereinafter) is reached in 90 minutes. The pressure was held for an additional 60 minutes. The phenol vapor produced as a by-product with the polymerization reaction was led to a reflux condenser. The components condensed in the reflux condenser were returned to the polymerization reaction apparatus, and the phenol vapor that was not condensed was subsequently recovered by guiding it to a condenser using 45 ° C. hot water as a refrigerant.

The content oligomerized in the polymerization reactor is once restored to atmospheric pressure, and then transferred to another polymerization reactor equipped with a stirring blade and a reflux condenser controlled in the same manner as described above. Depressurization was started, and an internal temperature of 220 ° C. and a pressure of 200 Pa were achieved in 60 minutes. Thereafter, the internal temperature was set to 228 ° C. and the pressure was set to 133 Pa or less over 20 minutes, and when the predetermined stirring power was reached, the pressure was restored.
Furthermore, the molten polycarbonate copolymer was continuously supplied to a twin-screw extruder provided with three vent ports and water injection equipment, and Irganox 1010 was used as an antioxidant with respect to 100 parts by mass of the polycarbonate copolymer. 0.1 parts by mass (BASF Japan Ltd., pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]), ADK STAB 2112 (manufactured by ADEKA Corporation, Tris) While continuously adding 0.05 parts by weight of (2,4-di-tert-butylphenyl) phosphite) and 0.3 parts by weight of Unistar E-275 (manufactured by NOF Corporation) as a release agent, After low-molecular weight products such as phenol were devolatilized under reduced pressure at each vent section provided in the twin-screw extruder, the pelletizer was used. It performed pelletized to obtain a polycarbonate resin (A) -1. The reduced viscosity η _sp / c of the polycarbonate resin (A) -1 was 0.44 dL / g.

[Example 1]
97.6 parts by mass of the polycarbonate resin (A) -1 obtained in Production Example 1, 2.4 parts by mass of (B) -1 as the slidability modifier (B), and 0. Using 1 part by mass, these were blended in advance, using a twin-screw kneader (manufactured by Nippon Steel Works, TEX30SST42BW: screw diameter 30 mm, L / D = 42), absolute vacuum with a vacuum pump from one place in the middle While adjusting the pressure to 10 to 20 kPa, extruding into a strand at a cylinder temperature of 240 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 15 kg / hr, a pellet-shaped resin composition sample was obtained using a strand cutter.
The obtained pellet-like sample was dried at 100 ° C. for 5 hours with a hot air dryer, and then evaluated according to the evaluation methods (2) to (3) described above. The results are shown in Table 1.

[Examples 2-3]
Except that the formulation shown in Table 1 was used, extrusion was performed in the same manner as in Example 1 to obtain a pellet-like sample, and evaluation was performed in the same manner.

[Comparative Examples 1-4]
Except that the formulation shown in Table 1 was used, extrusion was performed in the same manner as in Example 1 to obtain a pellet-like sample, evaluation was performed 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 slidability modifier (B) and satisfying the above formulas (2) and (3) is excellent in scratch resistance. I understand.

Claims (7)

Polycarbonate resin (A) containing a structural unit (a) derived from a dihydroxy compound represented by the following formula (1), having a reduced viscosity of 0.35 dL / g or more and 0.80 dL / g or less, and slidability A polycarbonate resin composition containing a modifier (B),
The sliding modifier (B) is at least one selected from the group consisting of exfoliated graphite powder, pitch-based milled carbon fiber, and polytetrafluoroethylene powder,
A polycarbonate resin composition characterized by satisfying the following formulas (2) and (3).

μk ≦ 0.20 (2)
μs ≤ 0.25 (3)
(Μk in the above equation (2) indicates a dynamic friction coefficient measured by the following friction coefficient measurement test, and μs in the above equation (3) indicates a static friction coefficient.
<Friction coefficient measurement test>
The polycarbonate resin composition is formed into a sheet (100 mm × 100 mm × 2 mmt) test piece by an injection molding machine, and a steel plate (material: SK-5) whose surface is previously polished with # 1000 sandpaper is laminated on the test piece. In addition, on the test piece, the steel plate is moved at a surface pressure of 3.1 kPa and a moving speed of 100 mm / min. The value is a dynamic friction coefficient μk. )   The polycarbonate resin (A) is represented by the structural unit (a) derived from the dihydroxy compound represented by the formula (1), the aliphatic dihydroxy compound, the alicyclic dihydroxy compound, and the formula (1). The polycarbonate according to claim 1, which is a copolymer polycarbonate resin comprising a structural unit (b) derived from one or more dihydroxy compounds selected from the group consisting of ether group-containing dihydroxy compounds other than dihydroxy compounds. Resin composition.   3. The polycarbonate resin according to claim 1, comprising 0.01 to 5 parts by mass of the slidability modifier (B) with respect to 100 parts by mass of the polycarbonate resin (A). Composition. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the slidability modifier (B) is exfoliated graphite powder. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the slidability modifier (B) is a pitch-based milled carbon fiber. A molded article formed by molding the polycarbonate resin composition according to any one of claims 1 to 5 . The molded article according to claim 6 , which is an automobile interior part or an exterior part.