JP2020158596A - Polycarbonate resin composition - Google Patents

Abstract

To provide a polycarbonate resin composition that is excellent in heat resistance, impact resistance, scratch resistance (high hardness), amine resistance, dry heat resistance, weather resistance, and reduction of mold adhesion during injection molding.SOLUTION: A polycarbonate resin composition, containing, for 100 pts.mass of a polycarbonate resin (D) composed of three main structural units having a specific structure and the proportion (mol%) of each structural unit is in a specific range, a phosphorus stabilizer (E) having a melting point of 100°C or higher by 0.01 to 0.5 pts.mass, a hindered phenol stabilizer (F) by 0.01 to 1 pts.mass, and a UV absorber (G) having a melting point of 130°C or higher by 0.1 to 5 pts.mass.SELECTED DRAWING: None

Description

The present invention relates to a polycarbonate resin composition capable of suppressing polymer decomposition under conditions exposed to a basic environment containing an amine. The present invention also relates to a polycarbonate resin molded product (sheet, film, etc.) having excellent amine resistance, which is suitable for manufacturing interior parts for automobiles. Further, the present invention is excellent in heat resistance, impact resistance, scratch resistance (high hardness), amine resistance, dry heat resistance, weather resistance, and reduction of mold adhesion during injection molding, which are made of a polycarbonate resin having a specific structural unit. Regarding interior parts for automobiles.

Polyurethane foam is manufactured using polyol and polyisocyanate as the main raw materials, and is foamed while mixing foaming agents, foam stabilizers, catalysts, colorants, etc. and resinifying them. Especially in the field of automobiles, seat cushions. , Door trim, headrest, armrest, handle, floor and ceiling, etc. Sound absorbing / damping material, cushioning material, sun visor, etc. are widely used. The tertiary amine compound used as a catalyst is an indispensable substance in the resinification and foaming / expansion reaction of polyurethane foam, but the amine catalyst gradually volatilizes from the polyurethane foam after production, causing discoloration of other interior parts and discoloration. It is known to cause bleaching.

Further, in the field of automobiles, paint-less interior parts are being studied for the purpose of reducing environmental load and improving production efficiency, and paint-less materials that do not require coating treatment for surface protection are required. .. Therefore, such paintless materials require amine resistance.

Polycarbonate resin has excellent transparency, impact resistance, heat resistance, and dimensional stability. Therefore, as engineering plastics, housings for electrical and electronic equipment, automobile interior / exterior parts, building materials, furniture, musical instruments, miscellaneous goods, etc. It is used in a wide range of fields such as. Furthermore, compared to inorganic glass, it has a lower specific gravity, can be made lighter, and has excellent productivity, so it is used for windows such as automobiles.

Further, sheets and films using polycarbonate resin are widely used as various display devices and protective parts for automobile interiors by subjecting them to additional secondary processing such as coating treatment, laminate, and surface modification.

However, the problem with the polycarbonate resin that has not been coated is that when it is exposed to a basic environment containing amines, the polymer decomposes and the surface of the molded product is whitened, resulting in poor appearance. Further, the general paint test method described in JIS K5600-5-4-Part 5: Mechanical properties of the coating film-Section 4: The pencil hardness of the polycarbonate resin measured in accordance with the scratch hardness (pencil method) is 2B. It can be said that the problem is that the surface is easily scratched as a paint-less material.

Therefore, it is known to use a copolymerized polycarbonate resin having a high surface hardness (for example, Patent Document 1). However, although the copolymerized polycarbonate resin has a high surface hardness and is excellent in ammonia resistance, it has a problem that it is inferior in impact resistance.

Further, a method of using polycarbonate or copolycarbonate having 2,2-bis (4-hydroxy-3-methylphenyl) propane as a constituent unit is described (for example, Patent Documents 2 to 6). The surface hardness of the polycarbonate resin is improved, but the heat resistance is inferior to that of the polycarbonate resin.

Further, a method of using polycarbonate or copolycarbonate containing 9,9-bis (4-hydroxyphenyl) fluorene as a constituent unit is described (Patent Document 7). The polycarbonate resin is excellent in surface hardness, impact resistance, heat resistance, and amine resistance, but no specific method has been specified regarding dry heat resistance, weather resistance, and reduction of mold adhesion during injection molding.

Therefore, there is still no polycarbonate resin composition that has heat resistance, impact resistance, scratch resistance (high hardness), amine resistance, dry heat resistance, weather resistance, and reduction of mold adhesion during injection molding.

Japanese Patent No. 5173803 Japanese Unexamined Patent Publication No. 64-069625 Japanese Unexamined Patent Publication No. 08-183852 Japanese Unexamined Patent Publication No. 08-034846 JP-A-2002-117580 Japanese Patent No. 3768903 International Publication No. 2017/073508

An object of the present invention is to provide a polycarbonate resin composition having excellent heat resistance, impact resistance, scratch resistance (high hardness), amine resistance, dry heat resistance, weather resistance, and reduction of mold adhesion during injection molding. is there. Another object of the present invention is to provide a polycarbonate resin molded product particularly suitable for automobile interior parts.

As a result of diligent research to achieve the above object, the present inventors have used a specific phosphorus-based stabilizer, a hindered phenol-based stabilizer, and a specific ultraviolet absorber in specific amounts in a specific polycarbonate resin. , The present invention has been reached by finding that the above object is achieved. That is, the dry heat resistance of the polycarbonate resin composition obtained by combining a phosphorus-based stabilizer having a specific melting point, a hindered phenol-based stabilizer, and an ultraviolet absorber having a specific melting point and using each in a specific amount range. It has been found that the weather resistance and the effect of suppressing mold adhesion during injection molding are significantly improved.

（式（１）中、Ｒ^１〜Ｒ^２は夫々独立して水素原子、芳香族基を含んでもよい炭素原子数１〜９の炭化水素基またはハロゲン原子である。）
で表される構成単位（Ａ）、
（Ｂ）下記式（２）

（式（２）中、Ｒ^３〜Ｒ^４は夫々独立して炭素原子数１〜６のアルキル基またはハロゲン原子である。Ｘは、単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のアルキリデン基、硫黄原子または酸素原子である。）
で表される構成単位（Ｂ）、および
（Ｃ）下記式（３）

（式（３）中、Ｗは、単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のアルキリデン基、硫黄原子または酸素原子を示す。）
で表される構成単位（Ｃ）から構成され、全構成単位における構成単位（Ａ）の割合が５〜１５モル％、構成単位（Ｂ）の割合が２０〜６０モル％、構成単位（Ｃ）の割合が２５〜７５モル％であるポリカーボネート樹脂（Ｄ）１００質量部に対し、融点が１００℃以上であるリン系安定剤（Ｅ）０．０１〜０．５質量部、ヒンダードフェノール系安定剤０．０１〜１質量部（Ｆ）、及び融点１３０℃以上の紫外線吸収剤（Ｇ）０．１〜５質量部を含有することを特徴とするポリカーボネート樹脂組成物。 According to the present invention, the following (configuration 1) to (configuration 11) are provided.
(Structure 1)
As the main building blocks, (A) the following formula (1)

(In the formula (1), R ^{1 to} R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms or a halogen atom which may contain an aromatic group.)
Structural unit (A) represented by
(B) The following formula (2)

(In formula (2), R ^{3 to} R ⁴ are independently alkyl or halogen atoms having 1 to 6 carbon atoms. X is a single-bonded, substituted or unsubstituted alkylene group, substituted or unsubstituted. Alkylidene group, sulfur atom or oxygen atom.)
The structural unit (B) represented by, and (C) the following formula (3)

(In formula (3), W represents a single bond, substituted or unsubstituted alkylene group, substituted or unsubstituted alkylidene group, sulfur atom or oxygen atom.)
It is composed of the structural unit (C) represented by, the ratio of the structural unit (A) in all the structural units is 5 to 15 mol%, the ratio of the structural unit (B) is 20 to 60 mol%, and the structural unit (C). 0.01 to 0.5 parts by mass of phosphorus-based stabilizer (E) having a melting point of 100 ° C. or higher, and hindered phenol-based stable, with respect to 100 parts by mass of the polycarbonate resin (D) having a proportion of 25 to 75 mol%. A polycarbonate resin composition containing 0.01 to 1 part by mass (F) of an agent and 0.1 to 5 parts by mass of an ultraviolet absorber (G) having a melting point of 130 ° C. or higher.

(Structure 2)
R ^{1 to} R ² in the formula (1) are independently hydrogen atoms and alkyl groups having 1 to 6 carbon atoms, and R ^{3 to} R ⁴ in the formula (2) are independently independent carbon atoms 1 to 1. It is an alkyl group of 6, and X is a single bond, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms, and W in the formula (3). The polycarbonate resin composition according to the above item 1, wherein is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms.
(Structure 3)
The polycarbonate resin composition according to item 1 or 2, wherein the viscosity average molecular weight is 15,000 to 40,000.
(Structure 4)
The polycarbonate resin composition according to any one of items 1 to 3 above, wherein the structural unit (A) is a structural unit derived from 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.
(Structure 5)
The polycarbonate resin composition according to any one of the above items 1 to 4, wherein the structural unit (B) is a structural unit derived from 2,2-bis (4-hydroxy-3-methylphenyl) propane.
(Structure 6)
The polycarbonate resin composition according to any one of the above items 1 to 5, wherein the structural unit (C) is a structural unit derived from 2,2-bis (4-hydroxyphenyl) propane.
(Structure 7)
The polycarbonate resin composition according to any one of the above items 1 to 6, wherein the degree of yellow change (ΔYI) at around 2000 hr in the weather resistance acceleration test is 10 or less.
(Structure 8)
The polycarbonate resin composition according to any one of the above items 1 to 7, wherein the degree of yellow change (ΔYI) after a dry heat test of 120 ° C. and 2000 hr is 6 or less.
(Structure 9)
A molded product obtained by injection molding the polycarbonate resin composition according to any one of the above items 1 to 8.
(Structure 10)
A sheet or film obtained by extruding the polycarbonate resin composition according to any one of the above items 1 to 8.
(Structure 11)
An automobile interior part using the molded product according to the preceding item 9 or the sheet or film according to the preceding item 10.

The polycarbonate resin composition of the present invention and a molded product made of the same are excellent in heat resistance, impact resistance, scratch resistance (high hardness), amine resistance, dry heat resistance, weather resistance, and reduction of mold adhesion during injection molding. Therefore, it is suitably used for automobile interior parts. Therefore, the industrial effect it produces is exceptional.

（式（１）中、Ｒ^１〜Ｒ^２は夫々独立して水素原子、芳香族基を含んでもよい炭素原子数１〜９の炭化水素基またはハロゲン原子である。）
で表される構成単位（Ａ）、 The details of the present invention will be described below.
<Polycarbonate resin (D)>
The polycarbonate resin (D) used in the present invention (including a polycarbonate copolymer and a copolymerized polycarbonate blend) has (A) the following formula (1) as a main constituent unit.

(In the formula (1), R ^{1 to} R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms or a halogen atom which may contain an aromatic group.)
Structural unit (A) represented by

（式（２）中、Ｒ^３〜Ｒ^４は夫々独立して炭素原子数１〜６のアルキル基またはハロゲン原子である。Ｘは、単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のアルキリデン基、硫黄原子または酸素原子である。）
で表される構成単位（Ｂ）、および (B) The following formula (2)

(In formula (2), R ^{3 to} R ⁴ are independently alkyl or halogen atoms having 1 to 6 carbon atoms. X is a single-bonded, substituted or unsubstituted alkylene group, substituted or unsubstituted. Alkylidene group, sulfur atom or oxygen atom.)
The structural unit (B) represented by, and

（式（３）中、Ｗは、単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のアルキリデン基、硫黄原子または酸素原子を示す。）
で表される構成単位（Ｃ）から構成される。 (C) The following formula (3)

(In formula (3), W represents a single bond, substituted or unsubstituted alkylene group, substituted or unsubstituted alkylidene group, sulfur atom or oxygen atom.)
It is composed of a structural unit (C) represented by.

Here, the term "main" means 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, most preferably, out of 100 mol% of all carbonate constituent units excluding the terminal. It is preferably shown in a proportion of 100 mol%.

In the structural unit (A) represented by the formula (1), it is preferable that R ₁ and R ₂ are independently hydrogen atoms and alkyl groups having 1 to 6 carbon atoms, respectively.

Examples of the dihydric phenol that induces the structural unit (A) include 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. The most suitable divalent phenol is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.

In the polycarbonate resin (D), the ratio of the structural unit (A) to all the structural units is 5 to 15 mol%. When the ratio of the structural unit (A) exceeds 15 mol%, the heat resistance is improved, but the impact resistance, the weather resistance, and the dry heat resistance are inferior, which is not preferable. If the ratio of the structural unit (A) is less than 5 mol%, the heat resistance is inferior, which is not preferable.

In the structural unit (B) represented by the formula (2), R ^{3 to} R ⁴ are preferably alkyl groups having 1 to 6 carbon atoms independently, and X is a single bond, substituted or unsubstituted. It is preferable that the alkylene group has 1 to 10 carbon atoms and the substituted or unsubstituted alkylidene group has 1 to 10 carbon atoms.

Examples of the dihydric phenol that induces the structural unit (B) include 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter referred to as bisphenol C) and 2,2-bis (4-hydroxy-3). Examples thereof include −isopropylphenyl) propane and 2,2-bis (3-t-butyl-4-hydroxyphenyl) propane. The most suitable divalent phenol is bisphenol C.

In the polycarbonate resin (D), the ratio of the structural unit (B) to all the structural units is 20 to 60 mol%, preferably 30 to 50 mol%. If the ratio of the structural unit (B) exceeds 60 mol%, the impact resistance and heat resistance are inferior, which is not preferable. If the proportion of the structural unit (B) is less than 20 mol%, the amine resistance is inferior, which is not preferable.

In the structural unit (C) represented by the formula (3), W is a single-bonded, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms. Is preferable.

Examples of the divalent phenol that induces the structural unit (C) include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 4,4'-dihydroxy-1,1-biphenyl, 4, 4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylthioether, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 1,1-bis (4-) Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4-bis (4,4-bis) Examples thereof include 4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane, and 1,1-bis (4-hydroxyphenyl) decane. The most suitable divalent phenol is bisphenol A.

In the polycarbonate resin (D), the ratio of the constituent unit (C) to all the constituent units is 25 to 75 mol%, preferably 30 to 70 mol%, more preferably 35 to 65 mol%, and 40 to 60 mol%. More preferred. If the ratio of the structural unit (C) exceeds 75 mol%, scratch resistance and amine resistance are inferior, which is not preferable. If the ratio of the structural unit (C) is less than 25 mol%, the impact resistance is inferior, which is not preferable.

Further, as the divalent phenol for inducing a structural unit other than the structural units (A), (B) and (C), 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, and an alkyl group having 1 to 3 carbon atoms are preferable. Resolsinol substituted with, 3- (4-hydroxyphenyl) -1,1,3-trimethylindan-5-ol, 1- (4-hydroxyphenyl) -1,3,3-trimethylindan-5-ol, 6,6'-dihydroxy-3,3,3', 3'-tetramethylspirindan, 1-methyl-1,3-bis (4-hydroxyphenyl) -3-isopropylcyclohexane, 1-methyl-2- ( Examples thereof include 4-hydroxyphenyl) -3- [1- (4-hydroxyphenyl) isopropyl] cyclohexane and 1,6-bis (4-hydroxyphenyl) -1,6-hexanedione. Other details of such polycarbonate are described in, for example, WO03 / 080728 pamphlet, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, JP-A-2002-117580 and the like. Has been done.

The polycarbonate resin is obtained by reacting a divalent phenol with a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a molten transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. In the case of interfacial polycondensation, a terminal terminator of monohydric phenols is usually used. Further, it may be a branched polycarbonate obtained by polymerizing a trifunctional component, or may be a copolymerized polycarbonate obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and a vinyl-based monomer.

In reactions using, for example, phosgene as the carbonate precursor, the reaction is usually carried out in the presence of an acid binder and solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. A catalyst such as a tertiary amine or a quaternary ammonium salt can also be used to promote the reaction. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.

The transesterification reaction using, for example, a carbonic acid diester as a carbonic acid precursor is carried out by a method of distilling the produced alcohol or phenol by stirring a predetermined ratio of aromatic dihydroxy components with the carbonic acid diester while heating in an inert gas atmosphere. It is said. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed by distilling off the produced alcohols or phenols under reduced pressure from the initial stage. It is also possible to use a catalyst usually used in transesterification reactions to accelerate the reaction. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferable.

Monofunctional phenols commonly used as terminal inhibitors can be used. Especially in the case of reactions using phosgene as a carbonate precursor, monofunctional phenols are commonly used as terminal terminators for molecular weight regulation, and the resulting polycarbonate resin is based on monofunctional phenols at the ends. Since it is sealed by the group, it has better thermal stability than the other. Specific examples of the monofunctional phenols include, for example, phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, and the like. Examples thereof include p-cumylphenol, isooctylphenol, and p-long-chain alkylphenol.

The polycarbonate resin (D) can be copolymerized with an aliphatic diol, if necessary. For example, isosorbide: 1,4: 3,6-dianhydro-D-sorbitol, tricyclodecanedimethanol (TCDDM), 4,8-bis (hydroxymethyl) tricyclodecane, tetramethylcyclobutanediol (TMCBD), 2, 2,4,4-Tetramethylcyclobutane-1,3-diol, mixed isomer, cis / trans-1,4-cyclohexanedimethanol (CHDM), cis / trans-1,4-bis (hydroxymethyl) cyclohexane, Cyclohex-1,4-yldimethanol, trans-1,4-cyclohexanedimethanol (tCHDM), trans-1,4-bis (hydroxymethyl) cyclohexane, cis-1,4-cyclohexanedimethanol (cCHDM), cis -1,4-bis (hydroxymethyl) cyclohexane, cis-1,2-cyclohexanedimethanol, 1,1'-bi (cyclohexyl) -4,4'-diol, spiroglycol, dicyclohexyl-4,4'-diol , 4,4'-Dihydroxybicyclohexyl, and poly (ethylene glycol).

The polycarbonate resin (D) can be copolymerized with fatty acids, if necessary. For example, 1,10-dodecandioic acid (DDDA), adipic acid, hexanedioic acid, isophthalic acid, 1,3-benzenedicarboxylic acid, terephthalic acid, 1,4-benzenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, Examples thereof include 3-hydroxybenzoic acid (mHBA) and 4-hydroxybenzoic acid (pHBA).

The polycarbonate resin (D) contains a polyester carbonate copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of aliphatic bifunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosandioic acid, and cyclohexanedicarboxylic acid. An alicyclic dicarboxylic acid such as an acid is preferably used. These carboxylic acids may be copolymerized as long as they do not impair the purpose.
The polycarbonate resin (D) can also be copolymerized with a structural unit containing a polyorganosiloxane unit, if necessary.

The polycarbonate resin (D) can also be obtained as a branched polycarbonate by copolymerizing a structural unit containing a trifunctional or higher-functional polyfunctional aromatic compound, if necessary. Trifunctional or higher polyfunctional aromatic compounds used in branched polycarbonate include 4,6-dimethyl-2,4,6-tris (4-hydroxidiphenyl) heptene-2,2,4,6-trimethyl-. 2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1 -Tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, and 4- {4- [1,1-bis (1,1-bis) Trisphenols such as 4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol are preferably exemplified. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane is preferable. The structural unit derived from such a polyfunctional aromatic compound is preferably 0.03 to 1.5 mol%, more preferably 0.1, based on a total of 100 mol% with the structural unit from other divalent components. It is ~ 1.2 mol%, particularly preferably 0.2 ~ 1.0 mol%.

Further, the branched structural unit is not only derived from a polyfunctional aromatic compound, but is also derived without using a polyfunctional aromatic compound such as a side reaction occurring during a polymerization reaction by a melt transesterification method. You may. The ratio of such branched structures can be calculated by ^{1 1} H-NMR measurement.

The polycarbonate resin (D) has a viscosity average molecular weight (Mv) of preferably 15,000 to 40,000, more preferably 16,000 to 30,000, and even more preferably 18,000 to 28, It is 000. A polycarbonate resin having a viscosity average molecular weight less than the above range may not have sufficient toughness and crack resistance for practical use. On the other hand, a polycarbonate resin having a viscosity average molecular weight exceeding the above range is inferior in versatility because it requires a high molding temperature or a special molding method, and further depends on the injection rate due to an increase in melt viscosity. The property tends to be high, and the yield may decrease due to poor appearance or the like.

The viscosity average molecular weight of the polycarbonate resin (D) is first determined by using an Ostwald viscometer from a solution in which 0.7 g of the polycarbonate resin is dissolved in 100 ml of methylene chloride at 20 ° C. for the specific viscosity (η _SP ) calculated by the following formula. Ask,
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall]
The viscosity average molecular weight Mv was calculated from the obtained specific viscosity (η _SP ) by the following mathematical formula.
η _SP / c = [η] + 0.45 × [η] ² c (where [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 Mv ^0.83
c = 0.7

<Phosphorus stabilizer (E)>
Various phosphorus-based stabilizers (E) are blended in the polycarbonate resin composition of the present invention mainly for the purpose of improving the thermal stability during the molding process. Examples of such phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid, and esters thereof. Further such phosphorus-based stabilizers include tertiary phosphine.

As the phosphorus-based stabilizer (E), a phosphorus-based stabilizer having a melting point of 100 ° C. or higher is used. When a phosphorus-based stabilizer having a melting point lower than the lower limit is used, it is not preferable because it is inferior in dry heat resistance. The melting point of the phosphorus-based stabilizer (E) is preferably 130 ° C. or higher, more preferably 150 ° C. or higher, still more preferably 180 ° C. or higher, and particularly preferably 220 ° C. or higher. The upper limit is not particularly limited, but it has sufficient characteristics at 300 ° C. or lower.

Specifically, examples of the phosphorus-based stabilizer (E) having a melting point of 100 ° C. or higher include tris (2,4-di-tert-butylphenyl) phosphite and tris (2,6-di-tert-butylphenyl). Phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6) -Di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite and the like. Of these, tris (2,4-di-tert-butylphenyl) phosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite are preferable. The phosphorus-based stabilizer (E) can be used not only by one type but also by mixing two or more types.

The content of the phosphorus-based stabilizer (E) is 0.01 to 0.5 parts by mass, preferably 0.02 to 0.4 parts by mass, based on 100 parts by mass of the polycarbonate resin (D). It is more preferably 0.03 to 0.3 parts by mass, further preferably 0.04 to 0.2 parts by mass, and particularly preferably 0.05 to 0.1 parts by mass.

If the content of the phosphorus-based stabilizer (E) is too large, the physical properties (impact strength and hardness) and moisture resistance of the material are lowered, and mold contamination during molding is likely to occur, which is not preferable. Further, if the content of the phosphorus-based stabilizer (E) is too small, the transparency, hue and dry heat resistance tend to deteriorate, which is not preferable.

<Hindered phenol-based stabilizer (F)>
The polycarbonate resin composition of the present invention contains a hindered phenolic stabilizer mainly for the purpose of improving the thermal stability, heat aging resistance and dry heat resistance of the molded product during the molding process.

Examples of such hindered phenol-based stabilizers include α-tocopherol, butylhydroxytoluene, cinapyl alcohol, vitamin E, and tetrakis [methylene-3- (3', 5'-di-tert-butyl-4-hydroxyphenyl). ) Propionate], 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenylacrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-Dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis ( 4-Methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-) 5-Methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-Butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4' -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide , 4,4'-di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-) Butylphenol), 2,2-thiodiethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy) -3', 5'-di-tert-butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl) Phenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4) -Hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethyl) Benzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and pentaerythritol tetrakis (3- (3,5-) Di-tert-butyl-4-hydroxyphenyl) propionate) and the like are exemplified.

Among the hindered phenolic stabilizers (F), pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and octadecyl-3- (3,5-di-tert-) Butyl-4-hydroxyphenyl) -propionate is preferred. The melting point of the hindered phenolic stabilizer (F) is not particularly limited, but is preferably in the range of 30 to 300 ° C, more preferably in the range of 40 to 250 ° C, and further preferably in the range of 50 to 200 ° C. is there. When the melting point is within the above range, it is excellent in dry heat resistance, weather resistance, and the effect of suppressing mold adhesion during injection molding. The above hindered phenolic antioxidants can be used alone or in combination of two or more.

The content of the hindered phenol-based stabilizer (F) is 0.01 to 1 part by mass, preferably 0.02 to 0.8 parts by mass, based on 100 parts by mass of the polycarbonate resin (D). It is more preferably 0.03 to 0.5 parts by mass, further preferably 0.04 to 0.3 parts by mass, and most preferably 0.05 to 0.2 parts by mass.

If the content of the hindered phenol-based stabilizer (F) is too large, the physical properties (impact strength and hardness) of the material are deteriorated, and the mold is contaminated during molding, which is not preferable. Further, if the content of the hindered phenol-based stabilizer (F) is too small, the transparency, hue and dry heat resistance tend to deteriorate, which is not preferable.

Further, by using the phosphorus-based stabilizer (E) and the hindered phenol-based stabilizer (F) in combination, a polycarbonate having a good balance of physical properties (impact strength and hardness), dry heat resistance and mold adhesion suppressing effect. A resin composition can be obtained.

<Ultraviolet absorber (G)>
The polycarbonate composition used in the present invention contains an ultraviolet absorber (G). As the ultraviolet absorber (G), an ultraviolet absorber having a melting point of 130 ° C. or higher is used. When an ultraviolet absorber having a melting point of less than the lower limit is used, the dry heat resistance and weather resistance are inferior, and the amount of mold deposits during injection molding increases, resulting in mold contamination and deterioration of the hue and appearance of the obtained molded product. This is not preferable. The melting point of the ultraviolet absorber (G) is preferably 140 ° C. or higher, more preferably 150 ° C. or higher, further preferably 170 ° C. or higher, and particularly preferably 190 ° C. or higher.

Specific examples of the ultraviolet absorber (G) having a melting point of 130 ° C. or higher include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2', 4,4'-. Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (4,6-diphenyl-1,3,5-triazine-2-yl)- 5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, and 2,4 Examples thereof include 6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine.

Further, the ultraviolet absorber (G) has a structure of a monomer compound capable of radical polymerization, whereby the photostable monomer having such an ultraviolet absorbing monomer and / or a hindered amine structure and an alkyl ( It may be a polymer-type ultraviolet absorber copolymerized with a monomer such as meta) acrylate. As the ultraviolet absorbing monomer, a compound containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth) acrylic acid ester is preferably exemplified. To.

Among the above, benzotriazole-based and hydroxyphenyltriazine-based are preferable in terms of ultraviolet absorption ability. Among the UV absorbers (G), 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-hexyloxy-phenol is preferred. The ultraviolet absorber (G) may be used alone or in a mixture of two or more kinds.

The content of the ultraviolet absorber (G) is 0.1 to 5 parts by mass, preferably 0.2 to 4 parts by mass, and more preferably 0. parts by mass with respect to 100 parts by mass of the polycarbonate resin (D). It is 25 to 3 parts by mass, more preferably 0.3 to 2 parts by mass. If the content of the ultraviolet absorber (G) is too large, the physical properties (impact strength and hardness) of the material are deteriorated, the heat resistance during molding is deteriorated, and the mold is contaminated during molding, which is not preferable. Further, if the content of the ultraviolet absorber (G) is too small, sufficient weather resistance cannot be obtained, which is not preferable.

<Other ingredients>
The polycarbonate resin composition of the present invention may contain a functional agent known per se, such as a mold release agent, a flow modifier, and an antistatic agent, as long as the effects of the present invention are not impaired.

(I) Release agent The polycarbonate resin composition of the present invention may be used in combination with a release agent as long as the effects of the present invention are not impaired. As the release agent, for example, fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which is modified with a functional group-containing compound such as acid modification can also be used), fluorine compound (polyfluoroalkyl). Fluorine oil typified by ether), paraffin wax, beeswax, etc. can be mentioned. Among these, fatty acid esters are preferable from the viewpoint of easy availability, releasability and transparency. The ratio of the release agent to be contained is preferably 0.005 to 0.5 parts by weight, more preferably 0.007 to 0.4 parts by weight, still more preferably 0, based on 100 parts by weight of the polycarbonate resin (D). It is 0.01 to 0.3 parts by weight. When the content is at least the lower limit of the above range, the effect of improving the mold releasability is clearly exhibited, and when it is at least the upper limit, adverse effects such as mold contamination during molding are reduced, which is preferable.

Among the above, the fatty acid ester used as a preferable release agent will be described in more detail. Such fatty acid esters are esters of fatty alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a divalent or higher polyhydric alcohol. The carbon number of the alcohol is preferably in the range of 3 to 32, and more preferably in the range of 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, triacontanol and the like. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester, a polyhydric alcohol is more preferable.

On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanic acid, and icosanoic acid. And saturated aliphatic carboxylic acids such as docosanoic acid (bechenic acid), and unsaturated aliphatic carboxylic acids such as palmitic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and sethalic acid. it can. Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferable. Since such aliphatic carboxylic acids are usually produced from natural fats and oils such as animal fats and oils (such as beef tallow and lard) and vegetable fats and oils (such as palm oil), these aliphatic carboxylic acids usually have carbon atoms. It is a mixture containing other carboxylic acid components different from each other. Therefore, it is also produced from such natural fats and oils in the production of aliphatic carboxylic acids, and is in the form of a mixture containing other carboxylic acid components. The acid value of the fatty acid ester is preferably 20 or less (substantially 0 can be taken). However, in the case of all esters (full esters), it is preferable to contain not a small amount of free fatty acids in order to improve releasability, and in this respect, the acid value of full esters is preferably in the range of 3 to 15. The iodine value of the fatty acid ester is preferably 10 or less (substantially 0 can be taken). These characteristics can be obtained by the method specified in JIS K 0070.

The fatty acid ester described above may be either a partial ester or a full ester, but a partial ester is preferable in terms of better releasability and durability, and a glycerin monoester is particularly preferable. The glycerin monoester is mainly composed of a monoester of glycerin and a fatty acid, and suitable fatty acids include saturated fatty acids such as stearic acid, partiminic acid, behenic acid, araquinic acid, montanic acid, and lauric acid, and oleic acid and linoleic acid. , And unsaturated fatty acids such as sorbic acid, and those containing glycerin monoesters of stearic acid, behenic acid, and partiminic acid as main components are particularly preferable. The fatty acid is synthesized from a natural fatty acid and becomes a mixture as described above. Even in such a case, the ratio of the glycerin monoester in the fatty acid ester is preferably 60% by weight or more.

In addition, the partial ester is often inferior to the full ester in terms of thermal stability. In order to improve the thermal stability of the partial ester, the partial ester preferably has a sodium metal content of less than 20 ppm, more preferably less than 5 ppm, still more preferably less than 1 ppm. The fatty acid partial ester having a sodium metal content of less than 1 ppm can be produced by producing the fatty acid partial ester by a usual method and then purifying it by molecular distillation or the like.

Specifically, after removing gas and low boiling point substances with a spray nozzle type degassing device, glycerin is used under the conditions of a distillation temperature of 120 to 150 ° C. and a vacuum degree of 0.01 to 0.03 kPa using a downflow film type distillation device. Etc., and a high-purity fatty acid partial ester is distilled off under the conditions of a distillation temperature of 160 to 230 ° C. and a vacuum degree of 0.01 to 0.2 Torr using a centrifugal molecular distillation apparatus. Sodium metal can be removed as a distillation residue. By repeatedly performing molecular distillation on the obtained distillate, it is possible to further increase the purity and obtain a fatty acid partial ester having a lower sodium metal content. It is also important to thoroughly clean the inside of the molecular distillation apparatus by an appropriate method in advance and to prevent the mixing of sodium metal components from the external environment by improving the airtightness. Such fatty acid esters can be obtained from specialists (for example, RIKEN Vitamin Co., Ltd.).

(Ii) Flow modifier The polycarbonate resin composition of the present invention may contain a fluid modifier as long as the effects of the present invention are not impaired. Examples of such flow modifiers include styrene-based oligomers, polycarbonate oligomers (including highly branched, hyperbranched and cyclic oligomer types), and polyalkylene terephthalate oligomers (including highly branched, hyperbranched and cyclic oligomer types). Branched and hyperbranched aliphatic polyester oligomers, terpene resins, polycaprolactone and the like are preferably exemplified. The flow modifier is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, still more preferably 2 to 15 parts by weight, per 100 parts by weight of the polycarbonate resin (D). Polycaprolactone is particularly preferable, and the composition ratio is 2 to 7 parts by weight, particularly preferably 2 to 7 parts by weight, per 100 parts by weight of the polycarbonate resin (D). The molecular weight of polycaprolactone is 1,000 to 70,000 in terms of number average molecular weight, preferably 1,500 to 40,000, more preferably 2,000 to 30,000, and 2,500 to 15,000. More preferred.

(Iii) Antistatic Agent The polycarbonate resin composition of the present invention may contain an antistatic agent mainly for the purpose of improving antistatic properties. As the antistatic agent, a sulfonic acid phosphonium salt, a phosphite ester, a caprolactone-based polymer and the like can be used, and the sulfonic acid phosphonium salt is preferably used. Specific examples of such sulfonic acid phosphonium salts include tetrabutylphosphonium dodecylsulfonic acid, tetrabutylphosphonium dodecylbenzenesulfonate, tributyloctylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, tetraethylphosphonium octadecylbenzenesulfonate, and dibutyl. Examples thereof include tributylmethylphosphonium benzenesulfonate, triphenylphosphonium dibutylnaphthylsulfonate, and trioctylmethylphosphonium diisopropylnaphthylsulfonate. Of these, tetrabutylphosphonium dodecylbenzenesulfonate is preferable because of its compatibility with polycarbonate and easy availability. The amount of the antistatic agent is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 3.0 parts by weight, still more preferably 0.3 to 0.3 parts by weight, based on 100 parts by weight of the polycarbonate resin (D). It is blended in an amount of 2.0 parts by weight, particularly preferably 0.5 to 1.8 parts by weight. When it is 0.1 part by weight or more, the effect of antistatic is obtained, and when it is 5.0 parts by weight or less, the transparency and mechanical strength are excellent, and silver or peeling does not occur on the surface of the molded product, and it is difficult to cause a poor appearance.

The polycarbonate resin composition of the present invention can also contain various additives such as a brewing agent, a fluorescent dye, a flame retardant, and a dye pigment. These can be appropriately selected and contained as long as the effects of the present invention are not impaired.

The brewing agent preferably contains 0.05 to 3.0 ppm (weight ratio) in the polycarbonate resin (D). Typical examples of the brewing agent include Bayer's Macrolex Violet B and Macrolex Blue RR, and Clariant's Polysynthslen Blue RLS.

Examples of fluorescent dyes (including fluorescent whitening agents) include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthracinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, and xantone-based fluorescent dyes. , Thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, diaminostilben-based fluorescent dyes, and the like. The blending amount of the fluorescent dye (including the fluorescent whitening agent) is preferably 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the polycarbonate resin (D).

Examples of the flame retardant include a sulfonic acid metal salt-based flame retardant, a halogen-containing compound-based flame retardant, a phosphorus-containing compound-based flame retardant, and a silicon-containing compound-based flame retardant. Among these, sulfonic acid metal salt flame retardants are preferable. The blending amount of the flame retardant is usually preferably 0.01 to 1 part by weight, more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin (D).

The method for blending the additive with the polycarbonate resin composition of the present invention is not particularly limited, and a known method can be used. The most commonly used method is to premix the polycarbonate resin and additives, then put them in an extruder for melt kneading, cool the extruded threads, and cut them with a pelletizer to produce pellet-shaped molding materials. There is a way to do it.

As the extruder in the above method, either a single-screw extruder or a twin-screw extruder can be used, but a twin-screw extruder is preferable from the viewpoint of productivity and kneading property. As a typical example of such a twin-screw extruder, ZSK (manufactured by Werner & Pfreederer, trade name) can be mentioned. Specific examples of similar types include TEX (Japan Steel Works, Ltd., product name), TEM (Toshiba Machine Co., Ltd., product name), KTX (Kobe Steel, Ltd., product name), etc. Can be mentioned. As the extruder, one having a vent capable of degassing the moisture in the raw material and the volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed from the vent to efficiently discharge the generated water and volatile gas to the outside of the extruder. It is also possible to install a screen for removing foreign substances and the like mixed in the extruded raw material in the zone in front of the die portion of the extruder to remove the foreign substances from the resin composition. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (disc filter, etc.) and the like.

Further, although the additive can be independently supplied to the extruder, it is preferable to premix it with the resin raw material as described above. Examples of such premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. A more preferable method is, for example, to prepare a master agent by mixing a part of the raw material resin and the additive with a high-speed stirrer such as a Henschel mixer, and then leaving the remaining amount of the master agent as a total amount of the resin raw material and a Nauter mixer. This is a method of mixing with a non-high speed stirrer.

The resin composition extruded from the extruder is directly cut and pelletized, or the strands are cut with a pelletizer after forming the strands and pelletized. When it is necessary to reduce the influence of external dust and the like, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods already proposed for polycarbonate resins for optical discs are used to narrow the shape distribution of pellets, further reduce miscuts, and generate fine powder during transportation or transportation. It is preferable to further reduce the amount of air bubbles (vacuum air bubbles) generated inside the strands and pellets. To reduce miscuts, measures such as controlling the temperature of the threads during cutting with a pelletizer, blowing ion air during cutting, optimizing the rake angle of the pelletizer, and properly blending the release agent, and cutting were performed. Examples thereof include a method of filtering a mixture of pellets and water to separate pellets from water and miscuts. An example of the measuring method is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-2000421. With these formulations, it is possible to increase the cycle of molding and reduce the rate of defects such as silver.

The amount of miscut in the molding material (pellet) is preferably 10 ppm or less, more preferably 5 ppm or less. Here, the miscut means a powder or granular material finer than a pellet of a desired size that passes through a JIS standard sieve having a mesh size of 1.0 mm. The shape of the pellet can be a general shape such as a cylinder, a prism, and a sphere, but is more preferably a cylinder (including an elliptical pillar), and the diameter of the cylinder is preferably 1.5 to 4 mm, more preferably. Is 2 to 3.5 mm. In the elliptical column, the ratio of the minor axis to the major axis is preferably 60% or more, more preferably 65% or more. On the other hand, the length of the cylinder is preferably 2 to 4 mm, more preferably 2.5 to 3.5 mm.

<Characteristics of polycarbonate resin composition>
The polycarbonate resin composition of the present invention can suppress polymer decomposition in a basic environment containing amines. As a result of various studies, it was found that in the depolymerization reaction of polycarbonate by an amine compound, the depolymerization proceeds while the amine compound acts on the carbonate bond of the polycarbonate and produces a carbamic acid ester oligomer as an intermediate. Therefore, in order to suppress the reaction of the amine compound to the carbonate bond, the substituent of the aromatic ring is attached to the carbonate bond by being composed of the structural unit (B) represented by the above formula (2) as the main structural unit. We found that it plays a role of steric hindrance.

Further, the polycarbonate resin composition of the present invention has (A) a structural unit (A) represented by the above formula (1), (B) a structural unit (B) represented by the above formula (2), and (C). ) By configuring the structural unit (C) represented by the above formula (3) in a specific ratio, the balance between scratch resistance (high hardness), impact resistance, and heat resistance is excellent while maintaining amine resistance. I found.

Further, the polycarbonate resin composition of the present invention comprises a specific polycarbonate resin (D), a phosphorus-based stabilizer (E) having a specific melting point, a hindered phenol-based stabilizer (F), and ultraviolet absorption having a specific melting point. By combining the agent (G) and blending each in a specific amount range, the above-mentioned amine resistance, scratch resistance (high hardness), impact resistance, and heat resistance are maintained, and the dry heat resistance and weather resistance are further excellent. In addition, it has been found that mold deposits during injection molding are suppressed.

The polycarbonate resin composition of the present invention has a viscosity average molecular weight (Mv) of preferably 15,000 to 40,000, more preferably 16,000 to 30,000, and even more preferably 18,000 to. It is 28,000. A polycarbonate resin composition having a viscosity average molecular weight less than the above range may not have sufficient toughness and crack resistance for practical use. On the other hand, a polycarbonate resin composition having a viscosity average molecular weight exceeding the above range is inferior in versatility because it requires a high molding temperature or a special molding method, and is further injected due to an increase in melt viscosity. The speed dependence tends to be high, and the yield may decrease due to poor appearance or the like.

To determine the viscosity average molecular weight of the polycarbonate resin composition, first, use an Ostwald viscometer from a solution in which 0.7 g of the polycarbonate resin composition is dissolved in 100 ml of methylene chloride at 20 ° C. for the specific viscosity (η _SP ) calculated by the following formula. Ask,
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall]
The viscosity average molecular weight Mv was calculated from the obtained specific viscosity (η _SP ) by the following mathematical formula.
η _SP / c = [η] + 0.45 × [η] ² c (where [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 Mv ^0.83
c = 0.7

The polycarbonate resin composition of the present invention preferably has a glass transition temperature of 130 to 160 ° C, more preferably 135 to 155 ° C, and even more preferably 140 to 150 ° C. When the glass transition temperature is at least the lower limit of the above range, the heat resistance is sufficient, and when it is at least the upper limit of the above range, it is not necessary to raise the molding processing temperature and molding becomes easy.

The polycarbonate resin composition of the present invention preferably has an impact energy of 25 J or more, more preferably 30 J or more, as determined by a high-speed surface impact test measured according to JIS K7211-2. Further, it is preferable that the fracture form is ductile fracture. When the impact energy is equal to or higher than the above value, brittle fracture does not occur and the impact resistance is excellent, which is preferable. The impact energy is 50 J or less and has sufficient characteristics.

The polycarbonate resin composition of the present invention conforms to JIS K7202-2 and has a Rockwell hardness of 90 or more, more preferably 95 or more, as measured on an M scale. When the Rockwell hardness is equal to or higher than the above value, it is preferable because it has excellent scratch resistance. The Rockwell hardness of 120 or less has sufficient characteristics.

The polycarbonate resin composition of the present invention was measured according to the general paint test method described in JIS K5600-5-4-Part 5: Mechanical properties of the coating film-Section 4: Scratch hardness (pencil method). The pencil hardness is preferably F to 4H, more preferably H to 2H. When the pencil hardness is within the above range, it is preferable that the surface of the molded product is not easily scratched.

The polycarbonate resin composition of the present invention has excellent dry heat resistance. Regarding the dry heat resistance, ΔYI measured by the following method is preferably 6 or less, more preferably 5.8 or less, and further preferably 5.6 or less.

Measurement method of dry heat resistance; Using a mold having a cavity surface with an arithmetic average roughness (Ra) of 0.03 μm for the polycarbonate resin composition pellets, using an injection molding machine J-75E3 manufactured by Japan Steel Works, Ltd. Under the conditions of cylinder temperature 290 ° C and mold temperature 80 ° C, width 50 mm, length 90 mm, thickness 3 mm (length 20 mm), 2 mm (length 45 mm) from the gate side at a holding time of 20 seconds and a cooling time of 20 seconds. ), A three-stage plate having a length of 1 mm (length 25 mm) was formed. The obtained plate was treated with a hot air dryer at 120 ° C. for 2,000 hr. The YI (yellowness) of the plate thickness 2 mm portion was measured before and after the dry heat test of 2,000 hr, and the yellow change degree (ΔYI) was evaluated. As an evaluation device, SE2000 type manufactured by Nippon Denshoku Co., Ltd. was used for measurement with a C light source, a viewing angle of 2 °, and a transmission method.

The polycarbonate resin composition of the present invention has excellent weather resistance. The weather resistance of ΔYI measured by the following method is preferably 12 or less, more preferably 11.5 or less, further preferably 11 or less, and particularly preferably 10.5 or less.

Weather resistance measurement method; Polycarbonate resin composition pellets are molded using a mold having a cavity surface with an arithmetic average roughness (Ra) of 0.03 μm, and an injection molding machine J-75E3 manufactured by Japan Steel Works is used. Under the conditions of cylinder temperature 290 ° C and mold temperature 80 ° C, width 50 mm, length 90 mm, thickness 3 mm (length 20 mm), 2 mm (length 45 mm) from the gate side at a holding time of 20 seconds and a cooling time of 20 seconds. ), A three-stage plate having a length of 1 mm (length 25 mm) was formed. For the obtained plate, using the Super Xenon Weather Meter Tester SX75 manufactured by Suga Test Instruments Co., Ltd., irradiance 180 W / m ² (300-400 nm), with rain (18 minutes / 120 minutes), irradiation: black panel temperature At 63 ° C. and humidity of 50%, during rainfall: 2,000 hr treatment was performed under the conditions of a tank temperature of 38 ° C. and a humidity of 95%. Before and after the weather resistance acceleration test of 2,000 hr, YI (yellowness) of a plate thickness of 2 mm was measured, and the degree of yellow change (ΔYI) was evaluated. As an evaluation device, SE2000 type manufactured by Nippon Denshoku Co., Ltd. was used for measurement with a C light source, a viewing angle of 2 °, and a transmission method.

In the polycarbonate resin composition of the present invention, the molded product was cut from the soft urethane foam used for the seat cushion material into a shape having a length and width of 50 mm and a thickness of 5 mm, both of which were sealed in a closed glass container and set at 85 ° C. It is preferable that the appearance of the test piece does not change after being left in the hot air dryer for 1,000 hours.

<Amine compounds used to form polyurethane foam>
Polyurethane resins are generally produced by reacting a polyol and a polyisocyanate in the presence of a catalyst and, if necessary, a foaming agent, a surfactant, a flame retardant, a cross-linking agent and the like. It is known that many metal compounds and tertiary amine compounds are used as catalysts in the production of polyurethane resins. These catalysts are widely used industrially when used alone or in combination. In the production of polyurethane foam using water, a low boiling point organic compound, or both as a foaming agent, among these catalysts, a tertiary amine compound is widely used because of its excellent productivity and moldability. There is. Examples of such a tertiary amine compound include conventionally known triethylenediamine, N, N, N', N'-tetramethylhexanediamine, N, N, N', N'-tetramethylpropanediamine, and N. , N, N', N'-tetramethylethylenediamine, bis (2-dimethylaminoethyl) ether, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N', N'-trimethylamino Examples thereof include ethyl piperazine, N, N-dimethylbenzylamine, N-methylmorpholin, N-ethylmorpholin, N, N-dimethylethanolamine and the like.

<Molded products, automobile interior parts>
The polycarbonate resin composition of the present invention can obtain a desired molded product by a method such as injection molding, injection compression molding, injection blow molding, two-color molding, extrusion molding or blow molding.

The production method of the polycarbonate resin composition of the present invention is not particularly limited, and a sheet-shaped or film-shaped molded product can be obtained by a method such as a melt extrusion method or a solution casting method (casting method). .. As a specific method of the melt extrusion method, for example, a polycarbonate resin composition is quantitatively supplied to an extruder, melted by heating, and the molten resin is extruded from the tip of a T-die into a sheet on a mirror surface roll to form a plurality of rolls. When it is solidified, it is cut to an appropriate size or wound up. A specific method of the solution casting method is, for example, a solution (concentration of 5% to 40%) in which a polycarbonate resin composition is dissolved in methylene chloride is poured from a T-die onto a mirror-polished stainless steel plate in a stepwise manner. A method is used in which the sheet is peeled off while passing through a temperature-controlled oven, the solvent is removed, and then the solution is cooled and wound up.

The polycarbonate resin composition can also be a laminate. Any method may be used for producing the laminated body, and it is particularly preferable to use a thermocompression bonding method or a coextrusion method. Any method is adopted as the thermocompression bonding method. For example, a method of thermocompression bonding a sheet with a laminating machine or a press machine, a method of thermocompression bonding immediately after extrusion, and particularly a method of continuously thermocompression bonding to a sheet immediately after extrusion is preferable. The method is industrially advantageous.

Moreover, since the polycarbonate resin composition of the present invention is excellent in scratch resistance, impact resistance, amine resistance, dry heat resistance and weather resistance, it is suitably used as an automobile interior part. Automotive interior parts include interior lighting lamp lenses, display meter covers, meter dials, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, head-up displays, etc. Various display devices, protective parts, translucent parts, etc. Further, since the automobile interior parts of the present invention have the above-mentioned characteristics, there is an advantage that a molded product obtained from the polycarbonate resin composition can be used as it is without requiring a coating treatment.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the measurement method of each characteristic is as follows.
(1) Viscosity Average Molecular Weight The viscosity average molecular weight of the polycarbonate resin composition is measured and calculated by the following method.
First, the polycarbonate resin composition pellets obtained by extrusion were mixed with 30 times the weight of methylene chloride to dissolve them, and the soluble component was collected by Celite filtration. After removing the solvent from the obtained solution, the obtained solid was sufficiently dried, and 0.7 g of the solid was dissolved in 100 ml of methylene chloride to obtain the specific viscosity (η _sp ) of the solution at 20 ° C. It was measured. Then, Mv calculated by the following formula was used as the viscosity average molecular weight.
η _sp / c = [η] +0.45 × [η] ² c
[Η] = 1.23 × 10 ^-4 Mv ^0.83
η _sp : Specific viscosity η: Extreme viscosity c: Constant (= 0.7)
Mv: Viscosity average molecular weight

(2) Composition ratio 40 mg of polycarbonate resin was dissolved in 0.6 ml deuterated chloroform solution, ¹ H-NMR was measured by a nuclear magnetic resonance apparatus manufactured by JEOL Ltd. at 400 MHz, and the spectral peak area ratio characteristic of each structural unit was used. , The composition ratio of the polycarbonate resin was calculated.

(3) Glass transition temperature Using the thermal analysis system DSC-2910 manufactured by TA Instruments, under the conditions of nitrogen atmosphere (nitrogen flow rate: 40 ml / min) and heating rate: 20 ° C./min according to JIS K7121. Measured in.

(4) High-speed surface impact test Using Shimadzu Hydroshot HTM-1, the test speed was 7 m / sec, the impact core radius was 6.4 mm, and the thickness of the 3-stage plate obtained during the measurement of pencil hardness was 2 mm. The impact energy was measured and the fracture morphology was visually observed.

(5) Push-in hardness (Rockwell hardness)
The test was carried out on the M scale in accordance with JIS K7202-2. As the test piece, a flat plate having a length and width of 100 mm and a thickness of 8 mm was used.

(6) Pencil hardness Using a mold having a cavity surface with an arithmetic average roughness (Ra) of 0.03 μm, using an injection molding machine J-75E3 manufactured by Japan Steel Works, a cylinder temperature of 280 ° C. and a mold temperature. Under the condition of 80 ° C., the holding time is 20 seconds and the cooling time is 20 seconds, the width is 50 mm, the length is 90 mm, and the thickness is 3 mm (length 20 mm), 2 mm (length 45 mm), 1 mm (length 25 mm) from the gate side. A three-stage plate was formed. The pencil hardness of the three-stage plate at a thickness of 2 mm was measured according to JIS K5600.

(7) Evaluation of amine resistance Using a mold having a cavity surface with an arithmetic average roughness (Ra) of 0.03 μm, a mold with a cylinder temperature of 290 ° C. using an injection molding machine J-75E3 manufactured by Japan Steel Works, Ltd. Under the condition of a temperature of 80 ° C., the holding time is 20 seconds and the cooling time is 20 seconds, the width is 50 mm, the length is 90 mm, and the thickness is 3 mm (length 20 mm), 2 mm (length 45 mm), 1 mm (length 25 mm) from the gate side. ), A three-stage plate was formed. The soft urethane foam used for the automobile seat cushion material is cut into a shape with a length and width of 50 mm and a thickness of 5 mm using a cutter, sealed in a glass airtight container together with a three-stage plate, and inside a hot air dryer set at 85 ° C. The appearance of the test piece after being left for 1000 hours was visually observed.
○: No change ×: Surface whitening

(8) Dry heat The pellets obtained in each example were used in a mold having a cavity surface having an arithmetic mean roughness (Ra) of 0.03 μm, and an injection molding machine J-75E3 manufactured by Japan Steel Works was used. Width 50 mm, length 90 mm, thickness 3 mm (length 20 mm), 2 mm (length) from the gate side under the conditions of cylinder temperature 290 ° C and mold temperature 80 ° C, holding time 20 seconds and cooling time 20 seconds. A three-stage plate having a size of 45 mm) and 1 mm (length 25 mm) was formed. The obtained plate was treated with a hot air dryer at 120 ° C. for 2,000 hr. The YI (yellowness) of the plate thickness 2 mm portion was measured before and after the dry heat test of 2,000 hr, and the yellow change degree (ΔYI) was evaluated. As an evaluation device, SE2000 type manufactured by Nippon Denshoku Co., Ltd. was used for measurement with a C light source, a viewing angle of 2 °, and a transmission method.

(9) Weather resistance For the pellets obtained in each example, a mold having a cavity surface with an arithmetic mean roughness (Ra) of 0.03 μm was used, and an injection molding machine J-75E3 manufactured by Japan Steel Works was used. Width 50 mm, length 90 mm, thickness 3 mm (length 20 mm), 2 mm (length) from the gate side under the conditions of cylinder temperature 290 ° C and mold temperature 80 ° C, holding time 20 seconds and cooling time 20 seconds. A three-stage plate having a size of 45 mm) and 1 mm (length 25 mm) was formed. For the obtained plate, using the Super Xenon Weather Meter Tester SX75 manufactured by Suga Test Instruments Co., Ltd., irradiance 180 W / m ² (300-400 nm), with rain (18 minutes / 120 minutes), irradiation: black panel temperature At 63 ° C. and humidity of 50%, during rainfall: 2,000 hr treatment was performed under the conditions of a tank temperature of 38 ° C. and a humidity of 95%. Before and after the weather resistance acceleration test of 2,000 hr, YI (yellowness) of a plate thickness of 2 mm was measured, and the degree of yellow change (ΔYI) was evaluated. As an evaluation device, SE2000 type manufactured by Nippon Denshoku Co., Ltd. was used for measurement with a C light source, a viewing angle of 2 °, and a transmission method.

(10) Die deposits The pellets obtained in each example were molded using a mold having a cavity surface with an surgical average roughness (Ra) of 0.03 μm, and an injection molding machine J-75E3 manufactured by Japan Steel Works, Ltd. With a cylinder temperature of 350 ° C. and a mold temperature of 85 ° C., with a holding time of 30 seconds and a cooling time of 40 seconds, the width is 50 mm, the length is 90 mm, and the thickness is 3 mm (length 20 mm) and 2 mm (length 20 mm) from the gate side. A three-stage plate having a length of 45 mm and a length of 1 mm (length 25 mm) was formed. After 300 shots of molding were continuously performed, the exposed surface coloring state was visually observed when the inside of the molded product on the movable part side of the mold and the portion in contact with the molded product on the fixed portion side were wiped with bleaching.
◯: Almost no coloring is observed in bleaching △: Slight coloring is observed in bleaching ×: Significant coloring is observed in bleaching

<Manufacturing of polycarbonate resin>
[Manufacturing Example 1]
A reactor equipped with a thermometer, a stirrer and a reflux cooler was charged with 4,555 parts of a 48% sodium hydroxide aqueous solution and 22,730 parts of ion-exchanged water, and 9,9-bis (4-hydroxyphenyl) was added thereto. 596 parts of Fluoren (manufactured by Honshu Kagaku), 1,618 parts of bisphenol C (manufactured by Honshu Kagaku), 1,799 parts of bisphenol A (manufactured by Nippon Steel Chemical Co., Ltd.), and 7.94 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries). After dissolution, 13,415 parts of methylene chloride was added, and 2,000 parts of bisphenol was blown at 15 to 25 ° C. over about 70 minutes with stirring. After the injection of phosgene was completed, 650 parts of a 48% aqueous sodium hydroxide solution and 87.6 parts of p-tert-butylphenol were added, and stirring was resumed. After emulsification, 3.94 parts of triethylamine was added, and the mixture was further stirred at 28 to 35 ° C. for 1 hour. And the reaction was finished.

After completion of the reaction, the product was diluted with methylene chloride and washed with water, then hydrochloric acid was added to make it acidic and washed with water, and then repeated with water until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water. A methylene solution was obtained. Next, this solution was passed through a filter having an opening of 0.3 μm, and further added dropwise to warm water in a kneader with an isolation chamber having a foreign matter outlet in the bearing, and the polycarbonate resin was flaked while distilling off methylene chloride, and subsequently, the said solution. The liquid-containing flakes were pulverized and dried to obtain a powder (D-1). The results of evaluating the powder are shown in Table 1.

[Manufacturing Example 2]
9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Honshu Chemical Industry Co., Ltd.) 298 parts, bisphenol C (manufactured by Honshu Chemical Industry Co., Ltd.) 1,820 parts, bisphenol A (manufactured by Nippon Steel Chemical Industry Co., Ltd.) 1,799 parts, p-tert- Polycarbonate resin powder (D-2) was obtained by the same method as in Production Example 1 except that 71.0 parts of butylphenol was used. The results of evaluating the powder are shown in Table 1.

[Manufacturing Example 3]
9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Honshu Chemical Industry Co., Ltd.) 894 parts, bisphenol C (manufactured by Honshu Chemical Industry Co., Ltd.) 1,213 parts, bisphenol A (manufactured by Nippon Steel Chemical Industry Co., Ltd.) 1,979 parts, p-tert- Polycarbonate resin powder (D-3) was obtained in the same manner as in Production Example 1 except that 106.5 parts of butylphenol was used. The results of evaluating the powder are shown in Table 1.

[Manufacturing Example 4]
9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Honshu Chemical Industry Co., Ltd.) 179 parts, bisphenol C (manufactured by Honshu Chemical Industry Co., Ltd.) 2,023 parts, bisphenol A (manufactured by Nippon Steel Chemical Industry Co., Ltd.) 1,691 parts, p-tert- Polycarbonate resin powder (D-4) was obtained in the same manner as in Production Example 1 except that 92.3 parts of butylphenol was used. The results of evaluating the powder are shown in Table 1.

[Manufacturing Example 5]
9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Honshu Chemical Industry) 1,193 parts, bisphenol C (manufactured by Honshu Chemical Industry) 1,618 parts, bisphenol A (manufactured by Nippon Steel Chemical Industry) 1,439 parts, p- A polycarbonate resin powder (D-5) was obtained in the same manner as in Production Example 1 except that 92.3 parts of tert-butylphenol was used. The results of evaluating the powder are shown in Table 1.

[Examples 1 to 9, Comparative Examples 1 to 7]
<Manufacturing of polycarbonate resin composition>
Each component shown in Tables 1 and 2 is weighed and mixed at the ratios shown in Tables 1 and 2, mixed by a blender, and then melt-kneaded using a bent twin-screw extruder to prepare a polycarbonate resin composition. Pellets were obtained. The additive to be added to the PC was completely mixed by a blender. The vent type twin-screw extruder was manufactured by Japan Steel Works, Ltd .: TEX30α (complete meshing, rotating in the same direction, double-threaded screw). The kneading zone is one type in front of the vent opening. The extrusion conditions are a discharge rate of 30 kg / hr, a screw rotation speed of 250 rpm, a vent vacuum degree of 1 kPa, and an extrusion temperature of 220 to 250 ° C. from the first supply port to the front of the kneading zone and 250 to 260 ° C. in the kneading zone. After that, the temperature up to the die was set to 260 to 270 ° C. The above resin composition was produced in an atmosphere in which clean air passed through a HEPA filter circulates, and sufficient care was taken not to allow foreign matter to enter during the work.

<Phosphorus stabilizer (E)>
E-1; Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (melting point: 235 ° C, manufactured by ADEKA Corporation)
E-2; Tris (2,4-di-tert-butylphenyl) phosphite (melting point: 184 ° C, manufactured by BASF)
E-3; Tetrakis (2,4-di-tert-butylphenyl) -4,4-biphenyldiphosphonite (melting point: 90 ° C., manufactured by Clariant)
<Phenolic stabilizer (F)>
F-1; octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate (melting point: 52 ° C., manufactured by BASF)
F-2; pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (melting point: 183 ° C, manufactured by BASF)
<Ultraviolet absorber (G)>
G-1; 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol] (melting point: 200 ° C., manufactured by ADEKA Corporation) )
G-2; 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- (hexyl) oxy-phenol (melting point: 152 ° C., manufactured by BASF)
G-3; 2- (2'hydroxy-5'-tert-octylphenyl) benzotriazole (melting point: 108 ° C., manufactured by BASF)

The polycarbonate resin composition of the present invention does not require a coating treatment, and does not require a coating treatment, and is a lamp lens for indoor lighting, a meter cover for display, a meter dial, various switch covers, a display cover, a heat control panel, an instrument panel, a center cluster, and a center. It can be suitably used as a material for various display devices such as panels, room lamp lenses, head-up displays, protective parts, and automobile interior parts such as translucent parts.

Claims (11)

As the main building blocks, (A) the following formula (1)

(In the formula (1), R ^{1 to} R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms or a halogen atom which may contain an aromatic group.)
Structural unit (A) represented by
(B) The following formula (2)

(In formula (2), R ^{3 to} R ⁴ are independently alkyl or halogen atoms having 1 to 6 carbon atoms. X is a single-bonded, substituted or unsubstituted alkylene group, substituted or unsubstituted. Alkylidene group, sulfur atom or oxygen atom.)
The structural unit (B) represented by, and (C) the following formula (3)

(In formula (3), W represents a single bond, substituted or unsubstituted alkylene group, substituted or unsubstituted alkylidene group, sulfur atom or oxygen atom.)
It is composed of the structural unit (C) represented by, the ratio of the structural unit (A) in all the structural units is 5 to 15 mol%, the ratio of the structural unit (B) is 20 to 60 mol%, and the structural unit (C). 0.01 to 0.5 parts by mass of phosphorus-based stabilizer (E) having a melting point of 100 ° C. or higher, and hindered phenol-based stable, with respect to 100 parts by mass of the polycarbonate resin (D) having a proportion of 25 to 75 mol%. A polycarbonate resin composition containing 0.01 to 1 part by mass of an agent (F) and 0.1 to 5 parts by mass of an ultraviolet absorber (G) having a melting point of 130 ° C. or higher. R ^{1 to} R ² in the formula (1) are independently hydrogen atoms and alkyl groups having 1 to 6 carbon atoms, and R ^{3 to} R ⁴ in the formula (2) are independently independent carbon atoms 1 to 1. It is an alkyl group of 6, and X is a single bond, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms, and W in the formula (3). The polycarbonate resin composition according to claim 1, wherein is a single bond, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms. The polycarbonate resin composition according to claim 1 or 2, wherein the viscosity average molecular weight is 15,000 to 40,000. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the structural unit (A) is a structural unit derived from 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the constitutional unit (B) is a constitutional unit derived from 2,2-bis (4-hydroxy-3-methylphenyl) propane. The polycarbonate resin composition according to any one of claims 1 to 5, wherein the constitutional unit (C) is a constitutional unit derived from 2,2-bis (4-hydroxyphenyl) propane. The polycarbonate resin composition according to any one of claims 1 to 6, wherein the degree of yellow change (ΔYI) around 2000 hr in the weather resistance acceleration test is 12 or less. The polycarbonate resin composition according to any one of claims 1 to 7, wherein the degree of yellow change (ΔYI) at 120 ° C. and around 2000 hr in the dry heat test is 6 or less. A molded product obtained by injection molding the polycarbonate resin composition according to any one of claims 1 to 8. A sheet or film obtained by extruding the polycarbonate resin composition according to any one of claims 1 to 8. An automobile interior part using the molded product according to claim 9 or the sheet or film according to claim 10.