JP2018154756A - Polycarbonate resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin excellent in light fastness, transparency, color tone, heat resistance, thermal stability and mechanical strength.SOLUTION: The polycarbonate resin composition contains (A) a polycarbonate resin comprising a constitutional unit derived from a dihydroxy compound represented by the general formula (1), (B) an ultraviolet absorber, (C) a photostabilizer, and (D) an antioxidant having a sterically hindered substituent on only one of two carbon atoms neighboring a carbon atom having a phenolic hydroxyl group.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition excellent in weather resistance, moldability, hue, heat resistance, thermal stability, and mechanical strength.

Polycarbonate resins are generally composed of bisphenols as monomer components, taking advantage of transparency, heat resistance, mechanical strength, etc., and electrical / electronic parts, automotive parts, medical parts, building materials, films, sheets, bottles It is widely used as so-called engineering plastics in the fields of optical recording media and lenses.
However, conventional polycarbonate resins are limited in use outdoors or in the vicinity of lighting devices, because their hue, transparency, and mechanical strength deteriorate when used in places exposed to ultraviolet rays or visible light for a long time. . Further, when used as various molded products, there has been a problem that the releasability is poor at the time of melt molding and it is difficult to use it for a transparent material or an optical material.

In order to solve such a problem, a method of adding a benzophenone-based UV absorber, a benzotriazole-based UV absorber, or a benzoxazine-based UV absorber to a polycarbonate resin is widely known (for example, see Non-Patent Document 1). ).
However, when such an ultraviolet absorber is added, although the hue after UV irradiation is improved, the hue, heat resistance, and transparency of the resin are deteriorated in the first place. There were problems such as contamination of the mold.

In addition, hindered amine light stabilizers are known as light stabilizers, but polycarbonate resins are unstable to basic components such as alkalis at room temperature, and are reported to be hydrolyzed to hindered amine compounds. (For example, refer nonpatent literature 2).
Since the bisphenol compound used in the conventional polycarbonate resin has a benzene ring structure, it absorbs a large amount of ultraviolet rays. This causes a deterioration in the light resistance of the polycarbonate resin. Therefore, an aliphatic dihydroxy compound having no benzene ring structure in the molecular skeleton. If a cyclic dihydroxy compound monomer unit having an ether bond in the molecule, such as a compound, an alicyclic dihydroxy compound, or isosorbide, is used, it is expected that light resistance is improved in principle. Among these, polycarbonate resins using isosorbide as a monomer obtained from biomass resources are excellent in heat resistance and mechanical strength, so that many studies have been made in recent years (for example, Patent Documents 1 to 4). .

  In addition, a polycarbonate resin composition using a cyclic dihydroxy compound having an ether bond in its molecule, such as isosorbide, isomannide, isoitide, etc., which does not have a benzene ring structure in the molecular skeleton, and a benzotriazole-based, benzophenone as an ultraviolet absorber. It is known to add a cyanoacrylate type or a hindered amine type light stabilizer (for example, Patent Documents 5 and 6).

International Publication No. 2004/111106 Pamphlet Japanese Patent Laid-Open No. 2006-232897 JP 2008-24919 A JP 2008-274007 A JP 2007-70391 A International Publication No. 2011/118768 Pamphlet

Polycarbonate resin handbook (issued by Seiichi Honma, published by Nikkan Kogyo Shimbun, August 28, 1992) G.L.Gains, Jr .: Polym. Degradation Stab., 27, 13 (1990)

  However, a cyclic dihydroxy compound having an ether bond in the molecule like isosorbide does not have a phenolic hydroxyl group. A polycarbonate resin obtained using such a dihydroxy compound having no phenolic hydroxyl group is inferior in thermal stability to a polycarbonate resin obtained using a dihydroxy compound having a phenolic hydroxyl group such as bisphenol A. For this reason, coloration occurs during polymerization or molding that is exposed to high temperatures, and as a result, there is a problem in that ultraviolet rays and visible light are absorbed to deteriorate weather resistance. In particular, when a cyclic dihydroxy compound having an ether bond in the molecule such as isosorbide is used, the initial hue, hue deterioration after light resistance test, gloss deterioration, and molding appearance deterioration are remarkable, and significant improvement is required. It was.

  The object of the present invention is to solve the above-mentioned conventional problems and not only have moldability, transparency, hue, heat resistance, thermal stability, and mechanical strength, but also excellent initial color tone and weather resistance, and light resistance. Polycarbonate resin that has good color tone, gloss and good appearance after testing, and can be applied to a wide range of fields such as electrical and electronic parts, injection molding fields such as automotive parts, film and sheet fields, and building materials. The object is to provide a composition and a molded article thereof.

As a result of intensive studies to solve the above problems, the present inventor not only has the following resin compositions having moldability, transparency, hue, heat resistance, thermal stability, and mechanical strength. The present inventors have found that the initial color tone and weather resistance are excellent, the color tone and gloss are good even after the light resistance test, and the molded appearance is good, and the present invention has been achieved.
(A) a polycarbonate resin containing a structural unit derived from a dihydroxy compound represented by the following general formula (1);
(B) Ultraviolet absorber (C) Light stabilizer (D) Polycarbonate comprising an antioxidant having a sterically hindered substituent only on one of two carbon atoms adjacent to a carbon atom having a phenolic hydroxyl group Resin composition.

According to the present invention, not only has moldability, transparency, hue, heat resistance, thermal stability, and mechanical strength, but also excellent initial color tone and weather resistance, and good color tone and gloss after light resistance test. Molding appearance is also good, injection molding field such as electrical / electronic parts, automotive parts, film, sheet field,
Furthermore, it becomes possible to provide a polycarbonate resin composition applicable to a wide range of fields such as building member applications and molded articles thereof.

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.
(1) Polycarbonate resin composition The polycarbonate resin composition of the present invention is as follows.
(A) a polycarbonate resin containing a structural unit derived from a dihydroxy compound represented by the following general formula (1);
(B) Ultraviolet absorber (C) Light stabilizer (D) Polycarbonate comprising an antioxidant having a sterically hindered substituent only on one of two carbon atoms adjacent to a carbon atom having a phenolic hydroxyl group Resin composition.

  Hereinafter, the polycarbonate resin composition of the present invention will be described in detail. In addition, although content of the following (A)-(F) is not specifically limited normally, in the following description, when it is set as "when it is set as a total of 100 weight part of the following (A) and the following (E)." The preferable content of each component will be described. In addition, the following description means that the same content is preferable even when not using a component (E).

(A) Polycarbonate resin The polycarbonate resin used in the polycarbonate resin composition of the present invention (hereinafter sometimes referred to as “the polycarbonate resin (A) of the present invention”) is a structural unit derived from a dihydroxy compound linked by a carbonate bond. It is a polycarbonate resin and contains at least a structural unit derived from a dihydroxy compound represented by the following general formula (1) (hereinafter sometimes referred to as “dihydroxy compound (1)”). In addition, the structural unit derived from the dihydroxy compound which comprises the polycarbonate resin (A) used by this invention removes a hydrogen atom from the hydroxyl group of a dihydroxy compound.

Examples of the dihydroxy compound represented by the above formula (1) include isosorbide, isomannide, and isoide which are in a stereoisomeric relationship. Among these dihydroxy compounds (1), they are abundant as resources and can be easily obtained, and isosorbide obtained by dehydrating condensation of sorbitol produced from various starches is easy to obtain and produce. Most preferable in terms of formability.
These dihydroxy compounds (1) may be used individually by 1 type, and may be used in combination of 2 or more type.

The dihydroxy compound (1) having a cyclic ether structure such as isosorbide is easily oxidized gradually by oxygen. For this reason, when storing or handling during manufacture, it is important to prevent moisture from being mixed in, and to use an oxygen scavenger or handle under a nitrogen atmosphere in order to prevent decomposition by oxygen. When isosorbide is oxidized, decomposition products such as formic acid are generated. For example, when polycarbonate resin (A) is produced using isosorbide containing these decomposition products, the resulting polycarbonate resin (A) is colored. Or cause a significant deterioration in physical properties. Moreover, it may affect the polymerization reaction, and a high molecular weight polymer may not be obtained.
Therefore, it is preferable to use a stabilizer for the dihydroxy compound (1). As the stabilizer, it is preferable to use stabilizers such as a reducing agent, an antacid, an antioxidant, an oxygen scavenger, a light stabilizer, a pH stabilizer, a heat stabilizer, and the like, and particularly under acidic conditions, the dihydroxy compound (1) It is preferable that a basic stabilizer is contained because of being easily altered. Among these, examples of the reducing agent include sodium borohydride and lithium borohydride, and examples of the antacid include alkalis such as sodium hydroxide. However, the addition of such an alkali metal salt is not preferable because the added alkali metal may serve as a polymerization catalyst during the production of the polycarbonate resin (A).
Basic stabilizers include group 1 or group 2 metal hydroxides, carbonates, phosphates, phosphites, hypophosphorous acid in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). Salts, borates, fatty acid salts, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium Basic ammonium compounds such as um hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide, 4-aminopyridine, 2-aminopyridine, N, N -Dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole And amine compounds such as aminoquinoline. Of these, sodium or potassium phosphates and phosphites are preferable, and disodium hydrogen phosphate and disodium hydrogen phosphite are particularly preferable because of their effects and ease of distillation removal described later.

Although there is no restriction | limiting in particular in content in the dihydroxy compound (1) of these basic stabilizers, if too little, there exists a possibility that the effect which prevents the modification of dihydroxy compound (1) may not be acquired, and if too much, a dihydroxy compound Since the modification of (1) may be caused, it is usually 0.0001% by weight to 1% by weight, preferably 0.001% by weight to 0.1% by weight, based on the dihydroxy compound (1).
When the dihydroxy compound (1) to which these stabilizers are added is used as a raw material for the polycarbonate resin (A), depending on the type of the stabilizer, the resulting polycarbonate resin (A) may be colored or the physical properties may be significantly deteriorated. There is a case. For example, when the dihydroxy compound (1) containing the above basic stabilizer is used as a raw material for producing the polycarbonate resin (A), the basic stabilizer itself becomes a polymerization catalyst, and it becomes difficult to control the polymerization rate and quality. In addition, the initial hue is deteriorated, and as a result, the weather resistance of the molded product of the polycarbonate resin (A) is deteriorated.
For this reason, before using dihydroxy compound (1) as a manufacturing raw material of polycarbonate resin (A), it is preferable to remove stabilizers, such as a basic stabilizer, by ion exchange resin or distillation.
Moreover, as mentioned above, when the dihydroxy compound (1) containing the oxidative decomposition product of the dihydroxy compound (1) is used as a raw material for producing the polycarbonate resin (A), the resulting polycarbonate resin (A) may be colored. In addition, there is a possibility that not only the physical properties may be remarkably deteriorated, but also the polymerization reaction is affected and a high molecular weight polymer may not be obtained.

  For this reason, in order to obtain the dihydroxy compound (1) which does not contain an oxidative decomposition product, and in order to remove the above-mentioned basic stabilizer, it is preferable to perform distillation purification of the dihydroxy compound (1). The distillation in this case may be simple distillation or continuous distillation, and is not particularly limited. As distillation conditions, it is preferable to carry out distillation under reduced pressure in an inert gas atmosphere such as argon or nitrogen. In order to suppress thermal denaturation, it is 250 ° C. or lower, preferably 200 ° C. or lower, particularly 180 °. It is preferable to carry out under the conditions of ℃ or less.

<Dihydroxy compounds other than dihydroxy compound (1)>
The polycarbonate resin (A) of the present invention contains a structural unit (a-2) derived from a dihydroxy compound other than the dihydroxy compound (1) in addition to the structural unit derived from the dihydroxy compound (1).
The polycarbonate resin (A) containing the structural unit (a-2) derived from the dihydroxy compound other than the dihydroxy compound (1) is, for example, other than the dihydroxy compound (1) according to the production method of the polycarbonate resin (A) described later. Manufactured using one or more dihydroxy compounds.

  The structural unit (a-2) derived from a dihydroxy compound other than the dihydroxy compound (1) contained in the polycarbonate resin (A) of the present invention is a group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and an aromatic dihydroxy compound. A structural unit derived from a dihydroxy compound selected from In particular, from the viewpoint of weather resistance, it is preferable to have a structural unit derived from a dihydroxy compound selected from the group consisting of an aliphatic dihydroxy compound and an alicyclic dihydroxy compound, and in particular, a structural unit derived from an alicyclic dihydroxy compound. It is preferable to have. When the polycarbonate resin (A) has such a structural unit, the obtained polycarbonate resin (A) can be further given flexibility, and is durable when a resin composition containing the polycarbonate resin (A) is molded. Improves.

(Aliphatic dihydroxy compound)
Examples of the aliphatic dihydroxy compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2 -Pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1 , 12-dodecanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl- , 6-hexanediol, 1,10-decanediol, hydrogenated dilinoleyloxy glycol, hydrogenated dioleyl glycol. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1 , 9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol are preferred.

(Alicyclic dihydroxy compound)
Although it does not specifically limit as an alicyclic dihydroxy compound, The compound containing a 5-membered ring structure or a 6-membered ring structure is mentioned. The six-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond. Carbon number contained in an alicyclic dihydroxy compound is 70 or less normally, Preferably it is 50 or less, More preferably, it is 30 or less. When the carbon number is excessively large, the heat resistance becomes high, but synthesis tends to be difficult and purification tends to be difficult. The smaller the carbon number, the easier it is to purify and the easier it is to obtain, but if it is too small, the ring structure is unstable and the synthesis becomes difficult.

Examples of alicyclic dihydroxy compounds include 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 2-methyl. Cyclohexanediols such as -1,4-cyclohexanediol, cyclohexenediols such as 4-cyclohexene-1,2-diol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4- Cyclohexane dimethanol such as cyclohexane dimethanol, norbornane dimethanol such as 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 1,3- Adamantanediol, 2 2-adamantane diol.
Among the specific examples of the alicyclic dihydroxy compounds described above, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 -Cyclohexane dimethanol such as cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 1,3-adamantanediol, 2,2-adamantanediol, ease of availability and ease of handling From these viewpoints, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, tricyclodecane dimethanol, and pentacyclopentadecanedimethanol are preferable. Among these, 2,2, 4,4-tetramethyl-1,3- Clobutanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, and pentacyclopentadecane dimethanol are particularly preferred, and 2,2,4,4-tetramethyl-1,3-cyclobutane Most preferred are diol, 1,4-cyclohexanedimethanol, and tricyclodecane dimethanol.
In addition, the said exemplary compound is an example of the alicyclic dihydroxy compound which can be used for this invention, Comprising: It is not limited to these at all. These alicyclic dihydroxy compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

(Aromatic dihydroxy compounds)
Examples of the aromatic dihydroxy compound include substituted or unsubstituted bisphenol compounds, and specifically include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis. (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 1,1 -Bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -3-
Methylbutane, 1,1-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) hexane, 3,3-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxy) Bisphenol compounds having no substituent on the aromatic ring such as phenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane; (3-phenyl-4-hydroxyphenyl) methane, 1,1-bis (3-phenyl-4-hydroxyphenyl) ethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2- Bisphenol having an aryl group as a substituent on an aromatic ring such as bis (3-phenyl-4-hydroxyphenyl) propane Compounds: bis (4-hydroxy-3-methylphenyl) methane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) propane 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, bis (4-hydroxy-3-ethylphenyl) methane, 1-bis (4-hydroxy-3-ethylphenyl) ethane, 1,1-bis (4-hydroxy-3-ethylphenyl) propane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane, , 1-bis (4-hydroxy-3-ethylphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane 2,2-bis (4-hydroxy-3- (sec-butyl) phenyl) propane, bis (4-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,5- Dimethylphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, bis (4-hydroxy-3) , 6-Dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,6-dimethylphenyl) ethane, 2,2-bis (4-hydroxy-3,6-dimethylphenyl) propane, bis (4- Hydroxy-2,3,5-trimethylphenyl) methane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) ethane, 2,2-bis (4- Hydroxy-2,3,5-trimethylphenyl) propane, bis (4-hydroxy-2,3,5-trimethylphenyl) phenylmethane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) Bisphenol compounds having an alkyl group as a substituent on an aromatic ring such as phenylethane and 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) cyclohexane; bis (4-hydroxyphenyl) phenylmethane; 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-phenylpropane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) Divalent groups connecting aromatic rings such as dibenzylmethane have aryl groups as substituents Bisphenol compounds; bisphenol compounds in which aromatic rings such as 4,4′-dihydroxydiphenyl ether and 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl ether are connected by an ether bond; 4,4′- Bisphenol compounds in which aromatic rings such as dihydroxydiphenylsulfone and 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylsulfone are linked by a sulfone bond; 4,4′-dihydroxydiphenylsulfide, 3, Bisphenol compounds in which aromatic rings such as 3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfide are linked by sulfide bonds, etc., 6,6′-dihydroxy-3,3,3 ′, 3 ′ -Tetramethyl-1,1'-spirobiindane, preferably 2,2-bis (4-hydro Shifeniru) propane (hereinafter sometimes abbreviated as "bisphenol A". ), 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane.
Dihydroxy compounds other than the above-mentioned dihydroxy compound (1) may be used individually by 1 type, and 2 or more types may be mixed and used for them.
[Mixing of polycarbonate resin]
The polycarbonate resin as component A described above may be only one type of polycarbonate, or may contain a plurality of polycarbonate copolymers having different copolymerization ratios. That is, as the component A, a polycarbonate resin mixture obtained by melting and mixing a plurality of polycarbonate copolymers having different copolymerization ratios can be used. The resin temperature at the melt extrusion port during the melt mixing is preferably 235 ° C. to 245 ° C., more preferably 238 ° C. to 242 ° C. By setting it within this range, the polycarbonate resin can be prevented from being colored, thermally deteriorated, or burned, and a good polycarbonate resin mixture having higher impact strength can be obtained.

  As for the range of copolymerization ratios of a plurality of polycarbonate copolymers having different copolymerization ratios and the mixture ratio of the plurality of polycarbonate copolymers, the copolymerization ratio of the polycarbonate resin mixture obtained after mixing satisfies a predetermined range. It is appropriately selected depending on conditions. When only one type of polycarbonate is used as the polycarbonate resin (A) and when a plurality of polycarbonate copolymers are mixed, the preferred range of the copolymerization ratio of the polycarbonate resin mixture obtained after mixing is the same as described below. To do. That is, with respect to the structural units derived from all dihydroxy compounds contained in the polycarbonate resin (A) of the present invention, the amount of structural units derived from the dihydroxy compound represented by the general formula (1) (however, the number of moles) is 40 mol% or more, preferably 45 mol% or more, more preferably 50 mol% or more, and most preferably 55 mol% or more. Moreover, 90 mol% or less is preferable, 80 mol% or less is more preferable, 75 mol% or less is especially preferable, and 70 mol% or less is the most preferable. Further, the content ratio of the structural unit (a-2) derived from the dihydroxy compound other than the dihydroxy compound (1) in the polycarbonate resin (A) used in the present invention is not particularly limited, but the total content in the polycarbonate resin (A) is not limited. In the structural unit derived from the dihydroxy compound, 10 mol% or more is preferable, 20 mol% or more is more preferable, 25 mol% or more is particularly preferable, and 30 mol% or more is most preferable. Moreover, 60 mol% or less is preferable, 55 mol% or less is more preferable, 50 mol% or less is especially preferable, and 45 mol% or less is the most preferable. When the polycarbonate resin (A) is in the above range, the impact resistance and heat resistance are good.

  In the polycarbonate resin (A) of the present invention, the content of the structural unit derived from the above aromatic dihydroxy compound is relative to the structural unit derived from all the dihydroxy compounds contained in the polycarbonate resin (A) of the present invention. 0 mol% or more and less than 40 mol% is preferable, 0 mol% or more and less than 20 mol% is more preferable, and 0 mol% or more and less than 10 mol% is more preferable. When the polycarbonate resin (A) has a structural unit derived from an aromatic dihydroxy compound, improvements in heat resistance, surface impact resistance, molding processability and the like can be expected. However, since the structural unit derived from the aromatic dihydroxy compound may be markedly colored, it is most preferable from the viewpoint of weather resistance that it does not have the structural unit derived from the aromatic dihydroxy compound.

(Carbonated diester)
The polycarbonate resin of the present invention can be obtained by polycondensation by a transesterification reaction using the above-mentioned dihydroxy compound containing the dihydroxy compound of the present invention and a carbonic acid diester as raw materials.
As a carbonic acid diester used, what is normally represented by following General formula (6) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.

In the above formula (6), A ¹ and A ² are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic group.
Examples of the carbonic acid diester represented by the above formula (6) include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, preferably diphenyl carbonate. Carbonates and substituted diphenyl carbonates, particularly preferably diphenyl carbonate. The carbonic acid diester may contain impurities such as chloride ions, and these impurities may hinder the polymerization reaction or may deteriorate the hue of the resulting polycarbonate resin (A). Accordingly, it is preferable to use a product purified by distillation or the like.

The carbonic acid diester is preferably used in a molar ratio of 0.90 to 1.20, more preferably in a molar ratio of 0.95 to 1.10, based on all dihydroxy compounds used in the melt polymerization. It is even more preferable to use at a molar ratio of .96 to 1.10, and particularly preferable to use at a molar ratio of 0.98 to 1.04.
When this molar ratio is less than 0.90, the terminal hydroxyl group of the produced polycarbonate resin (A) is increased, the thermal stability of the polymer is deteriorated, and coloring is caused when molding the thermoplastic resin composition. Or the rate of the transesterification reaction may be reduced, or the desired high molecular weight product may not be obtained.

  If this molar ratio is greater than 1.20, the rate of the transesterification reaction decreases under the same conditions, making it difficult to produce a polycarbonate resin (A) having a desired molecular weight. The amount of residual carbonic acid diester in (A) increases, and this residual carbonic acid diester may be unfavorable at the time of molding or the odor of the molded product, increasing the heat history during the polymerization reaction, resulting in The hue and weather resistance of the obtained polycarbonate resin (A) may be deteriorated.

  Furthermore, when the molar ratio of the carbonic acid diester to the total dihydroxy compound increases, the amount of residual carbonic acid diester in the resulting polycarbonate resin (A) increases, and these absorb the ultraviolet rays to increase the light resistance of the polycarbonate resin (A). It may worsen and is not preferable. The concentration of the carbonic acid diester remaining in the polycarbonate resin (A) of the present invention is preferably 200 ppm by weight or less, more preferably 100 ppm by weight or less, particularly preferably 60 ppm by weight or less, and particularly preferably 30 ppm by weight or less. However, actually, the polycarbonate resin (A) may contain an unreacted carbonic acid diester, and the lower limit value of the unreacted carbonic acid diester concentration in the polycarbonate resin (A) is usually 1 ppm by weight.

<Transesterification reaction catalyst>
The polycarbonate resin (A) of the present invention can be produced by transesterifying the dihydroxy compound containing the dihydroxy compound (1) and the carbonic acid diester represented by the formula (6) as described above. More specifically, it can be obtained by transesterification to remove by-product monohydroxy compounds and the like out of the system. In this case, melt polymerization is usually carried out by transesterification in the presence of a transesterification catalyst.

  Examples of the transesterification catalyst (hereinafter sometimes referred to as “catalyst”) that can be used in the production of the polycarbonate resin (A) of the present invention include 1 in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). A basic compound such as a metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound of a group or group 2 (hereinafter simply referred to as “group 1” or “group 2”) Can be mentioned. Among these, Preferably a group 1 metal compound and / or a group 2 metal compound are used.

It is possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound in combination with the Group 1 metal compound and / or the Group 2 metal compound. It is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.
In addition, the group 1 metal compound and / or the group 2 metal compound are usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt. From the viewpoint of easiness, a hydroxide, carbonate, and acetate are preferable, and acetate is preferable from the viewpoint of hue and polymerization activity.

  Examples of the Group 1 metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, Cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride , Sodium borohydride, potassium borohydride, lithium phenide boron, cesium phenide boron, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, 2 sodium hydrogen phosphate 2 potassium potassium phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, lithium, Examples include cesium alcoholate, phenolate, disodium salt of bisphenol A, 2 potassium salt, 2 lithium salt, 2 cesium salt, etc. Among them, cesium compound and lithium compound are preferable.

  Examples of the Group 2 metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, Strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like, among which magnesium compounds, calcium compounds and barium compounds are preferred, magnesium compounds and / or Or a calcium compound is still more preferable.

  Examples of basic boron compounds include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzyl. Examples include sodium, potassium, lithium, calcium, barium, magnesium, or strontium salts such as boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, etc. It is done.

Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.
Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide Sid, butyl triphenyl ammonium hydroxide, and the like.

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

Among the above, at least one metal compound selected from the group consisting of a Group 2 metal compound and a lithium compound is used as a catalyst. Various properties such as transparency, hue, and light resistance of the resulting polycarbonate resin (A) are used. It is preferable in order to make the physical properties excellent.
Moreover, in order to make the polycarbonate resin (A) particularly excellent in transparency, hue and light resistance, the catalyst is at least one metal compound selected from the group consisting of magnesium compounds, calcium compounds and barium compounds. It is preferable that it is at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds.

In the case of a Group 1 metal compound and / or a Group 2 metal compound, the amount of the catalyst used is preferably 0.1 to 300 μmol, more preferably as a metal equivalent with respect to 1 mol of all dihydroxy compounds subjected to the reaction. It is in the range of 0.1 to 100 μmol, more preferably 0.5 to 50 μmol, and even more preferably 1 to 25 μmol.
Among the above, when using a compound containing at least one metal selected from the group consisting of lithium and group 2 metals, at least one metal compound selected from the group consisting of magnesium compounds, calcium compounds and barium compounds is used. When used, the amount in terms of metal is preferably 0.1 μmol or more, more preferably 0.5 μmol or more, and particularly preferably 0.7 μmol or more per 1 mol of all dihydroxy compounds subjected to the reaction. The upper limit is preferably 20 μmol, more preferably 10 μmol, particularly preferably 3 μmol, and most preferably 2.0 μmol.

  If the amount of the catalyst used is too small, the polymerization activity necessary for producing the polycarbonate resin (A) having a desired molecular weight cannot be obtained, and sufficient breaking energy may not be obtained. On the other hand, if the amount of the catalyst used is too large, not only will the hue of the resulting polycarbonate resin (A) be deteriorated, but also by-products may be generated, resulting in a decrease in fluidity and the generation of gel, resulting in brittle fracture. This may cause the production of polycarbonate resin (A) having a target quality.

<Production method of polycarbonate resin (A)>
The polycarbonate resin (A) of the present invention is obtained by melt polymerization of a dihydroxy compound containing the dihydroxy compound (1) and a carbonic acid diester by an ester exchange reaction. The raw material dihydroxy compound and the carbonic acid diester are transesterified. It is preferable to mix uniformly before.

  The mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and the upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. Among these, 100 ° C. or higher and 120 ° C. or lower is preferable. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often causing problems such as solidification, and if the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated. There is a possibility that the hue of the polycarbonate resin (A) obtained will deteriorate and the light resistance will be adversely affected.

The operation of mixing the dihydroxy compound and the carbonic acid diester is an oxygen concentration of 10% by volume or less, further 0.0001% by volume to 10% by volume, especially 0.0001% by volume to 5% by volume, and particularly 0.0001% by volume. It is preferable to carry out in an atmosphere of 1% to 1% by volume from the viewpoint of preventing hue deterioration of the obtained polycarbonate resin (A).
The polycarbonate resin (A) of the present invention is preferably produced by melt polymerization in multiple stages using a plurality of reactors using a catalyst. The reason for carrying out melt polymerization in multiple reactors is that at the beginning of the melt polymerization reaction, it is important to suppress the volatilization of the monomer while maintaining the required polymerization rate because there are many monomers contained in the reaction solution. In the latter stage of the melt polymerization reaction, it is important to sufficiently distill off the by-produced monohydroxy compound in order to shift the equilibrium to the polymerization side. Thus, in order to set different polymerization reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of reactors arranged in series. As described above, the number of the reactors may be at least two, but from the viewpoint of production efficiency, the number of reactors is three or more, preferably 3 to 5, and particularly preferably four.

The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.
Furthermore, it is effective to use a reflux condenser for the polymerization reactor in order to suppress the amount of the monomer to be distilled off, and the effect is particularly great in a reactor at the initial stage of polymerization where there are many unreacted monomer components. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected according to the monomer used, but the temperature of the refrigerant introduced into the reflux condenser is usually 45 to 180 ° C. at the inlet of the reflux condenser. Yes, preferably 80 to 150 ° C, particularly preferably 100 to 130 ° C. If the temperature of the refrigerant introduced into the reflux condenser is too high, the reflux amount is reduced and the effect is reduced. If it is too low, the distillation efficiency of the monohydroxy compound to be originally distilled tends to be reduced. As the refrigerant, hot water, steam, heat medium oil or the like is used, and steam or heat medium oil is preferable.

In order to maintain the polymerization rate appropriately and suppress the distillation of the monomer, while maintaining the hue, thermal stability, light resistance, etc. of the finally obtained polycarbonate resin (A), the above-mentioned catalyst is used. It is important to select the type and amount.
In the production of the polycarbonate resin (A) of the present invention, if there are two or more reactors, the reactor is further provided with a plurality of reaction stages having different conditions, and the temperature and pressure are continuously changed. You may go.

In the production of the polycarbonate resin (A) of the present invention, the catalyst can be added to the raw material preparation tank, the raw material storage tank, or can be directly added to the reactor. The catalyst supply line is installed in the middle of the raw material line before being supplied to the reactor, and preferably supplied as an aqueous solution.
As the polymerization conditions, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum in the initial stage of polymerization and to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum in the late stage of polymerization. Appropriate selection of the jacket temperature and internal temperature at the stage and the pressure in the reaction system is important from the viewpoint of the hue and light resistance of the resulting polycarbonate resin (A). For example, if either the temperature or the pressure is changed too quickly before the polymerization reaction reaches a predetermined value, the unreacted monomer will be distilled, causing the molar ratio of the dihydroxy compound and the carbonic acid diester to change, resulting in a decrease in the polymerization rate. Or a polymer having a predetermined molecular weight or terminal group may not be obtained, and as a result, the object of the present invention may not be achieved.

If the temperature of the transesterification reaction is too low, the productivity is lowered and the thermal history of the product is increased. If the temperature is too high, not only the evaporation of the monomer is caused, but also the decomposition and coloring of the polycarbonate resin (A) can be promoted. There is sex.
In the production of the polycarbonate resin (A) of the present invention, the method of transesterifying the dihydroxy compound containing the dihydroxy compound (1) and the carbonic acid diester in the presence of a catalyst is usually carried out in a multistage process of two or more stages. . Specifically, the first stage transesterification reaction temperature (hereinafter sometimes referred to as “internal temperature”) is preferably 140 ° C. or higher, more preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and even more. Preferably it is 200 degreeC or more. Further, the transesterification temperature in the first stage is preferably 270 ° C. or lower, more preferably 240 ° C. or lower, further preferably 230 ° C. or lower, and even more preferably 220 ° C. or lower. The residence time in the first stage transesterification is usually 0.
1 to 10 hours, preferably 0.5 to 3 hours, and the transesterification reaction in the first stage is carried out while distilling off the generated monohydroxy compound to the outside of the reaction system. In the second and subsequent stages, the transesterification reaction temperature is increased, and the transesterification reaction is usually performed at a temperature of 210 to 270 ° C., preferably 220 to 250 ° C., while simultaneously removing the monohydroxy compound generated outside the reaction system. The pressure of the reaction system is gradually lowered from the pressure in the first stage, so that the pressure of the reaction system finally becomes 200 Pa or less, usually 0.1 to 10 hours, preferably 0.5 to 6 hours, Particularly preferably, the polycondensation reaction is performed for 1 to 3 hours.

  When the transesterification reaction temperature is excessively high, the hue is deteriorated when formed into a molded product, which may easily cause brittle fracture. When the transesterification reaction temperature is too low, the target molecular weight does not increase, the molecular weight distribution becomes wide, and the impact strength may be inferior. Further, if the residence time of the transesterification reaction is excessively long, brittle fracture may easily occur. If the residence time is too short, the target molecular weight may not increase and the impact strength may be inferior.

The by-produced monohydroxy compound is preferably reused as a raw material for carbonic acid diesters and various bisphenol compounds after purification as necessary from the viewpoint of effective utilization of resources.
In particular, in order to obtain a good polycarbonate resin (A) having a high impact strength by suppressing the coloring, thermal deterioration or burn of the polycarbonate resin (A), the maximum temperature of the reactor in all reaction stages is less than 255 ° C. Preferably it is 250 degrees C or less, It is especially preferable that it is 225-245 degreeC. In addition, in order to suppress the lowering of the polymerization rate in the latter half of the polymerization reaction and to minimize the thermal deterioration of the polycarbonate resin (A) due to the thermal history, a horizontal reaction excellent in plug flow property and interface renewability at the final stage of the reaction. It is preferable to use a vessel.

  In addition, in order to obtain a polycarbonate resin (A) having a high impact strength and obtaining a polycarbonate resin (A) having a high molecular weight, the polymerization temperature may be increased as much as possible to increase the polymerization time. Foreign matter and burns in the resin (A) are generated and tend to be brittlely broken. Therefore, in order to satisfy both the high impact strength and the difficulty of brittle fracture, the polymerization temperature is kept low, the use of a highly active catalyst for shortening the polymerization time, and the appropriate reaction system pressure setting. Etc. are preferably adjusted. Furthermore, it is preferable to remove foreign matters or burns generated in the reaction system by a filter or the like in the middle of the reaction or at the final stage of the reaction in order to prevent brittle fracture.

In addition, when manufacturing polycarbonate resin (A) using substituted diphenyl carbonates, such as diphenyl carbonate and ditolyl carbonate, as carbonic acid diester represented by said Formula (6), phenol and substituted phenol are by-produced and polycarbonate. Residue in the resin (A) is unavoidable, but phenol and substituted phenol also have an aromatic ring, which absorbs ultraviolet rays and may cause deterioration of light resistance. It may be a cause. The polycarbonate resin (A) contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of 1000 ppm by weight or more after a normal batch reaction, but from the viewpoint of light resistance and odor reduction. The content of the aromatic monohydroxy compound in the polycarbonate resin (A) is preferably 700 ppm by weight or less, more preferably 500 ppm by weight, using a horizontal reactor excellent in devolatilization performance or an extruder with a vacuum vent. In the following, it is particularly preferable that the content be 300 ppm by weight or less. However, it is difficult to remove the aromatic monohydroxy compound completely industrially, and the lower limit of the content of the aromatic monohydroxy compound in the polycarbonate resin (A) is usually 1 ppm by weight. In addition, these aromatic monohydroxy compounds may naturally have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.

  In addition, Group 1 metals, especially lithium, sodium, potassium, cesium, especially sodium, potassium, cesium, may be mixed not only from the catalyst used but also from raw materials and reactors. Since it may adversely affect the hue if contained in a large amount in (A), the total content of these compounds in the polycarbonate resin (A) of the present invention is preferably as small as possible, and the polycarbonate resin (A) The amount of the metal is usually 1 ppm by weight or less, preferably 0.8 ppm by weight or less, more preferably 0.7 ppm by weight or less.

The amount of metal in the polycarbonate resin (A) can be measured by various conventionally known methods. After recovering the metal in the polycarbonate resin (A) by a method such as wet ashing, atomic emission, It can be measured by using a method such as absorption, Inductively Coupled Plasma (ICP).
The polycarbonate resin (A) of the present invention is usually cooled and solidified after melt polymerization as described above, and pelletized with a rotary cutter or the like.

  The method of pelletization is not limited. For example, the polycarbonate resin (A) is extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand, and pelletized, and melted from the final polymerization reactor. The resin is supplied to a single-screw or twin-screw extruder in a state, melt-extruded, and then cooled and solidified to be pelletized, or extracted from the final polymerization reactor in a molten state, and cooled and solidified in the form of a strand once. Examples of the method include a method of supplying the resin again to the single-screw or twin-screw extruder after being pelletized, melt-extruding, and then cooling and solidifying to pelletize.

At that time, in the extruder, the residual monomer under reduced pressure devolatilization, and generally known heat stabilizers, neutralizers, UV absorbers, mold release agents, colorants, antistatic agents, lubricants, lubricants, A plasticizer, a compatibilizer, a flame retardant, etc. can be added and kneaded.
The melt kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the polycarbonate resin (A), but is usually 150 to 300 ° C, preferably 200 to 270 ° C, and more preferably 230 to 260 ° C. When the melt kneading temperature is lower than 150 ° C., the melt viscosity of the polycarbonate resin (A) is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 300 ° C., the thermal degradation of the polycarbonate becomes severe, which causes a decrease in mechanical strength due to a decrease in molecular weight, coloring, generation of gas, generation of foreign matters, and further generation of burns. It is preferable to install a filter for removing the foreign matters and burns in the extruder or at the outlet of the extruder.

The size of the filter for removing foreign matter (aperture) is usually 400 μm or less, preferably 200 μm or less, particularly preferably 100 μm or less, with the goal of filtering accuracy of removing 99% or more of foreign matter. If the opening of the filter is excessively large, leakage may occur in the removal of foreign matters and burns, and when the polycarbonate resin (A) is molded, brittle fracture may occur. Moreover, the opening of the said filter can be adjusted according to the use of the thermoplastic resin composition of this invention. For example, when applied to film applications, the aperture of the filter is preferably 40 μm or less and more preferably 10 μm or less because of the requirement to eliminate defects.

Further, a plurality of the filters may be used in series, or a filtration device in which a plurality of leaf disk polymer filters are stacked may be used.
Moreover, when cooling and pelletizing the melt-extruded polycarbonate resin (A), it is preferable to use cooling methods, such as air cooling and water cooling. The air to be used for air cooling should be air from which foreign substances in the air have been removed in advance using a HEPA filter (a filter specified in JIS Z8112), etc., to prevent the reattachment of foreign substances in the air. desirable. More preferably, it is preferably carried out in a clean room having a higher degree of cleanliness than class 7, as defined in JIS B 9920 (2002), and more preferably higher than class 6. 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 foreign matter in water has been removed with a filter. There are various openings of the filter to be used, but a filter of 10 to 0.45 μm is preferable.

When the polycarbonate resin (A) of the present invention is produced by a melt polymerization method, one or more of a phosphoric acid compound and a phosphorous acid compound can be added during polymerization for the purpose of preventing coloring.
As the phosphoric acid compound, one or more of trialkyl phosphates such as trimethyl phosphate and triethyl phosphate are preferably used. These are preferably added in an amount of 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less, based on the total hydroxy compounds subjected to the reaction. preferable. When the addition amount of the phosphorus compound is less than the lower limit, the effect of preventing coloring is small, and when the addition amount is more than the upper limit, the transparency is lowered, or conversely, the coloring is promoted or the heat resistance is lowered.

  Moreover, as a phosphorous acid compound, the heat stabilizer shown below can be selected arbitrarily and used. In particular, trimethyl phosphite, triethyl phosphite, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) One or more of pentaerythritol diphosphites can be suitably used. These phosphorous acid compounds are preferably added in an amount of 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol%, based on the total hydroxy compounds subjected to the reaction. It is preferable to add below. If the addition amount of the phosphorous acid compound is less than the lower limit, the effect of preventing coloring is small, and if it is more than the upper limit, the transparency may be reduced, or conversely, the coloring may be promoted or the heat resistance may be reduced. Sometimes.

  The phosphoric acid compound and the phosphorous acid compound can be added in combination, but the addition amount in that case is the total amount of the phosphoric acid compound and the phosphorous acid compound, with respect to all the hydroxy compounds subjected to the reaction, The content is preferably 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less. If this addition amount is less than the lower limit, the effect of preventing coloring is small, and if it is more than the upper limit, it may cause a decrease in transparency, or conversely promote coloring or reduce heat resistance. .

In addition, the polycarbonate resin (A) produced in this manner may be blended with one or more thermal stabilizers in order to prevent a decrease in molecular weight and a deterioration in hue at the time of molding or the like. .
Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, 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-butylenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, Trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), dimethylbenzenephosphonate, Examples include diethyl benzenephosphonate and dipropyl benzenephosphonate. Among them, trisnonylphenyl phosphite, trimethyl phosphate, 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 and dimethyl benzenephosphonate are preferably used.

  Such a heat stabilizer can be further added in addition to the addition amount added at the time of melt polymerization. That is, after blending an appropriate amount of a phosphorous acid compound or phosphoric acid compound to obtain a polycarbonate resin (A), and further blending a phosphorous acid compound by the blending method described later, the transparency during polymerization is improved. More heat stabilizers can be blended while avoiding reduction, coloring, and heat resistance reduction, and hue deterioration can be prevented.

  The content of these heat stabilizers is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, with respect to 100 parts by weight of the polycarbonate resin (A), and 0.001 to 0. More preferred is 2 parts by weight.

<Physical properties of polycarbonate resin (A)>
The preferred physical properties of the polycarbonate resin (A) of the present invention are shown below.

(Glass-transition temperature)
The polycarbonate resin (A) of the present invention has a glass transition temperature (Tg) of less than 145 ° C. When the glass transition temperature of the polycarbonate resin (A) is too high beyond this range, the polycarbonate resin (A) is likely to be colored, and it may be difficult to improve the impact strength. In this case, it is necessary to set the mold temperature high when transferring the shape of the mold surface to the molded product during molding. For this reason, the temperature controller that can be selected may be limited, or the transferability of the mold surface may be deteriorated.

The glass transition temperature of the polycarbonate resin (A) of the present invention is more preferably less than 140 ° C, and still more preferably less than 135 ° C.
The glass transition temperature of the polycarbonate resin (A) of the present invention is usually 90 ° C. or higher, preferably 95 ° C. or higher.
As a method of setting the glass transition temperature of the polycarbonate resin (A) of the present invention to less than 145 ° C., the proportion of the structural unit (1) in the polycarbonate resin (A) is reduced or used for the production of the polycarbonate resin (A). Examples of the dihydroxy compound include a method of selecting an alicyclic dihydroxy compound having low heat resistance or reducing the proportion of structural units derived from an aromatic dihydroxy compound such as a bisphenol compound in the polycarbonate resin (A). It is done.
In addition, the glass transition temperature (Tg) of the polycarbonate resin (A) of the present invention is measured using a differential scanning calorimeter (DSC 6220 manufactured by SII Nano Technology) in accordance with JIS K7121 (1987). It is.

(Reduced viscosity)
The degree of polymerization of the polycarbonate resin (A) of the present invention is such that a mixed solvent of phenol and 1,1,2,2-tetrachloroethane in a weight ratio of 1: 1 is used as a solvent, and the concentration of the polycarbonate resin (A) is 1.00 g / The reduced viscosity measured precisely at dl and measured at a temperature of 30.0 ° C. ± 0.1 ° C. (hereinafter sometimes simply referred to as “reduced viscosity”) is preferably 0.40 dl / g or more, more preferably Is 0.42 dl / g or more, particularly preferably 0.45 dl / g or more, but depending on the use of the polycarbonate resin composition of the present invention, it is 0.60 dl / g or more, more preferably 0.85 dl / g or more. May be preferably used. The reduced viscosity of the polycarbonate resin (A) of the present invention is preferably 2.0 dl / g or less, more preferably 1.7 dl / g or less, and particularly preferably 1.4 dl / g or less. If the reduced viscosity of the polycarbonate resin (A) is excessively low, the mechanical strength may be weakened. If the reduced viscosity of the polycarbonate resin (A) is excessively high, the fluidity at the time of molding is lowered, and the cycle characteristics. , The distortion of the molded product becomes large and tends to be deformed by heat.

(B) Ultraviolet absorber The ultraviolet absorber is not particularly limited as long as it is a compound having ultraviolet absorbing ability. In the present embodiment, examples of the compound having ultraviolet absorbing ability include organic compounds and inorganic compounds. Of these, organic compounds are preferred because they are easy to ensure affinity with the polycarbonate resin and are easily dispersed uniformly.
The molecular weight of the organic compound having ultraviolet absorbing ability is not particularly limited, but is usually 200 or more, preferably 250 or more. Also. Usually, it is 600 or less, preferably 450 or less, more preferably 400 or less. When the molecular weight is equal to or more than the lower limit value, it is possible to suppress a decrease in UV resistance after long-term use. Moreover, the transparency fall of the resin composition by long-term use can be suppressed because molecular weight is below the said upper limit.
Preferred ultraviolet absorbers include benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, salicylic acid phenyl ester compounds, cyanoacrylate compounds, malonic acid ester compounds, oxalic acid anilide compounds, and the like. . Of these, benzotriazole compounds, hydroxybenzophenone compounds, and malonic ester compounds are preferably used. These may be used alone or in combination of two or more.

  More specific examples of the benzotriazole compounds include 2- (2′-hydroxy-3′-methyl-5′-hexylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl- 5'-hexylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-t -Octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-dodecylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-t-dodecylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, methyl-3- (3- (2H-benzotriazol-2-yl ) -5-t-butyl-4-hydroxyphenyl) propionate and the like.

  Examples of the hydroxybenzophenone compounds include 2,2'-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone and the like.

  Examples of the malonic ester compounds include 2- (1-arylalkylidene) malonic esters, tetraethyl-2,2 '-(1,4-phenylene-dimethylidene) -bismalonate, and the like.

  Examples of the triazine compound include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3. 5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -s-triazine, 2- (4,6-diphenyl-1,3, 5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (manufactured by Ciba Geigy, Tinuvin 1577FF) and the like.

Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenyl acrylate, 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like.
Examples of the oxalic acid anilide compound include 2-ethyl-2′-ethoxy-oxalanilide (manufactured by Clariant Japan, Sanduvor VSU).

  The content of the ultraviolet absorber is not particularly limited, but is preferably 0.01 parts by weight or more when the total amount of (A) and (E) below is 100 parts by weight in the polycarbonate resin composition. More preferably, by weight or more, more preferably 0.05 part by weight or more, and most preferably 0.08 part by weight or more. On the other hand, it is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, further preferably 1 part by weight or less, and most preferably 0.5 parts by weight or less. When the content of the ultraviolet absorber is not less than the lower limit, the effect of improving the weather resistance due to the inclusion of the ultraviolet absorber can be further obtained. On the other hand, when the content of the ultraviolet absorber is equal to or less than the upper limit value, it is possible to suppress the appearance failure due to the bleeding out of the ultraviolet absorber.

(C) Light stabilizer The light stabilizer is not particularly limited as long as it is a compound having an ability to prevent oxidative degradation due to light. Examples of the light stabilizer (C) used in the polycarbonate resin composition of the present invention include bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate and bis (1,2,2,6,6). -Pentamethyl-4-piperidyl) [[3,5-bis (1,1, -dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (2,2,6,6-tetramethyl-4- Piperidyl) succinate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-hexanoyloxy-2,2, 6,6-tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidi Bis (2,2,6,6-tetramethyl-4-piperidyl) diphenylmethane-p, p'-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1, 3-disulfonate, bis (2,2,6,6-tetramethyl-4-piperidyl) phenyl phosphite, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) = 1,2,3 Examples thereof include hindered amines such as 4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate. These agents may be used alone or in combination of two or more.

The content of the light stabilizer is not particularly limited, but in the polycarbonate resin composition (A
) And the following (E) in a total of 100 parts by weight, preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight or more, still more preferably 0.05 parts by weight or more, and 0.08 parts by weight. The above is most preferable. On the other hand, it is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, still more preferably 1 part by weight or less, and most preferably 0.5 parts by weight or less.
When the content of the light stabilizer is equal to or higher than the lower limit, the weather resistance of the obtained polycarbonate resin composition is further improved. The effect can be confirmed from the results of a weather resistance test described later. On the other hand, when the content of the light stabilizer is less than or equal to the above upper limit value, it is possible to prevent the occurrence of deposits on the mold during injection molding and to improve the surface appearance of the resulting product.

(D) Antioxidant having a sterically hindered substituent only on one of two carbon atoms adjacent to a carbon atom having a phenolic hydroxyl group The polycarbonate resin composition of the present invention is adjacent to a carbon atom having a phenolic hydroxyl group. An antioxidant having a sterically hindered substituent only on one of the two carbon atoms. Such an antioxidant has a sterically hindered substituent only on one of the two carbon atoms adjacent to the carbon atom having a phenolic hydroxyl group, and thus has excellent radical scavenging properties at room temperature, Good weather resistance. Here, the sterically hindered substituent is not particularly limited, and examples thereof include an isopropyl group, a tert-butyl group, a mesityl group, and an adamantyl group. Among these, from the viewpoint of weather resistance, an isopropyl group, a tert-butyl group, and an adamantyl group are preferable, an isopropyl group and a tert-butyl group are more preferable, and a tert-butyl group is particularly preferable. The antioxidant having a sterically hindered substituent only on one of two carbon atoms adjacent to the carbon atom having a phenolic hydroxyl group may be a compound having a structure represented by the following general formula (7). From the viewpoint of weather resistance, it is preferable. More specifically, for example, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5) -T-butylphenyl) butane, 4,4'-thiobis (6-t-butyl-m-methylphenol), 4,4'-butylidenebis (
6-t-butyl-m-cresol), 2,5-di-t-butylhydroquinone, butylhydroxyanisole and the like. These compounds can be used alone or in combination of two or more.

In the above formula (7), n represents an integer of 1 to 4, and R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent. . Examples of the substituent include allyl group, methallyl group, crotyl group, 1,1-dimethyl-2-propenyl group, 2-methyl-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3- Chain unsaturated hydrocarbon groups such as butenyl group, 2-methyl-3-butenyl group, oleyl group, linole group, linolene group; cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, 4-methylcyclohexyl group , Alicyclic hydrocarbon groups such as 4-tert-butylcyclohexyl group, tricyclodecanyl group, isobornyl group, adamantyl group, dicyclopentanyl group, dicyclopentenyl group; glycidyl group, β-methylglycidyl group, β -Ethyl glycidyl group, 3,4-epoxycyclohexylmethyl group, 2-oxetanemethyl group, 3 -Cyclic ether groups such as methyl-3-oxetanemethyl group, 3-ethyl-3-oxetanemethyl group, tetrahydrofuranyl group, tetrahydrofurfuryl group, tetrahydropyranyl group, dioxazolanyl group, dioxanyl group; phenyl group, methylphenyl group Dimethylphenyl group, trimethylphenyl group, 4-tert-butylphenyl group, methoxyphenyl group, hydroxyphenyl group, benzyl group, diphenylmethyl group, diphenylethyl group, triphenylmethyl group, cinnamyl group, naphthyl group, anthranyl group, etc. An aryl group of methoxy group, ethoxy group, methoxyethoxy group, cyclohexyloxy group, phenoxy group, phenoxyethoxy group, etc .; butylthio group, octylthio group, laurylthio group, stearylthio group, Alkylthio groups such as nylthio group; acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, caproyl group; acetyloxy group, propionyloxy group, butyryloxy group, valeryloxy group, benzoyloxy group, Acyloxy groups such as trioyloxy group, caproyloxy group, (meth) acryloyloxy group; methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, lauryloxycarbonyl group, stearyloxycarbonyl group, phenoxycarbonyl group, Alkoxycarbonyl groups such as benzyloxycarbonyl group; butylthiocarbonyl group, octylthiocarbonyl group, laurylthiocarbonyl group, stearylthiocarbonyl group, Alkylthiocarbonyl groups such as nylthiocarbonyl group and benzylthiocarbonyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; ureido group; amide group; cyano group; hydroxyl group; phosphite group; Examples include ester groups; trimethylsilyl groups, and the like, but the present invention is not limited to such examples.

In the compound having the structure represented by the formula (7), it is preferable that n is an integer of 2 or more. That is, the compound having the structure represented by the above formula (7) is preferably a multimer linked via R ² . Examples of the multimer linked through R ² of the compound having the structure represented by the formula (7) include 4,4 ′, 4 ′-(1-methylpropynyl-3-ylidene) tris (6- tert-butyl-m-cresol) and 6,6′-di-tert-butyl-4,4′-butylidene-m-cresol. By being a multimer linked via R ² of the compound having the structure represented by the above formula (7), the weather resistance effect exhibited by the present invention is more excellent.

The content of the antioxidant having a sterically hindered substituent only on one of the two carbon atoms adjacent to the carbon atom having a phenolic hydroxyl group is not particularly limited. In the polycarbonate resin composition, (A) and When the total amount is 100 parts by weight of the following (E), preferably 0.001 or more, more preferably 0.01 parts by weight or more, particularly preferably 0.02 parts by weight or more, and 0.03 parts by weight or more. Most preferred. On the other hand, it is preferably 5 parts by weight or less, more preferably 4 parts by weight or less, still more preferably 1 part by weight or less, and most preferably 0.5 parts by weight or less.
The weather resistance of the polycarbonate resin composition obtained when the content of the antioxidant having a sterically hindered substituent only on one of two carbon atoms adjacent to the carbon atom having a phenolic hydroxyl group is not less than the lower limit. More improved. The effect can be confirmed from the discoloration during the weather resistance test described later. On the other hand, when the content of the antioxidant having a sterically hindered substituent on only one of the two carbon atoms adjacent to the carbon atom having a phenolic hydroxyl group is not more than the above upper limit value, gold at the time of injection molding Generation | occurrence | production of the deposit | attachment to a type | mold can be prevented and the surface external appearance of the product obtained can be made favorable.

  The polycarbonate resin composition of the present invention may contain (E) and (F) described in detail below in addition to the above (A) to (D).

(E) Elastomer having a core-shell structure “Elastomer having a core-shell structure” is composed of an innermost layer (core layer) and one or more layers (shell layer) covering it, and is copolymerizable with the core layer. A core-shell type graft copolymer obtained by graft copolymerization using a monomer component as a shell layer.

An elastomer having a core / shell structure is usually a core / shell type graft copolymer obtained by graft copolymerization using a polymer component called a rubber component as a core layer and a monomer component copolymerizable therewith as a shell layer. preferable.
The core / shell type graft copolymer may be produced by any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be one-stage graft or multi-stage graft. There may be. However, in the second aspect of the present invention, a commercially available core / shell type elastomer can be used as it is. Examples of commercially available core-shell type elastomers will be listed later.

  The polymer component forming the core layer has a glass transition temperature of usually 0 ° C. or lower, preferably −10 ° C. or lower, more preferably −20 ° C. or lower, and further preferably −30 ° C. or lower. Specific examples of the polymer component forming the core layer include polybutadiene, polyisoprene, polybutyl acrylate, poly (2-ethylhexyl acrylate), polyalkyl acrylates such as butyl acrylate / 2-ethyl hexyl acrylate copolymer, and polyorganosiloxane. Silicone rubber such as rubber, butadiene-acrylic composite, IPN (Interpenetrating Polymer Network) composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene copolymer, ethylene-propylene copolymer and ethylene -Butene copolymer, ethylene-α olefin copolymer such as ethylene-octene copolymer, ethylene-acrylic copolymer, fluoro rubber, etc. That. These may be used alone or in admixture of two or more. Among these, from the viewpoint of mechanical properties and surface appearance, polybutadiene, polyalkyl acrylate, polyorganosiloxane, a composite composed of polyorganosiloxane and polyalkyl acrylate, and a butadiene-styrene copolymer are preferable.

  Specific examples of the monomer component that can be graft-copolymerized with the polymer component of the core layer constituting the shell layer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic compounds. Acid group, epoxy group-containing (meth) acrylic acid ester compound such as glycidyl (meth) acrylate; maleimide compound such as maleimide, N-methylmaleimide, N-phenylmaleimide; α, β such as maleic acid, phthalic acid, itaconic acid -Unsaturated carboxylic acid compounds and their anhydrides (for example, maleic anhydride etc.) etc. are mentioned. These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable. A compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. Of these, methyl (meth) acrylate and ethyl (meth) acrylate, which are relatively easily available, are preferred, and methyl (meth) acrylate is more preferred. Here, “(meth) acryl” is a general term for “acryl” and “methacryl”.

The elastomer having a core-shell structure is, among others, at least one heavy polymer selected from polybutadiene-containing rubber, polybutylacrylate-containing rubber, polyorganosiloxane rubber, and IPN type composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber. A core-shell type graft copolymer comprising a shell layer formed by graft copolymerization of (meth) acrylic acid ester around the coalescence component as a core layer is particularly preferred. In the core-shell type graft copolymer, the core layer preferably contains 40% by weight or more, more preferably 60% by weight or more of the polymer component of the core layer. Moreover, what contains 10 weight% or more of (meth) acrylic acid ester components of a shell layer is preferable.

  Preferred examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone composite) copolymers.

  Examples of such core-shell type graft copolymers include “Paraloid (registered trademark) EXL2602”, “Paraloid (registered trademark) EXL2603”, and “Paraloid (registered trademark)” manufactured by Rohm and Haas Japan. "EXL2655", "Paraloid (registered trademark) EXL2311", "Paraloid (registered trademark) EXL2313", "Paraloid (registered trademark) EXL2315", "Paraloid (registered trademark) KM330", "Paraloid (registered trademark) KM336P", "Paraloid" (Registered Trademark) KCZ201 "," Metablene (Registered Trademark) C-223A "," Metablene (Registered Trademark) E-901 "," Metablene (Registered Trademark) S-2001 "," Metablene (Registered Trademark) "manufactured by Mitsubishi Rayon Co., Ltd. ) W-450A "" Metabrene (registered trademark) S "K-200", "Kaneace (registered trademark) M-511", "Kaneace (registered trademark) M-600", "Kaneace (registered trademark) M-400", "Kaneace (registered trademark) M-" manufactured by Kaneka Corporation 580 "," Kane Ace (registered trademark) MR-01 ", and the like.

  These impact strength modifiers having a core-shell structure such as a core-shell type graft copolymer may be used alone or in combination of two or more.

  The content of the elastomer having a core / shell structure in the resin composition of the present invention is not particularly limited, but in the polycarbonate resin composition, a total of 100 parts by weight of the above component (A) and the following component (E): (E) The content of the elastomer having a core / shell structure is preferably 0.1 to 50 parts by weight, more preferably 0.5 parts by weight or more, and 1 part by weight or more. More preferably, it is more preferably 5 parts by weight or more. On the other hand, it is more preferably 40 parts by weight or less, still more preferably 30 parts by weight or less, and most preferably 25 parts by weight or less. When the blending amount of the elastomer having a core / shell structure is equal to or more than the lower limit value, an effect of improving surface impact resistance and impact resistance is exhibited. On the other hand, when the blending amount of the elastomer having a core / shell structure is equal to or less than the upper limit value, it is possible to suppress the appearance defect and the heat resistance deterioration of the obtained molded product.

(F) Phosphite type antioxidants As phosphite type antioxidants, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite Phyto, 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, trimethyl phosphate, 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 can be used alone or in combination of two or more.

Here, the content of the phosphite antioxidant is not particularly limited, but is preferably 0.01 parts by weight or more when the total of (A) and (E) below is 100 parts by weight in the polycarbonate resin composition. 0.02 parts by weight or more is more preferable, 0.05 parts by weight or more is more preferable, and 0.08 parts by weight or more is most preferable. On the other hand, it is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, still more preferably 1 part by weight or less, and most preferably 0.5 parts by weight or less.
When the content of the phosphite antioxidant is equal to or more than the lower limit, a sufficient coloring suppression effect at the time of molding can be obtained. In addition, when the content of the phosphite antioxidant is less than or equal to the above upper limit, generation of deposits on the mold during injection molding and generation of deposits on the roll when forming a film by extrusion molding Can be prevented, and the surface appearance of the product can be improved.

(Other additives)
The polycarbonate resin composition of the present invention is not limited to the above-mentioned additives, and various known additives such as a mold release agent, a flame retardant, a flame retardant aid, and a hydrolysis inhibitor, as long as the object of the present invention is not impaired. It may be a resin composition containing an agent, an antistatic agent, a foaming agent, a dye and pigment, and the like.

(Inorganic filler)
The polycarbonate resin composition of the present invention may contain an inorganic filler. The compounding amount of the inorganic filler is usually 1 to 100 parts by weight, preferably 3 to 50 parts by weight, based on 100 parts by weight of the polycarbonate resin. When the blending amount of the inorganic filler is excessively small, the reinforcing effect is small, and when it is excessively large, the appearance tends to deteriorate.

  Examples of the inorganic filler include glass fiber, glass milled fiber, glass flake, glass bead, carbon fiber, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whisker, barium sulfate, talc, mica, and wallast. Calcium silicate such as knight; carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, potassium titanate fiber, whisker, etc. It is done. Among these, glass fiber filler, glass powder filler, glass flake filler; carbon fiber filler, carbon powder filler, carbon flake filler; various whiskers, mica Talc is preferred. More preferably, glass fiber, glass flake, glass milled fiber, carbon fiber, wollastonite, mica and talc are mentioned.

(Coloring agent)
The resin composition used in the present invention may contain a colorant. Examples of the colorant include organic dyes such as inorganic pigments, organic pigments, and organic dyes.
Inorganic pigments include barium yellow (CI pigment Yellow 31), yellow lead (CI pigment Yellow 34), zinc yellow (CI pigment Yellow 36), and nickel titanium yellow (CI pigment Yellow 36). 53), chromate such as chromium titanium yellow (CI Pigment Brown 24); ferrocyanide such as bitumen (CI pigment Blue 27); cadmium yellow (CI pigment Yellow 42), cadmium Sulfides such as red (C.I. pigment Red 108); iron black (C.I. pigment Black 11), Bengala (C.I. pigment Red 101), titanium dioxide (C.I. pigment White 6), etc. Acid Silicates such as ultramarine (CI pigment blue 29); or carbon blacks such as channel black, roller black, disc, gas furnace black, oil furnace black, thermal black, and acetylene black (CI pigment) Black 7).

  Examples of organic dyes such as organic pigments and organic dyes include C.I. I. pigmentBlack 1 (condensed aniline type), C.I. I. pigment Yellow 12 (monoazo type), C.I. I. pigment Yellow 23, C.I. I. solvent Green3, C.I. I. Solvent Yellow163, C.I. I. SolventRed111, C.I. I. SolventRed146, C.I. I. DisperseRed 22, C.I. I. SolventViolet 31, C.I. I. SolventViolet 13, C.I. I. SolventBlue 35, C.I. I. SolventBlue 36, C.I. I. SolventBlue 97, C.I. I. Solvent Blue 87 (anthraquinone), C.I. I. pigment Yellow 109 (isoindolinone series), C.I. I. pigment Yellow 138, C.I. I. Solvent Yellow 114, C.I. I. Solvent Yellow 33 (quinophthalone series), C.I. I. pigment Orange 5, C.I. I. Solvent Yellow 14 (monoazo type), C.I. I. Vat Orange 3, C.I. I. Solvent Red179, C.I. I. Solvent Orange 60, C.I. I. SolventRed135, C.I. I. SolventRed179 (perinone series), C.I. I. pigment Red 1, C.I. I. PigmentRed 170, C.I. I. Solvent Yellow 16, (monoazo), C.I. I. pigment Red 37 (pyrazolone azo type), C.I. I. pigment Red 87, C.I. I. Solvent Red 41 (thioindigo type), C.I. I. pigment Red 224, C.I. I. SolventGreen 5 (perylene type), C.I. I. pigment Violet 19 (quinacridone series), C.I. I. pigment Violet 3, C.I. I. Solvent Yellow 93 (azomethine series), C.I. I. pigment Violet 37 (dioxazine type), C.I. I. pigment blue 15 (phthalocyanine series), C.I. I. pigment green 1 (azomethine series), C.I. I. Solvent Yellow 104 (isoquinoline) C.I. I. Solvent Orange 63 (thioxanthene) C.I. I. SolventRed 149, C.I. I. Solvent Red 52 (naphthoquinoline type) and the like.

These colorants may be used alone or in combination of two or more.
The lower limit of the content of the colorant is not particularly limited, but is preferably at least 0.00001 parts by weight when the total of (A) and (E) below is 100 parts by weight in the polycarbonate resin composition. , Preferably it is 0.0001 weight part or more, More preferably, it is 0.0005 weight part or more. When the content of the colorant is equal to or more than the lower limit, it is possible to give a deep and clear color to the molded product of the resin composition to be obtained. On the other hand, the upper limit of the content of the colorant is not particularly limited, but in the polycarbonate resin composition, when the total of (A) and (E) below is 100 parts by weight, preferably 3 parts by weight or less. More preferably, it is 2 parts by weight or less. When the content of the colorant is not more than the above upper limit, the surface roughness of the molded product of the resin composition obtained can be reduced, and the molded product can be given a color with depth and clarity.

<Mixing method>
Examples of the method of blending the above-mentioned various additives into the thermoplastic resin composition of the present invention include mixing with a tumbler, V-type blender, super mixer, nauter mixer, Banbury mixer, kneading roll, extruder, etc. -There is a kneading method, or a solution blending method in which it is mixed in a common good solvent such as methylene chloride. However, this is not particularly limited, and any commonly used blending method may be used. Any method may be used.
Various additives are added to the thermoplastic resin composition of the present invention thus obtained, and the pellets are directly or once formed into a pellet by a melt extruder, and then an extrusion molding method, an injection molding method, a compression molding method, etc. Can be formed into a desired shape by a generally known forming method.

<Production method of polycarbonate resin composition>
In the embodiment of the present invention, sterically hindered substitution is carried out only on one of two carbon atoms adjacent to a carbon atom having a UV-absorbing agent, a light stabilizer, and a phenolic hydroxyl group, which can be blended in the polycarbonate resin composition. The mixing timing and mixing method of the antioxidant having a group are not particularly limited. As the mixing time, for example, when a polycarbonate resin is produced by the transesterification method, it may be mixed during the polymerization reaction or may be mixed at the end of the polymerization reaction. Regardless of the polymerization method, mixing may be performed using a kneading extruder or the like when the polycarbonate resin is melted, such as during the kneading of the polycarbonate resin and another compounding agent. Furthermore, a mixture in which a solid state polycarbonate resin such as pellets or powder and a compounding agent are mixed may be further heated and mixed.

The polycarbonate resin composition of the present invention is produced by mixing the above-mentioned blending components simultaneously or in any order with a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading roll, extruder or the like. Can do.
As a mixing method, the above-mentioned compounding components may be directly mixed or kneaded with a polycarbonate resin, or a high-concentration master batch prepared using a small amount of polycarbonate resin or other resin and the above-mentioned compounding components in advance is prepared. And the said masterbatch can also be mixed with the polycarbonate resin which concerns on this invention.

[Reason why the present invention is effective]
The reason why the present invention is effective is not yet clear, but is presumed as follows. In other words, when the polycarbonate resin (A) is colored due to heat deterioration during molding or aging deterioration due to the natural environment during use, deterioration due to ultraviolet rays proceeds. On the other hand, when an ultraviolet absorber is blended with the polycarbonate resin (A), the ultraviolet absorption of the polycarbonate resin (A) can be suppressed. However, the ultraviolet absorber excited by light reacts with oxygen molecules to generate active radicals, resulting in deterioration of the resin. Therefore, in addition to the ultraviolet absorber, an oxidation degradation inhibiting mechanism capable of capturing and deactivating active radicals generated by blending a hindered phenol antioxidant or a hindered amine light stabilizer (HALS). It has been known. On the other hand, in the present invention, by using an ultraviolet absorber, an antioxidant having a sterically hindered substituent only on one of two carbon atoms adjacent to a carbon atom having a phenolic hydroxyl group, HALS, An active radical generated from an ultraviolet absorber is firstly converted into an antioxidant having a sterically hindered substituent only on one of two carbon atoms adjacent to the carbon atom having a phenolic hydroxyl group, which has a small steric hindrance and excellent radical scavenging ability. "Agent" captures, then deactivates the active radical in HALS by radical exchange reaction with HALS, and regenerates by radical exchange only on one of the two carbon atoms adjacent to the carbon atom having a phenolic hydroxyl group Oxidation by combining conventional UV absorbers and antioxidants by capturing active radicals of `` antioxidants with sterically hindered substituents '' Can very efficiently deactivate active radical than suppression mechanism, is inferred that show excellent weather resistance as a result. Moreover, since the hydrolysis of the polycarbonate resin by HALS can be suppressed, the polycarbonate resin is not deteriorated. Further, since the polycarbonate resin composition of the present invention has good weather resistance and hardly deteriorates in appearance, when the elastomer having a core / shell structure is blended, the deterioration of the elastomer due to the natural environment is also suppressed. And should be able to maintain excellent impact resistance.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.
In the following, the physical properties and characteristics of polycarbonate resin compositions and molded articles were evaluated by the following methods.

[Test specimen preparation method and various evaluations]
(1) Preparation method of test piece The pellet of polycarbonate resin composition was dried at 90-100 degreeC for 10 hours in nitrogen atmosphere. Next, the pellets of the dried polycarbonate resin composition were supplied to an injection molding machine (J75EII type manufactured by Nippon Steel Works), and injection molded pieces (width 60 mm × length) under conditions of a resin temperature of 240 ° C. and a molding cycle of 40 seconds. 60 mm × thickness 2 mm) and an ISO test piece for evaluating mechanical properties.
(2) Jetness (L ^* )
In accordance with JIS Z8722, a spectral color difference meter (CM-5 manufactured by Konica Minolta) was used, and the color value L ^* was measured by D65 light source reflection method SCE (regular reflection removal).
A smaller L ^* value indicates better jetness. In this example, an L ^* value of 1.0 or less was defined as “◯”.

(3) Weather resistance (ΔE ^* )
The weather resistance was judged based on the results of color difference (ΔE ^* ) and gloss retention evaluated by the weather resistance test described in detail below.
[Weather resistance test]
In accordance with JIS B7753, the weather resistance test was performed by using a sunshine weather meter S60 manufactured by Suga Test Instruments Co., Ltd. with a sunshine carbon arc (4 pairs of ultra long life carbon) light source set to a discharge voltage of 50 V and a discharge current of 60 A. And a square surface of a flat plate (width 60 mm × length 60 mm × thickness 2 mm) of the injection-molded piece obtained by the above method under the conditions of black panel temperature 63 ° C. and relative humidity 50% by surface spray (rainfall) Irradiation treatment was performed for 1000 hours. The surface spray (rainfall) time was 12 minutes / 1 hour, and the A type glass filter was used.

[Color difference (ΔE ^* )]
The color difference (ΔE ^* ) was calculated as follows based on the above test results.
The injection molded pieces before and after the test are based on JIS Z8722, using a spectral color difference meter (CM-5 manufactured by Konica Minolta Co.), and color values L ^* , a ^* , b by D65 light source reflection method SCE (regular reflection removal). ^{* Was} measured, and ΔE * was determined from the following formula, with L ₀ ^* , a ₀ ^* , b ₀ ^* as the value before the test, and L ^* , a ^* , b ^{* as} the value after the test.
ΔL ^* = L ^* −L ₀ ^*
Δa ^* = a ^* −a ₀ ^*
Δb ^* = b ^* −b ₀ ^*
ΔE ^* = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2
The smaller the ΔE ^* value, the smaller the color difference before and after the weather resistance test, indicating excellent weather resistance without color differences due to natural environments such as sunlight, rain and snow, and humidity. In this example, the pass / fail was determined as follows.
ΔE ^* value of 1.0 or less: judged to be excellent in weather resistance, “◯”
ΔE ^* value of 0.5 or less: judged to be particularly excellent in weather resistance, and “◎”
ΔE ^* value exceeding 1.0: Judged that the weather resistance is not excellent, and “×”

[Gloss retention]
Using an injection-molded piece, the gloss value (Gs60 °) was measured with a spectrophotometer VC-2000 manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS Z8741, and the glossiness before and after the weather resistance test of (3) above. The gloss retention was calculated from the value according to the following formula.
Gloss retention (%) = {(Glossiness value after weather resistance test) / (Glossiness value before weather resistance test)} × 100
The higher the gloss retention value, the smaller the change in the gloss value before and after the weather resistance test, and the better the weather resistance without the gloss change of the surface appearance caused by the natural environment such as sunlight, rain and snow, and humidity. Indicates that In the present embodiment, the pass / fail was determined as follows.
Gloss retention rate of 90% or more: Judged as having excellent weather resistance, “◯”
Gloss retention rate of 98% or more: Judged to be particularly excellent in weather resistance, “◎”
Gloss retention less than 90%: Judged as not having excellent weather resistance, “×”

[Evaluation of weather resistance (color tone and gloss)]
Based on the results of the above color difference change (ΔE ^* ) and gloss retention, the evaluation was as follows.
When both color difference change (ΔE ^* ) and gloss retention were “◎”: Judged to be extremely excellent in weather resistance.
One of the color difference change (ΔE ^* ) and the gloss retention was “◎” and the other was “◯”: It was judged that the weather resistance was particularly excellent.
When both the color difference change (ΔE ^* ) and the gloss retention were “◯”: Judged as having excellent weather resistance.
Any of the color difference change (ΔE ^* ) and the gloss retention was “x”: It was judged that the weather resistance was poor.

(4) Appearance (3) The appearance of the injection-molded piece after the weather resistance (ΔE ^* ) test was visually confirmed, and “○” indicates that there is no crack on the surface of the injection-molded piece; Was marked “x”. It has been confirmed that the injection-molded piece used before the test has no cracks.

(5) Overall evaluation As a result of the above test, the overall evaluation was as follows. In addition, even if it satisfies the following acceptance criteria, the larger the number of ◎, the better.
Pass: Only ○ or ◎ Fail: There is ×

The abbreviations of the compounds used in the description of the following examples are as follows.
((A) Polycarbonate resin)
A-1: Isosorbide / 1,4-cyclohexanedimethanol = 70/30 mol% copolymer polycarbonate (manufactured by Mitsubishi Chemical Corporation: Durabio D7340R)
A-2: Isosorbide / 1,4-cyclohexanedimethanol = 50/50 mol% copolymer polycarbonate (manufactured by Mitsubishi Chemical Corporation: Durabio D5360R)
A-3: Bisphenol A type polycarbonate resin (Iupilon S3000R manufactured by Mitsubishi Engineering Plastics)

((B) UV absorber)
B-1: Benzotriazole-based ADEKA ADK STAB LA-29
B-2: Benzophenone Adeka Stab LA-31 manufactured by ADEKA
B-3: Triazine-based ADEKA ADK STAB LA-46

((C) Light stabilizer)
C-1: Hindered amine type ADEKA, ADK STAB LA-77G
C-2: Hindered amine system ADEKA company ADEKA STAB LA-57

((D) an antioxidant having a sterically hindered substituent only on one of the two carbon atoms adjacent to the carbon atom having a phenolic hydroxyl group)
D-1: 4,4 ′, 4 ′-(1-Methylpropynyl-3-ylidene) tris (6-tert-butyl-m-cresol) ADEKA ADK STAB AO-30
D-2: 6,6′-di-tert-butyl-4,4′-butylidene-m-cresol ADEKA ADK STAB AO-40

((E) Phosphite antioxidant)
F-1: ADEKA, ADK STAB PEP-36A
F-2: IRSFAF PEP-Q manufactured by BASF

(Hindered phenolic antioxidants other than (D))
X-1: [3- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionoroxy] -2,2-bis [3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propanyl] propionyloxy] propyl] 3- (3,5-di-tert
-Butyl-4-hydroxyphenyl) propionate manufactured by BASF IRGANOX1010
X-2: 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10 -Tetraoxaspiro [5.5] undecane ADEKA ADEKA STAB AO-80

(Coloring agent)
-Solvent Violet 36 Macrolex Violet 3R manufactured by LANXESS
・ Solvent Red 179 Macrox Red E2G manufactured by LANXESS ・ Solvent Green 3 Oil Green 5602 manufactured by Arimoto Chemical Co., Ltd.
-Solvent Blue 97 Macrolex Blue manufactured by LANXESS
RR

[Example 1]
The polycarbonate resin (A-1), the ultraviolet absorber (B-1), the light stabilizer (B-2), and two adjacent carbon atoms having a phenolic hydroxyl group so as to have the composition shown in Table 1. An antioxidant (D-1) having a sterically hindered substituent is mixed with only one of the carbon atoms, and the outlet is used by using a twin screw extruder (TEX-33) manufactured by Nippon Steel Works having one vent port. The resin was extruded in a strand shape so that the resin temperature became 250 ° C., cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump, and the pressure at the vent port was controlled to be 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table 1.

[Example 2]
A polycarbonate resin composition was obtained in the same manner as in Example 1 except that the formulation was changed as shown in Table 1. Table 1 shows the results obtained by evaluating the obtained polycarbonate resin composition in the same manner as in Example 1.

[Example 3]
A polycarbonate resin composition was obtained in the same manner as in Example 1 except that the formulation was changed as shown in Table 1. Table 1 shows the results obtained by evaluating the obtained polycarbonate resin composition in the same manner as in Example 1.

[Example 4]
A polycarbonate resin composition was obtained in the same manner as in Example 1 except that the formulation was changed as shown in Table 1. Table 1 shows the results obtained by evaluating the obtained polycarbonate resin composition in the same manner as in Example 1.

[Example 5]
A polycarbonate resin composition was obtained in the same manner as in Example 1 except that the formulation was changed as shown in Table 1. Table 1 shows the results obtained by evaluating the obtained polycarbonate resin composition in the same manner as in Example 1.

[Comparative Example 1]
A polycarbonate resin composition was obtained in the same manner as in Example 1 except that the formulation was changed as shown in Table 1. Table 1 shows the results obtained by evaluating the obtained polycarbonate resin composition in the same manner as in Example 1.
[Comparative Example 2]
A polycarbonate resin composition was obtained in the same manner as in Example 1 except that the formulation was changed as shown in Table 1. Table 1 shows the results obtained by evaluating the obtained polycarbonate resin composition in the same manner as in Example 1.

[Comparative Example 3]
An antioxidant (D-1) having a sterically hindered substituent only on one of the two carbon atoms adjacent to the carbon atom having a phenolic hydroxyl group of Example 2 was used as a hindered phenol antioxidant (G-1). The polycarbonate resin composition was obtained in the same manner as in Example 2 except that the above was changed. Table 1 shows the results obtained by evaluating the obtained polycarbonate resin composition in the same manner as in Example 1.
[Comparative Example 4]
An antioxidant (D-1) having a sterically hindered substituent only on one of the two carbon atoms adjacent to the carbon atom having a phenolic hydroxyl group of Example 2 is used as a hindered phenol antioxidant (G-2). The polycarbonate resin composition was obtained in the same manner as in Example 2 except that the above was changed. Table 1 shows the results obtained by evaluating the obtained polycarbonate resin composition in the same manner as in Example 1.

  The polycarbonate resin composition of the present invention has not only excellent transparency but also excellent moldability, weather resistance, hue, heat resistance, moldability, and mechanical strength, such as electrical / electronic parts, automotive parts, etc. Phase difference used in injection molding field, film and sheet field, bottle and container field where heat resistance is required, and lens applications such as camera lens, finder lens, CCD and CMOS lens, liquid crystal and plasma display It is possible to provide materials for a wide range of fields such as a film, a diffusion sheet, a film such as a polarizing film, a sheet, an optical disk, an optical material, an optical component, a dye, a charge transfer agent, and the like.

Claims (12)

(A) a polycarbonate resin containing a structural unit derived from a dihydroxy compound represented by the following general formula (1);
(B) Ultraviolet absorber (C) Light stabilizer (D) Polycarbonate comprising an antioxidant having a sterically hindered substituent only on one of two carbon atoms adjacent to a carbon atom having a phenolic hydroxyl group Resin composition.

The polycarbonate resin composition according to claim 1, wherein (D) is an antioxidant having a structure represented by the following formula (7).

In the above formula (7), n represents an integer of 1 to 4, and R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent. .   The polycarbonate resin composition contains (B) in an amount of 0.01 parts by weight or more and 5 parts by weight or less when the total amount of (A) and (E) below is 100 parts by weight. Polycarbonate resin composition.   The polycarbonate resin composition according to any one of claims 1 to 3, comprising (C) in an amount of 0.01 parts by weight to 5 parts by weight when the total amount of (A) and (E) below is 100 parts by weight. 2. The polycarbonate resin composition according to item 1.   The polycarbonate resin composition contains 0.001 part by weight or more and 5 parts by weight or less of (D) when the total amount of (A) and (E) below is 100 parts by weight. 2. The polycarbonate resin composition according to item 1.   In the polycarbonate resin composition, when the total amount of (A) and (E) below is 100 parts by weight, (E) the content of the elastomer having a core-shell structure is 0.1 to 50 parts by weight. The polycarbonate resin composition according to any one of 1 to 5.   The polycarbonate resin composition contains 0.01 to 5 parts by weight of (F) a phosphite antioxidant when the total amount of (A) and (E) below is 100 parts by weight. 7. The polycarbonate resin composition according to any one of 6.   The polycarbonate resin composition according to claim 6 or 7, wherein the shell layer of the elastomer component (E) having a core-shell structure is made of an alkyl (meth) acrylate.   The polycarbonate resin composition according to claim 1, wherein the light stabilizer (C) has a piperidine structure. The polycarbonate resin composition according to any one of claims 1 to 9, wherein a color value L ^* measured by D65 light source reflection method SCE (regular reflection removal) based on JIS Z8722 is 3 or less.   The molded article containing the polycarbonate resin of any one of Claims 1 thru | or 10.   The molded article according to claim 11, wherein the molded article is a part for automobiles.