JP6907625B2 - Polycarbonate resin composition and molded product - Google Patents

Description

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

Polycarbonate resin generally contains bisphenols as a monomer component, and takes advantage of its advantages such as transparency, heat resistance, and mechanical strength, and makes use of its advantages such as electrical / electronic parts, automobile parts, medical parts, building materials, films, sheets, and bottles. , Optical recording media, lenses, etc. are widely used as so-called engineering plastics.
However, when the conventional polycarbonate resin is used in a place exposed to ultraviolet rays or visible light for a long time, the hue, transparency, and mechanical strength deteriorate, so that the use of the conventional polycarbonate resin is restricted outdoors or in the vicinity of a lighting device. .. Further, when used as various molded products, there is a problem that the mold releasability is poor at the time of melt molding and it is difficult to use it as a transparent material, an optical material or the like.

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

In addition, hindered amine-based light stabilizers are known as light stabilizers, but it has been reported that polycarbonate resins are unstable to basic components such as alkalis even at room temperature, and are also hydrolyzed to hindered amine compounds. (See, for example, Non-Patent Document 2).
Since the bisphenol compound used in the conventional polycarbonate resin has a benzene ring structure, it absorbs a large amount of ultraviolet rays, which causes deterioration of the light resistance of the polycarbonate resin. Therefore, an aliphatic dihydroxy having no benzene ring structure in the molecular skeleton. In principle, it is expected that the light resistance will be improved by using a cyclic dihydroxy compound monomer unit having an ether bond in the molecule, such as a compound, an alicyclic dihydroxy compound, or isosorbide. Among them, polycarbonate resins using isosorbide as a monomer obtained from biomass resources are excellent in heat resistance and mechanical strength, and therefore, 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 the molecule, such as isosorbide, isomannide, and isoitid, which does not have a benzene ring structure in the molecular skeleton, is used as an ultraviolet absorber in a benzotriazole-based or benzophenone. It is known that a system, a cyanoacrylate system is added, or a hindered amine system light stabilizer is contained (for example, Patent Documents 5 and 6).

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

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

However, cyclic dihydroxy compounds having an ether bond in the molecule, such as isosorbide, do not have a phenolic hydroxyl group. The polycarbonate resin obtained by using such a dihydroxy compound having no phenolic hydroxyl group is inferior in thermal stability to the polycarbonate resin obtained by using a dihydroxy compound having a phenolic hydroxyl group such as bisphenol A. Therefore, there is a problem that coloring occurs during polymerization or molding, which is exposed to a high temperature, and as a result, it absorbs ultraviolet rays and visible light and causes deterioration of weather resistance. Above all, when a cyclic dihydroxy compound having an ether bond in the molecule such as isosorbide is used, the initial hue and the deterioration of the hue after the light resistance test, the deterioration of gloss, and the deterioration of the molded appearance are remarkably deteriorated, and a significant improvement is required. rice field.

An object of the present invention is to solve the above-mentioned conventional problems, to have moldability, transparency, hue, heat resistance, thermal stability, and mechanical strength, as well as excellent initial color tone and weather resistance, and light resistance. Polycarbonate resin that has good color tone and gloss even after the test and has a good molded appearance, and can be applied to a wide range of fields such as injection molding fields such as electrical / electronic parts and automobile parts, films, sheet fields, and building material applications. The purpose is to provide a composition and a molded product thereof.

As a result of diligent 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. We 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 also good, and the present invention has been reached.
(A) A polycarbonate resin containing a structural unit derived from a dihydroxy compound represented by the following general formula (1), and
(B) Ultraviolet absorber (C) Light stabilizer (D) Polycarbonate containing an antioxidant having a sterically hindering substituent in only 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 even after a light resistance test. The molded appearance is also good, and the injection molding field such as electrical / electronic parts and automobile parts, the film, sheet field, etc.
Furthermore, it becomes possible to provide a polycarbonate resin composition and a molded product thereof that can be applied to a wide range of fields such as building member applications.

Hereinafter, embodiments of the present invention will be described in detail, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is described below as long as the gist of the present invention is not exceeded. It is not limited to the contents of.
(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), and
(B) Ultraviolet absorber (C) Light stabilizer (D) Polycarbonate containing an antioxidant having a sterically hindering substituent in only 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. The contents of the following (A) to (F) are usually not particularly limited, but in the following description, it is described as "when the total of the following (A) and the following (E) is 100 parts by weight". The preferable content of each component will be described. The following description means that the same content is preferable even when the component (E) is not used.

(A) Polycarbonate Resin In the polycarbonate resin used in the polycarbonate resin composition of the present invention (hereinafter, may be referred to as "polycarbonate resin (A) of the present invention"), structural units derived from a dihydroxy compound are 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, may be referred to as “dihydroxy compound (1)”). The structural unit derived from the dihydroxy compound constituting the polycarbonate resin (A) used in the present invention is the hydroxyl group of the dihydroxy compound minus the hydrogen atom.

Examples of the dihydroxy compound represented by the above formula (1) include isosorbide, isomannide, and isoidet, which are in a stereoisomeric relationship. Among these dihydroxy compounds (1), isosorbide, which is abundant as a resource, is easily available, and is obtained by dehydration condensation of sorbitol produced from various starches, is easily available and produced. Most preferable from the viewpoint of moldability.
One of these dihydroxy compounds (1) may be used alone, or two or more thereof may be used in combination.

The dihydroxy compound (1) having a cyclic ether structure such as isosorbide is easily oxidized by oxygen. Therefore, in order to prevent decomposition by oxygen during storage and handling during manufacturing, it is important to prevent water from being mixed in, to use an oxygen scavenger, and to handle in a nitrogen atmosphere. When isosorbide is oxidized, decomposition products such as formic acid are generated. For example, when a polycarbonate resin (A) is produced using isosorbide containing these decomposition products, the obtained polycarbonate resin (A) is colored. Or, it may cause significant deterioration of physical properties. In addition, it may affect the polymerization reaction and a high molecular weight polymer may not be obtained, which is not preferable.
Therefore, it is preferable to use a stabilizer for the dihydroxy compound (1). As the stabilizer, it is preferable to use a stabilizer such as a reducing agent, an antacid, an antioxidant, an oxygen scavenger, a light stabilizer, a pH stabilizer, a heat stabilizer, and the like, especially under acidic conditions, the dihydroxy compound (1). It is preferable to contain a basic stabilizer because the substance is easily deteriorated. Among these, examples of the reducing agent include sodium borohydride, lithium borohydride and the like, and examples of the antacid include alkalis such as sodium hydroxide. However, such addition of 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), and if it is added excessively, the polymerization reaction cannot be controlled.
Basic stabilizers include hydroxides, carbonates, phosphates, phosphites, and hypophosphates of Group 1 or Group 2 metals in the Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005. Salts, borolates, fatty acid salts, tetramethylammonium hydroxides, tetraethylammonium hydroxides, tetrapropylammonium hydroxides, tetrabutylammonium hydroxides, trimethylethylammonium hydroxides, trimethylbenzylammonium hydroxides, trimethylphenylammonium hydroxides, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, Basic ammonium compounds such as butyltriphenylammonium hydroxide, 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4 Examples thereof include amine compounds such as −methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole and aminoquinolin. Among them, sodium or potassium phosphate and phosphite are preferable, and disodium hydrogen phosphate and disodium hydrogen phosphite are preferable because of their effects and ease of distillation removal described later.

The content of these basic stabilizers in the dihydroxy compound (1) is not particularly limited, but if it is too small, the effect of preventing alteration of the dihydroxy compound (1) may not be obtained, and if it is too large, the dihydroxy compound Since it may cause denaturation of (1), 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), the obtained polycarbonate resin (A) may be colored or the physical properties may be significantly deteriorated depending on the type of the stabilizer. May be done. 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. However, the initial hue is deteriorated, and the weather resistance of the resulting molded product of the polycarbonate resin (A) is deteriorated.
Therefore, before using the dihydroxy compound (1) as a raw material for producing the polycarbonate resin (A), it is preferable to remove the stabilizer such as the basic stabilizer by an ion exchange resin, distillation or the like.
Further, as described above, when the dihydroxy compound (1) containing the oxidation decomposition product of the dihydroxy compound (1) is used as a raw material for producing the polycarbonate resin (A), the obtained polycarbonate resin (A) may be colored. In addition to the possibility of significantly deteriorating the physical properties, it may affect the polymerization reaction and a high molecular weight polymer may not be obtained.

Therefore, it is preferable to carry out distillation purification of the dihydroxy compound (1) in order to obtain the dihydroxy compound (1) containing no oxidative decomposition product and to remove the above-mentioned basic stabilizer. The distillation in this case may be simple distillation or continuous distillation, and is not particularly limited. As the distillation conditions, it is preferable to carry out distillation under reduced pressure in an inert gas atmosphere such as argon or nitrogen, and in order to suppress denaturation due to heat, 250 ° C. or lower, preferably 200 ° C. or lower, particularly 180. It is preferable to carry out under the condition of ° C. or lower.

<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 other than the dihydroxy compound (1) according to, for example, the method for producing 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. It is preferable that it is 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 among them, a structural unit derived from an alicyclic dihydroxy compound. It is preferable to have. When the polycarbonate resin (A) has such a structural unit, it is possible to further impart flexibility to the obtained polycarbonate resin (A), and it is durable when a resin composition containing the polycarbonate resin (A) is molded. Improves sex.

(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, and 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-1,6-hexanediol, 1,10-decanediol, dilinoleyl glycol hydride, diorail hydride Glycol and the like can be mentioned. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1 , 9-Nonandiol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol are preferable.

(Alicyclic dihydroxy compound)
The alicyclic dihydroxy compound is not particularly limited, and examples thereof include a compound having a 5-membered ring structure or a 6-membered ring structure. The 6-membered ring structure may be fixed in a chair or boat shape by covalent bonds. The number of carbon atoms contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, and more preferably 30 or less. If the number of carbon atoms is excessively large, the heat resistance becomes high, but the synthesis tends to be difficult or the purification tends to be difficult. The smaller the number of carbon atoms, the easier it is to purify and obtain it, but if it is too small, the ring structure becomes unstable and synthesis becomes difficult.

Examples of the alicyclic dihydroxy compound 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- Cyclohexanedimethanol such as cyclohexanedimethanol, 2,3-norbornandimethanol, norbornandimethanol such as 2,5-norbornandimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, 1,3- Examples thereof include adamantandiol and 2,2-adamantandiol.
Among the specific examples of the alicyclic dihydroxy compound described above, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 -Cyclohexanedimethanol such as cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, 1,3-adamantandiol, 2,2-adamantandiol, easy to obtain and easy to handle. From this point of view, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, tricyclodecanedimethanol, and pentacyclopentadecanedimethanol are preferable, and among these, 2,2 4,4-Tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, and pentacyclopentadecanedimethanol are particularly preferable, and 2,2,4. Most preferred are 4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanedimethanol, and tricyclodecanedimethanol.
The example compound is an example of an alicyclic dihydroxy compound that can be used in the present invention, and is not limited thereto. These alicyclic dihydroxy compounds may be used alone or in combination of two or more.

(Aromatic dihydroxy compound)
Examples of the aromatic dihydroxy compound include substituted or unsubstituted bisphenol compounds, specifically, 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, and 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 compounds having an aryl group as a substituent on the aromatic ring such as bis (3-phenyl-4-hydroxyphenyl) propane; 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, 1,1-bis (4-hydroxy-3-ethylphenyl) ethane, 1,1-bis (4-hydroxy-) 3-Ethylphenyl) propane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane, 1,1-bis (4-hydroxy-3-ethylphenyl) cyclohexane, 2,2-bis (4-hydroxy) -3-Isopropyl phenyl) 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-dimethyl) Phenyl) 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 the aromatic ring such as phenylethane, 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) A bisphenol compound in which a divalent group linking an aromatic ring such as dibenzylmethane has an aryl group as a substituent; 4,4'-dihydroxydiphenyl ether, 3,3', 5,5'-tetramethyl-4,4' A bisphenol compound in which an aromatic ring such as −dihydroxydiphenylether is linked by an ether bond; aroma such as 4,4′-dihydroxydiphenylsulfone, 3,3′,5,5′-tetramethyl-4,4′-dihydroxydiphenylsulfone. A bisphenol compound in which a group ring is linked by a sulfone bond; an aromatic ring such as 4,4'-dihydroxydiphenylsulfide, 3,3', 5,5'-tetramethyl-4,4'-dihydroxydiphenylsulfide is bonded by a sulfide bond. Examples of the linked bisphenol compound include 6,6'-dihydroxy-3,3,3', 3'-tetramethyl-1,1'-spirobiindane, preferably 2,2-bis (4-hydroxyphenyl). Propane (hereinafter, may be abbreviated as "bisphenol A". ), 6,6'-dihydroxy-3,3,3', 3'-tetramethyl-1,1'-spirobiindane.
As the dihydroxy compound other than the above-mentioned dihydroxy compound (1), one type may be used alone, or two or more types may be mixed and used.
[Mixing of polycarbonate resin]
The above-mentioned polycarbonate resin which is the component A may be only one kind of polycarbonate, or may contain a plurality of polycarbonate copolymers having different copolymerization ratios. That is, as the component A, a polycarbonate resin mixture in which a plurality of polycarbonate copolymers having different copolymerization ratios are melt-mixed can also be used. The resin temperature of the melt extrusion port at the time of this melt mixing is preferably 235 ° C to 245 ° C, more preferably 238 ° C to 242 ° C. Within this range, coloring, thermal deterioration, or discoloration of the polycarbonate resin can be suppressed, and a good polycarbonate resin mixture having higher impact strength can be obtained.

As for the range of each copolymerization ratio of the plurality of polycarbonate copolymers having different copolymerization ratios and the mixing 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 according to the conditions. When only one type of polycarbonate is used as the polycarbonate resin (A) or when a plurality of polycarbonate copolymers are mixed, the preferable range of the copolymerization ratio of the polycarbonate resin mixture obtained after mixing is the same, which will be described below. do. That is, the amount (however, the number of moles) of the structural unit derived from the dihydroxy compound represented by the general formula (1) is larger than the structural unit derived from the total dihydroxy compound contained in the polycarbonate resin (A) of the present invention. , 40 mol% or more is preferable, 45 mol% or more is more preferable, 50 mol% or more is particularly preferable, and 55 mol% or more is most preferable. Further, 90 mol% or less is preferable, 80 mol% or less is more preferable, 75 mol% or less is particularly preferable, and 70 mol% or less is most preferable. 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 is the total in the polycarbonate resin (A). 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. Further, 60 mol% or less is preferable, 55 mol% or less is more preferable, 50 mol% or less is particularly preferable, and 45 mol% or less is most preferable. When the polycarbonate resin (A) has a structure within the above range, impact resistance and heat resistance are good.

In the polycarbonate resin (A) of the present invention, the content of the structural units derived from the above-mentioned aromatic dihydroxy compound is relative to the structural units 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%, more preferably 0 mol% or more and less than 20 mol%, still more preferably 0 mol% or more and less than 10 mol%. Since 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 significantly colored, it is most preferable not to have the structural unit derived from the aromatic dihydroxy compound from the viewpoint of weather resistance.

(Carbonate diester)
The polycarbonate resin of the present invention can be obtained by polycondensing the above-mentioned dihydroxy compound containing the dihydroxy compound of the present invention and a carbonic acid diester as raw materials by a transesterification reaction.
As the carbonic acid diester used, those represented by the following general formula (6) are usually mentioned. One of these carbonic acid diesters may be used alone, or two or more thereof may be mixed and used.

In the above formula (6), A ¹ and A ² are independently substituted or unsubstituted aliphatic groups having 1 to 18 carbon atoms, or substituted or unsubstituted aromatic groups, respectively.
Examples of the carbonic acid diester represented by the above formula (6) include substituted diphenyl carbonates such as diphenyl carbonate and ditril carbonate, dimethyl carbonate, diethyl carbonate and di-t-butyl carbonate, but diphenyl is preferable. It is a carbonate, a substituted diphenyl carbonate, and particularly preferably a diphenyl carbonate. The carbonic acid diester may contain impurities such as chloride ions, and these impurities may inhibit the polymerization reaction or worsen the hue of the obtained polycarbonate resin (A), so that it is necessary. Therefore, it is preferable to use one purified by distillation or the like.

The carbonic acid diester is preferably used in a molar ratio of 0.99 to 1.20, more preferably 0.95 to 1.10, with respect to the total dihydroxy compound used in the melt polymerization. It is even more preferably used in a molar ratio of .96 to 1.10, and particularly preferably in a molar ratio of 0.98 to 1.04.
When this molar ratio is smaller than 0.90, the terminal hydroxyl groups of the produced polycarbonate resin (A) increase, the thermal stability of the polymer deteriorates, and coloring occurs when molding the thermoplastic resin composition. There is a possibility that the speed of the transesterification reaction may be slowed down, or the desired high molecular weight compound may not be obtained.

Further, when this molar ratio is larger than 1.20, the speed of the transesterification reaction decreases under the same conditions, and not only is it difficult to produce the polycarbonate resin (A) having a desired molecular weight, but also the produced polycarbonate resin is produced. The amount of residual carbonic acid diester in (A) increases, and this residual carbonic acid diester may cause an odor during molding or a molded product, which may be unfavorable. As a result, the thermal history during the polymerization reaction is increased. There is a possibility that the hue and weather resistance of the obtained polycarbonate resin (A) may be deteriorated.

Furthermore, when the molar ratio of carbonic acid diester to the total dihydroxy compound increases, the amount of residual carbonic acid diester in the obtained polycarbonate resin (A) increases, and these absorb ultraviolet rays to improve the light resistance of the polycarbonate resin (A). It may be aggravated and is not preferable. The concentration of the carbon dioxide 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, in reality, the polycarbonate resin (A) may contain an unreacted carbonic acid diester, and the lower limit 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 a dihydroxy compound containing the dihydroxy compound (1) with a carbonic acid diester represented by the formula (6) as described above. More specifically, it is obtained by subjecting it to a transesterification reaction to remove by-produced monohydroxy compounds and the like from the system. In this case, melt polymerization is usually carried out by a transesterification reaction in the presence of a transesterification reaction catalyst.

Examples of the transesterification reaction catalyst (hereinafter, sometimes referred to as “catalyst”) that can be used in the production of the polycarbonate resin (A) of the present invention include 1 in the Long Periodic Table (Nomenclature of Organic Chemistry IUPAC Recommendations 2005). Basic compounds such as group or group 2 (hereinafter simply referred to as "group 1" and "group 2") metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds Can be mentioned. Among these, Group 1 metal compounds and / or Group 2 metal compounds are preferably used.

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

Examples of Group 1 metal compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, and the like. Cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium hydride, potassium hydride, lithium hydride, cesium hydride , Sodium phenylated, potassium phenylated, lithium phenylated boron, cesium phenylated, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, disodium hydrogen phosphate, phosphorus 2 lithium hydrogen acid, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, lithium, cesium alcoholate, phenolate, bisphenol Examples thereof include a disodium salt, a 2 potassium salt, a 2 lithium salt and a 2 cesium salt of A, and among them, a cesium compound and a lithium compound are preferable.

Examples of the Group 2 metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, and the like. Examples thereof include strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, etc. Among them, magnesium compounds, calcium compounds and barium compounds are preferable, and magnesium compounds and / Alternatively, a calcium compound is more preferable.

Examples of the basic boron compound include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron and tributylbenzyl. Examples include sodium salts such as boron, tributylphenyl boron, tetraphenyl boron, benzyl triphenyl boron, methyl triphenyl boron, and butyl triphenyl boron, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, and strontium salts. Be done.

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

Examples of amine compounds 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 can be mentioned.

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

In the case of group 1 metal compounds and / or group 2 metal compounds, the amount of the catalyst used is preferably 0.1 to 300 μmol, more preferably 0.1 to 300 μmol, as a metal equivalent amount with respect to 1 mol of the total dihydroxy compound to be subjected to the reaction. It is in the range of 0.1 to 100 μmol, more preferably 0.5 to 50 μmol, and even more preferably 1 to 25 μmol.
Among the above, when a compound containing at least one metal selected from the group consisting of lithium and group 2 metals is used, in particular, at least one metal compound selected from the group consisting of magnesium compound, calcium compound and barium compound 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 the total dihydroxy compound to be 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 required to produce the polycarbonate resin (A) having a desired molecular weight may not be obtained, and sufficient fracture energy may not be obtained. On the other hand, if the amount of the catalyst used is too large, not only the hue of the obtained polycarbonate resin (A) deteriorates, but also by-products are generated to reduce the fluidity and generate more gel, resulting in brittle fracture. May cause difficulty in producing the polycarbonate resin (A) of the target quality.

<Manufacturing method of polycarbonate resin (A)>
The polycarbonate resin (A) of the present invention is obtained by melt-polymerizing a dihydroxy compound containing the dihydroxy compound (1) and a carbonic acid diester by a transesterification reaction, but 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 thereof is usually 250 ° C. or lower, preferably 200 ° C. or lower, and more preferably 150 ° C. or lower. Above all, 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, which often leads to problems such as solidification, and if the mixing temperature is too high, thermal deterioration of the dihydroxy compound may occur, resulting in this. The hue of the polycarbonate resin (A) obtained in the above may deteriorate, which may adversely affect the light resistance.

Further, the operation of mixing the dihydroxy compound and the carbonic acid diester has an oxygen concentration of 10% by volume or less, further 0.0001% by volume to 10% by volume, particularly 0.0001% by volume to 5% by volume, particularly 0.0001 volume. It is preferable to carry out the operation in an atmosphere of% to 1% by volume from the viewpoint of preventing deterioration of the hue of the obtained polycarbonate resin (A).
The polycarbonate resin (A) of the present invention is preferably produced by melt-polymerizing in multiple stages using a plurality of reactors using a catalyst. The reason why melt polymerization is carried out in multiple reactors is that in the initial stage of the melt polymerization reaction, there are many monomers contained in the reaction solution, so it is important to suppress the volatilization of the monomers while maintaining the required polymerization rate. This is because, 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. As described above, in order to set different polymerization reaction conditions, it is preferable to use a plurality of reactors arranged in series from the viewpoint of production efficiency. As described above, the number of the reactors may be at least two or more, but from the viewpoint of production efficiency and the like, the number of the reactors is three or more, preferably three to five, and particularly preferably four.

The form of the reaction may be a batch type, a continuous type, or a combination of a batch type and a continuous type.
Furthermore, it is effective to use a reflux condenser as the polymerization reactor in order to suppress the amount of the monomer distilled, and the effect is particularly large in the reactor at the initial stage of polymerization having a large amount of unreacted monomer components. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected depending on the monomer used, but usually the temperature of the refrigerant introduced into the reflux condenser is 45 to 180 ° C. at the inlet of the reflux condenser. Yes, preferably 80-150 ° C, particularly preferably 100-130 ° C. If the temperature of the refrigerant introduced into the reflux condenser is too high, the amount of reflux decreases and its effect decreases, and if it is too low, the distillation efficiency of the monohydroxy compound that should be distilled off tends to decrease. As the refrigerant, hot water, steam, heat medium oil and the like are used, and steam and heat medium oil are preferable.

In order to maintain the polymerization rate appropriately, suppress the distillation of the monomer, and not impair the hue, thermal stability, light resistance, etc. of the finally obtained polycarbonate resin (A), the above-mentioned catalyst It is important to select the type and quantity of.
In the production of the polycarbonate resin (A) of the present invention, if there are two or more reactors, the temperature and pressure are continuously changed so that a plurality of reaction stages having different conditions are provided in the reactors. You may go, etc.

In the production of the polycarbonate resin (A) of the present invention, the catalyst can be added to the raw material preparation tank and the raw material storage tank, or can be added directly to the reactor, but from the viewpoint of supply stability and control of melt polymerization. From the above, a catalyst supply line is installed in the middle of the raw material line before being supplied to the reactor, and the catalyst supply line is preferably supplied as an aqueous solution.
As the polymerization conditions, it is preferable to obtain a prepolymer at a relatively low temperature and a low vacuum in the initial stage of polymerization, and to increase the molecular weight to a predetermined value at a relatively high temperature and a high vacuum in the latter stage of the 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 obtained polycarbonate resin (A). For example, if either the temperature or the pressure is changed too quickly before the polymerization reaction reaches a predetermined value, unreacted monomers are distilled out, the molar ratio of the dihydroxy compound and the carbonic acid diester is disturbed, and the polymerization rate is lowered. As a result, the object of the present invention may not be achieved because a polymer having a predetermined molecular weight or terminal group cannot be obtained.

If the temperature of the transesterification reaction is too low, it causes a decrease in productivity and an increase in the thermal history of the product, and if it is too high, it not only causes the monomer to volatilize, but also promotes the decomposition and coloring of the polycarbonate resin (A). There is sex.
In the production of the polycarbonate resin (A) of the present invention, the method of transesterifying a dihydroxy compound containing the dihydroxy compound (1) and a carbonic acid diester in the presence of a catalyst is usually carried out in two or more steps. .. Specifically, the transesterification reaction temperature of the first stage (hereinafter, may be referred to as "internal temperature") is preferably 140 ° C. or higher, more preferably 150 ° C. or higher, still more preferably 180 ° C. or higher, still higher. It is preferably 200 ° C. or higher. The transesterification reaction temperature in the first stage is preferably 270 ° C. or lower, more preferably 240 ° C. or lower, still more preferably 230 ° C. or lower, and even more preferably 220 ° C. or lower. The residence time in the first-stage transesterification reaction is usually 0.
The time is 1 to 10 hours, preferably 0.5 to 3 hours, and the transesterification reaction in the first stage is carried out while distilling the generated monohydroxy compound out of the reaction system. From the second stage onward, the transesterification reaction temperature is raised, and the transesterification reaction is usually carried out at a temperature of 210 to 270 ° C., preferably 220 to 250 ° C., while removing the monohydroxy compounds generated at the same time from the reaction system. , Usually 0.1 to 10 hours, preferably 0.5 to 6 hours so that the pressure of the reaction system is finally reduced to 200 Pa or less while gradually lowering the pressure of the reaction system from the pressure of the first stage. Particularly preferably, the polycondensation reaction is carried out for 1 to 3 hours.

If the transesterification reaction temperature is excessively high, the hue of the molded product may deteriorate and brittle fracture may occur easily. If the transesterification reaction temperature is excessively low, the target molecular weight may not increase, the molecular weight distribution may become wide, and the impact strength may be inferior. Further, if the residence time of the transesterification reaction is excessively long, brittle fracture may occur easily. If the residence time is excessively short, the target molecular weight may not increase and the impact strength may be inferior.

From the viewpoint of effective resource utilization, the by-produced monohydroxy compound is preferably purified as necessary and then reused as a raw material for carbonic acid diesters and various bisphenol compounds.
In particular, in order to suppress coloring, thermal deterioration or discoloration of the polycarbonate resin (A) and obtain a good polycarbonate resin (A) having high impact strength, the maximum temperature inside the reactor at all reaction stages is less than 255 ° C. It is preferably 250 ° C. or lower, particularly 225 to 245 ° C. Further, in order to suppress a decrease in 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 having excellent plug flow property and interface renewal property is excellent at the final stage of the reaction. It is preferable to use a vessel.

Further, in order to obtain a polycarbonate resin (A) having a high impact strength and to obtain a polycarbonate resin (A) having a high molecular weight, the polymerization temperature may be raised as much as possible and the polymerization time may be lengthened. In this case, polycarbonate is used. Foreign matter and burns in the resin (A) are generated, and there is a tendency for brittle fracture to occur easily. Therefore, in order to satisfy both the high impact strength and the difficulty of brittle fracture, the polymerization temperature should be kept low, a highly active catalyst should be used to shorten the polymerization time, and the appropriate reaction system pressure should be set. It is preferable to make adjustments such as. Further, it is also preferable to remove foreign substances and burns generated in the reaction system with a filter or the like during the reaction or at the final stage of the reaction in order to prevent brittle fracture.

When the polycarbonate resin (A) is produced by using a substituted diphenyl carbonate such as diphenyl carbonate or ditril carbonate as the carbonic acid diester represented by the formula (6), phenol and the substituted phenol are by-produced and the polycarbonate is polycarbonate. Although it is unavoidable that it remains in the resin (A), phenol and substituted phenol also have an aromatic ring, so they absorb ultraviolet rays and may cause deterioration of light resistance, as well as odor during molding. It may be the cause. The polycarbonate resin (A) contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of 1000 wtppm or more after a normal batch reaction, but from the viewpoint of light resistance and odor reduction, it is contained. Using a horizontal reactor or an extruder with a vacuum vent having excellent volatilization performance, the content of the aromatic monohydroxy compound in the polycarbonate resin (A) is preferably 700% by weight or less, more preferably 500% by weight ppm. Hereinafter, it is particularly preferable that the weight is 300 ppm by weight or less. However, it is difficult to completely remove the aromatic monohydroxy compound industrially, and the lower limit of the content of the aromatic monohydroxy compound in the polycarbonate resin (A) is usually 1 wt ppm. Of course, these aromatic monohydroxy compounds may have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.

Group 1 metals, especially lithium, sodium, potassium and cesium, especially sodium, potassium and cesium, may be mixed not only from the catalyst used but also from the raw materials and reaction equipment, but these metals are polycarbonate resins. If it is contained in a large amount in (A), it may adversely affect the hue. Therefore, the total content of these compounds in the potassium resin (A) of the present invention is preferably small, and the content of the polycarbonate resin (A) is preferably small. The amount of metal in the metal is usually 1 wt ppm or less, preferably 0.8 wt ppm or less, and more preferably 0.7 wt ppm or less.

The amount of metal in the polycarbonate resin (A) can be measured by various conventionally known methods, but after recovering the metal in the polycarbonate resin (A) by a method such as wet ashing, atomic emission or atomic absorption is performed. It can be measured using methods such as absorption and inductively coupled plastic (ICP).
As described above, the polycarbonate resin (A) of the present invention is melt-polymerized, usually cooled and solidified, and pelletized with a rotary cutter or the like.

The method of pelletization is not limited, but for example, a method of extracting the polycarbonate resin (A) from the final polymerization reactor in a molten state and cooling and solidifying it in the form of strands to pelletize it, or melting from the final polymerization reactor. The resin is supplied to a uniaxial or biaxial 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 strands. Examples thereof include a method in which the resin is supplied to a uniaxial or biaxial extruder again after being pelletized, melt-extruded, and then cooled and solidified to be pelletized.

At that time, in the extruder, the residual monomer is volatilized under reduced pressure, and commonly known heat stabilizers, neutralizers, ultraviolet absorbers, mold release agents, colorants, antistatic agents, lubricants, lubricants, etc. It is also possible to add and knead a plasticizer, a compatibilizer, a flame retardant and the like.
The melt-kneading temperature in the extruder depends on the glass transition temperature and the 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. If the temperature is higher than 300 ° C., the thermal deterioration 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 matter, and further generation of discoloration. The filter for removing foreign matter and burnt matter is preferably installed in the extruder or at the outlet of the extruder.

The size (opening) of the filter for removing foreign matter is usually 400 μm or less, preferably 200 μm or less, and 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 removing foreign substances and burns, and when the polycarbonate resin (A) is molded, brittle fracture may occur. Further, the opening of the filter can be adjusted according to the use of the thermoplastic resin composition of the present invention. For example, when applied to a film application, the opening 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 installed in series and used, or a filtration device in which a plurality of leaf disk type polymer filters are laminated may be used.
Further, when the melt-extruded polycarbonate resin (A) is cooled and pelletized, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is possible to prevent the reattachment of foreign substances in the air by using air from which foreign substances in the air have been removed in advance with a HEPA filter (preferably a filter specified by JIS Z8112) or the like. desirable. It is more preferably carried out in a clean room having a higher cleanliness than Class 7 defined in JIS B 9920 (2002), and more preferably Class 6. When using water cooling, it is desirable to use water from which metals in the water have been removed with an ion exchange resin or the like and foreign substances in the water have been removed with a filter. The spread of the filter used varies, but a filter having a thickness of 10 to 0.45 μm is preferable.

When the polycarbonate resin (A) of the present invention is produced by the melt polymerization method, one or more of a phosphoric acid compound and a phosphorous acid compound can be added at the time of 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 to be subjected to the reaction. preferable. If the amount of the phosphorus compound added is less than the lower limit, the anticoloring effect is small, and if it is more than the upper limit, the transparency may be lowered, the coloring may be promoted, or the heat resistance may be lowered.

Further, as the phosphorous acid compound, the heat stabilizers shown below can be arbitrarily selected and used. In particular, trimethyl phosphate, triethyl phosphate, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl). One or more of pentaerythritol diphosphite can be preferably 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% or more, based on the total hydroxy compounds to be subjected to the reaction. It is preferable to add the following. If the amount of the phosphorous acid compound added is less than the lower limit, the anti-coloring effect is small, and if it is more than the upper limit, the transparency may be lowered, or conversely, the coloring may be promoted or the heat resistance may be lowered. Sometimes.

The above phosphoric acid compound and phosphorous acid compound can be added in combination, but in that case, the amount of addition is the total amount of the phosphoric acid compound and the phosphorous acid compound, with respect to all the hydroxy compounds to be subjected to the reaction. It is preferably 0.0001 mol% or more and 0.005 mol% or less, and more preferably 0.0003 mol% or more and 0.003 mol% or less. If the amount added is less than the lower limit, the anti-coloring effect is small, and if it is more than the upper limit, the transparency may be lowered, on the contrary, the coloring may be promoted or the heat resistance may be lowered. ..

Further, the polycarbonate resin (A) produced in this manner may contain one or more heat stabilizers in order to prevent a decrease in molecular weight and a deterioration in hue during molding or the like. ..
Examples of such a heat stabilizer include phosphorous acid, phosphorous acid, phosphonic acid, phosphonic acid, and esters thereof, and specific examples thereof include triphenyl phosphite, tris (nonylphenyl) phosphite, and tris (nonylphenyl) phosphite. 2,4-Di-tert-butylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyl Diphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di) -Tert-Butylphenyl) octylphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributylphosphate, Triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxysenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, tetrakis 4,4'-biphenylenediphosphinate (2,4-di-tert-butylphenyl), benzenephosphones Examples thereof include dimethyl acid acid, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Among them, trisnonylphenyl phosphite, trimethylphosphate, 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 additionally blended in addition to the amount added at the time of melt polymerization. That is, when an appropriate amount of a phosphorous acid compound or a phosphorous acid compound is blended to obtain a polycarbonate resin (A), and then a phosphorous acid compound is further blended by the blending method described later, the transparency at the time of polymerization is increased. It is possible to add more heat stabilizers while avoiding deterioration, coloring, and deterioration of heat resistance, and it is possible to prevent deterioration of hue.

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

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

(Glass-transition temperature)
The glass transition temperature (Tg) of the polycarbonate resin (A) of the present invention is less than 145 ° C. If the glass transition temperature of the polycarbonate resin (A) exceeds this range, it becomes easy to color and it may be difficult to improve the impact strength. Further, in this case, it is necessary to set the mold temperature high when transferring the shape of the mold surface to the molded product at the time of molding. Therefore, 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, 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 for setting the glass transition temperature of the polycarbonate resin (A) of the present invention to less than 145 ° C., the ratio of the structural unit (1) in the polycarbonate resin (A) can be reduced, or the polycarbonate resin (A) can be produced. Examples of the dihydroxy compound include a method of selecting an alicyclic dihydroxy compound having low heat resistance and a method of reducing the proportion of structural units derived from an aromatic dihydroxy compound such as a bisphenol compound in the polycarbonate resin (A). Be done.
The glass transition temperature (Tg) of the polycarbonate resin (A) of the present invention was measured using a differential scanning calorimeter (DSC6220 manufactured by SII Nanotechnology) in accordance with JIS K7121 (1987). 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 (hereinafter, may be simply referred to as “reduced viscosity”) measured at a temperature of 30.0 ° C. ± 0.1 ° C., which is precisely adjusted to dl, is preferably 0.40 dl / g or more, more preferably 0.40 dl / g or more. 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, 0.60 dl / g or more, further 0.85 dl / g or more. May be preferably used. The reducing 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 reducing viscosity of the polycarbonate resin (A) is excessively low, the mechanical strength may be weakened, and if the reducing viscosity of the polycarbonate resin (A) is excessively high, the fluidity during molding is lowered and the cycle characteristics are reduced. There is a tendency that the strain of the molded product becomes large and the molded product is easily deformed by heat.

(B) Ultraviolet absorber The ultraviolet absorber is not particularly limited as long as it is a compound having an ultraviolet absorbing ability. In the present embodiment, examples of the compound having an ultraviolet absorbing ability include an organic compound and an inorganic compound. Among them, the organic compound is preferable because it is easy to secure the affinity with the polycarbonate resin and it is easy to disperse uniformly.
The molecular weight of the organic compound having an ultraviolet absorbing ability is not particularly limited, but is usually 200 or more, preferably 250 or more. also. It is usually 600 or less, preferably 450 or less, and more preferably 400 or less. When the molecular weight is at least the above lower limit value, deterioration of the ultraviolet resistance performance after long-term use can be suppressed. Further, when the molecular weight is not more than the above upper limit value, it is possible to suppress a decrease in transparency of the resin composition after long-term use.
Preferred ultraviolet absorbers include benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, salicylate phenyl ester compounds, cyanoacrylate compounds, malonic acid ester compounds, oxalic acid anilide compounds and the like. .. Of these, benzotriazole-based compounds, hydroxybenzophenone-based compounds, and malonic acid ester-based compounds are preferably used. These may be used alone or in two or more kinds.

More specific examples of 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-benzotriazole-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate, etc. Can be mentioned.

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

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

Examples of triazine compounds 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-Triazine-2-yl) -5-[(hexyl) oxy] -phenol (manufactured by Ciba Geigy, Tinuvin 1577FF) and the like can be mentioned.

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

The content of the ultraviolet absorber is not particularly limited, but is preferably 0.01 part by weight or more, preferably 0.02 when the total of the above (A) and the following (E) is 100 parts by weight in the polycarbonate resin composition. More is more preferably parts by weight or more, more preferably 0.05 parts by weight or more, and most preferably 0.08 parts by weight or more. On the other hand, 5 parts by weight or less is preferable, 3 parts by weight or less is more preferable, 1 part by weight or less is further preferable, and 0.5 part by weight or less is most preferable. When the content of the ultraviolet absorber is at least the above lower limit value, the effect of improving the weather resistance by containing the ultraviolet absorber can be further obtained. On the other hand, when the content of the ultraviolet absorber is not more than the above upper limit value, it is possible to suppress the occurrence of poor appearance due to 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 deterioration 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] butylmalonate, bis (2,2,6,6-tetramethyl-4-) Piperidil) 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-tetramethylpiperidine, 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) 2,6,6-tetramethyl-4-piperidyl) phenylphosphite, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, tetrakis (2,6,6-tetramethyl-4-piperidyl) Examples thereof include hindered amines such as 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, the above (A)
) And (E) below, 0.01 parts by weight or more is preferable, 0.02 parts by weight or more is more preferable, 0.05 parts by weight or more is further preferable, and 0.08 parts by weight is used. The above is the most preferable. On the other hand, 5 parts by weight or less is preferable, 3 parts by weight or less is more preferable, 1 part by weight or less is further preferable, and 0.5 part by weight or less is most preferable.
When the content of the light stabilizer is at least the above lower limit value, the weather resistance of the obtained polycarbonate resin composition is further improved. The effect can be confirmed from the results of the weather resistance test described later. On the other hand, when the content of the light stabilizer is not more than the upper limit value, it is possible to prevent the generation of deposits on the mold during injection molding and improve the surface appearance of the obtained product.

(D) Antioxidant having a steric hindrance substituent on only 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. It contains an antioxidant having a sterically hindering substituent only in one of the two carbon atoms. Such an antioxidant has a sterically hindering substituent only on one of the two carbon atoms adjacent to the carbon atom having a phenolic hydroxyl group, and thus has excellent radical catching property 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 steric hindrance substituent only on one of the 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). , Preferable from the viewpoint of weather resistance. 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-methylphenol)
6-t-butyl-m-cresol), 2,5-di-t-butylhydroquinone, butylhydroxyanisole and the like can be mentioned. These compounds may 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 represent an alkyl group having 1 to 5 carbon atoms which may independently have a hydrogen atom or a substituent. .. Examples of the substituent include an allyl group, a metalyl group, a crotyl group, a 1,1-dimethyl-2-propenyl group, a 2-methyl-butenyl group, a 3-methyl-2-butenyl group, and a 3-methyl-3-3. 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 , 4-tert-Butylcyclohexyl group, tricyclodecanyl group, isobornyl group, adamantyl group, dicyclopentanyl group, dicyclopentenyl group and other alicyclic hydrocarbon groups; glycidyl group, β-methylglycidyl group, β -Ethylglycidyl group, 3,4-epoxycyclohexylmethyl group, 2-oxetanmethyl group, 3-methyl-3-oxetanmethyl group, 3-ethyl-3-oxetanmethyl group, tetrahydrofuranyl group, tetrahydrofurfuryl group, tetrahydro Cyclic ether groups such as pyranyl group, dioxazolanyl group, dioxanyl group; phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, 4-tert-butylphenyl group, methoxyphenyl group, hydroxyphenyl group, benzyl group, diphenyl Aryl groups such as methyl group, diphenylethyl group, triphenylmethyl group, cinnamyl group, naphthyl group and anthranyl group; alkoxy groups such as methoxy group, ethoxy group, methoxyethoxy group, cyclohexyloxy group, phenoxy group and phenoxyethoxy group; Alkylthio groups such as butylthio group, octylthio group, laurylthio group, stearylthio group, phenylthio group; acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioil group, caproyl group and other acyl groups; acetyloxy group, propionyl Acyloxy groups such as oxy group, butyryloxy group, valeryloxy group, benzoyloxy group, trioiloxy group, caproyloxy group, (meth) acryloyloxy group; methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, lauryl Alkoxycarbonyl groups such as oxycarbonyl group, stearyloxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group; butylthiocarbonyl group, octylthiocarbonyl group, laurylthiocarbonyl group, stearylthiocarbonyl group, f. Alkylthiocarbonyl groups such as enylthiocarbonyl 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 ester group; phosphonic acid Examples thereof include an ester group; a trimethylsilyl group, but the present invention is not limited to these examples.

In the compound having the structure represented by the above formula (7), it is preferable that n is an integer of 2 or more. That is, a compound having a structure represented by the above formula (7) is preferably a multimer linked via R ^2. The multimers are linked through an ^{R 2} of compounds having the structure represented by the above formula (7), for example, 4,4 ', 4' - (1-methyl-propynyl over 3-ylidene) tris (6- tert-Butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene-m-cresol can be mentioned. The weather resistance effect of the present invention is more excellent because it is a multimer linked via ^{R 2} of the compound having the structure represented by the above formula (7).

The content of the antioxidant having a steric hindrance substituent only on one of the two carbon atoms adjacent to the carbon atom having a phenolic hydroxyl group is not particularly limited, but in the polycarbonate resin composition, the above (A) and When the total of 100 parts by weight of the following (E) is taken, it is preferably 0.001 part or more, more preferably 0.01 part by weight or more, particularly preferably 0.02 part by weight or more, and 0.03 part by weight or more. Most preferred. On the other hand, 5 parts by weight or less is preferable, 4 parts by weight or less is more preferable, 1 part by weight or less is further preferable, and 0.5 part by weight or less is most preferable.
The weather resistance of the obtained polycarbonate resin composition when the content of the antioxidant having a steric hindrance substituent on only one of the two carbon atoms adjacent to the carbon atom having a phenolic hydroxyl group is at least the above lower limit value. The sex is 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 steric hindrance 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, the gold at the time of injection molding It is possible to prevent the generation of deposits on the mold and improve the surface appearance of the obtained product.

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

(E) Elastomer having a core-shell structure The "elastomer having a core-shell structure" is composed of an innermost layer (core layer) and one or more layers (shell layers) covering the innermost layer (shell layer), and can be copolymerized with the core layer. It is a core-shell type graft copolymer obtained by graft-copolymerizing 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-copolymerizing a polymer component called a rubber component as a core layer and a monomer component copolymerizable with the polymer component as a shell layer. preferable.
The method for producing the core-shell type graft copolymer may be any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like, and the copolymerization method may be a one-step graft or a multi-step 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 elastomers are listed below.

The polymer component forming the core layer usually has a glass transition temperature of 0 ° C. or lower, particularly 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 and poly (2-ethylhexyl acrylate), polyalkyl acrylate such as butyl acrylate and 2-ethylhexyl acrylate copolymer, and polyorganosiloxane. IPN (Interpentrating Polymer Network) type composite rubber composed of silicone rubber such as rubber, butadiene-acrylic composite, polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene copolymer, ethylene-propylene copolymer and ethylene Examples thereof include ethylene-α olefin-based copolymers such as −butene copolymers and ethylene-octene copolymers, ethylene-acrylic copolymers, and fluororubbers. These may be used alone or in admixture of two or more. Among these, polybutadiene, polyalkyl acrylate, polyorganosiloxane, a composite composed of polyorganosiloxane and polyalkyl acrylate, and a butadiene-styrene copolymer are preferable from the viewpoint of mechanical properties and surface appearance.

Specific examples of the polymer component of the core layer and the monomer component that can be graft-copolymerized constituting the shell layer include an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylic acid ester compound, and (meth) acrylic. Epoxy group-containing (meth) acrylic acid ester compounds such as acid compounds and glycidyl (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α and β such as maleic acid, phthalic acid and itaconic acid. -Unsaturated carboxylic acid compounds and their anhydrides (for example, maleic anhydride) and the like can be 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, and (meth) acrylic acid ester is more preferable, from the viewpoint of mechanical properties and surface appearance. It is a compound. Specific examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and octyl (meth) acrylate. Of these, methyl (meth) acrylate and ethyl (meth) acrylate, which are relatively easily available, are preferable, and methyl (meth) acrylate is more preferable. Here, "(meth) acrylic" is a general term for "acrylic" and "methacrylic acid".

The elastomer having a core-shell structure is at least one weight selected from an IPN type composite rubber composed of a polybutadiene-containing rubber, a polybutyl acrylate-containing rubber, a polyorganosiloxane rubber, a polyorganosiloxane rubber and a polyalkylacrylate rubber. A core-shell type graft copolymer having a core layer as a coalescing component and a shell layer formed by graft-copolymerizing a (meth) acrylic acid ester around the core layer is particularly preferable. The core-shell type graft copolymer preferably contains 40% by weight or more of the polymer component of the core layer, and more preferably 60% by weight or more. Further, the (meth) acrylic acid ester component of the shell layer is preferably contained in an amount of 10% by weight or more.

Preferred specific examples of these core-shell graft copolymers are methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Combined (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- (acrylic / silicone composite) copolymers.

Examples of such a core-shell graft copolymer include "Paraloid (registered trademark) EXL2602", "Paraloid (registered trademark) EXL2603", and "Paraloid (registered trademark)" manufactured by Roam & 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)" (Registered Trademark) KCZ201 ”,“ Metabren (Registered Trademark) C-223A ”manufactured by Mitsubishi Rayon Co., Ltd. ) W-450A "" Metabren (registered trademark) SRK-200 "," Kaneace (registered trademark) M-511 "," Kaneace (registered trademark) M-600 "," Kaneace (registered trademark) M- "400", "Kaneace (registered trademark) M-580", "Kaneace (registered trademark) MR-01" and the like can be mentioned.

As the impact strength modifier having a core-shell structure such as these core-shell type graft copolymers, one type may be used alone, or two or more types may be used in combination.

The content of the elastomer having a core-shell structure in the resin composition of the present invention is not particularly limited, but is 100 parts by weight in total of the above component (A) and the following component (E) in the polycarbonate resin composition. The content of the elastomer having the core-shell structure (E) 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. It is more preferably present, and most preferably 5 parts by weight or more. On the other hand, it is more preferably 40 parts by weight or less, further 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 at least the above lower limit value, the effect of improving the surface impact resistance and the impact resistance is exhibited. On the other hand, when the blending amount of the elastomer having a core-shell structure is not more than the above upper limit value, it is possible to suppress poor appearance and deterioration of heat resistance of the obtained molded product.

(F) Phenyl Antioxidant Examples of the phosphite antioxidant include triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, and tridecylphos. Fight, Trioctylphosphite, Trioctadecylphosphite, Didecylmonophenylphosphite, Dioctylmonophenylphosphite, Diisopropylmonophenylphosphite, Monobutyldiphenylphosphite, Monodecyldiphenylphosphite, Monooctyldiphenylphosphite, Bis (2,6-di-tert
-Butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2, 4-Di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite and the like can be mentioned.

Among these, trisnonylphenyl phosphate, 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 may be used alone or in combination of two or more.

Here, the content of the phosphite-based antioxidant is not particularly limited, but is preferably 0.01 part by weight or more when the total of the above (A) and the following (E) 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 further preferable, and 0.08 parts by weight or more is most preferable. On the other hand, 5 parts by weight or less is preferable, 3 parts by weight or less is more preferable, 1 part by weight or less is further preferable, and 0.5 part by weight or less is most preferable.
When the content of the phosphite-based antioxidant is at least the above lower limit value, a sufficient effect of suppressing coloration during molding can be obtained. Further, when the content of the phosphite-based antioxidant is not more than the above upper limit value, deposits on the mold during injection molding and deposits on the roll when the film is formed by extrusion molding are generated. Can be prevented and the surface appearance of the product can be improved.

(Other additives)
In addition to the above-mentioned additives, the polycarbonate resin composition of the present invention contains various well-known additives such as a mold release agent, a flame retardant, a flame retardant aid, and an antistatic agent, 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 dyeing pigment and the like.

(Inorganic filler)
Further, the polycarbonate resin composition of the present invention may contain an inorganic filler. The blending amount of the inorganic filler is usually 1 part by weight or more and 100 parts by weight or less, preferably 3 parts by weight or more and 50 parts by weight or less, based on 100 parts by weight of the polycarbonate resin. If the blending amount of the inorganic filler is excessively small, the reinforcing effect is small, and if it is excessively large, the appearance tends to be deteriorated.

Examples of the inorganic filler include glass fiber, glass milled fiber, glass flakes, glass beads, 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 fiber, potassium titanate fiber, whisker, etc. Be done. Among these, glass fibrous filler, glass powder filler, glass flake filler; carbon fibrous filler, carbon powder filler, carbon flake filler; various whiskers, mica , Tark is preferred. More preferably, glass fiber, glass flake, glass milled fiber, carbon fiber, wallastnite, mica and talc can be mentioned.

(Colorant)
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.
Examples of the 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), chromates such as chrome titanium yellow (CI Pigment Brown 24); ferrocyanides such as dark blue (CI pigment Blue 27); cadmium yellow (CI pigment Yellow 42), cadmium. Sulphides such as red (CI pigment Red 108); iron black (CI pigment Black 11), Bengara (CI pigment Red 101), titanium dioxide (CI pigment White 6), etc. Oxides; silicates such as ultramarine (CI pigment Blue 29); or carbon blacks such as channel black, roller black, discs, gas furnace black, oil furnace black, thermal black, acetylene black (CI) . Pigment Black 7) and the like can be mentioned.

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 system), C.I. I. Pigment Yellow 23, C.I. I. Solvent Green3, C.I. I. Solvent Yellow 163, C.I. I. SolventRed111, C.I. I. SolventRed146, C.I. I. DisperseRed22, C.I. I. SolventViolet31, C.I. I. SolventViolet13, C.I. I. SolventBlue35, C.I. I. SolventBlue36, C.I. I. SolventBlue97, C.I. I. SolventBlue87 (anthraquinone type), C.I. I. pigment Yellow 109 (isoindolenone type), C.I. I. pigment Yellow 138, C.I. I. Solvent Yellow 114, C.I. I. SolventYellow33 (quinophthalone type), C.I. I. Pigment Orange 5, C.I. I. SolventYellow14 (monoazo system), 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 system), C.I. I. pigment Red 1, C.I. I. PigmentRed170, C.I. I. SolventYellow16, (monoazo system), C.I. I. Pigment Red 37 (pyrazolone azo system), C.I. I. Pigment Red 87, C.I. I. SolventRed41 (thioingigo system), C.I. I. Pigment Red 224, C.I. I. SolventGreen5 (perylene type), C.I. I. Pigment Violet 19 (quinacridone), C.I. I. Pigment Violet 3, C.I. I. SolventYellow93 (azomethine-based), C.I. I. Pigment Violet 37 (dioxazine type), C.I. I. Pigment Blue 15 (phthalocyanine type), C.I. I. Pigment Green 1 (azomethine type), C.I. I. SolventYellow104 (isoquinoline) C.I. I. SolventOrange63 (thioxanthene type) C.I. I. SolventRed149, C.I. I. SolventRed52 (naphthoquinolin type) and the like can be mentioned.

One of these colorants may be used alone, or two or more of these colorants may be mixed and used.
The lower limit of the content of the colorant is not particularly limited, but is preferably 0.00001 parts by weight or more when the total of the above (A) and the following (E) is 100 parts by weight in the polycarbonate resin composition. It is preferably 0.0001 parts by weight or more, and more preferably 0.0005 parts by weight or more. When the content of the colorant is at least the above lower limit, it is possible to impart a deep and clear color to the molded product of the obtained resin composition. On the other hand, the upper limit of the content of the coloring material is not particularly limited, but is preferably 3 parts by weight or less when the total of the above (A) and the following (E) is 100 parts by weight in the polycarbonate resin composition. It is more preferably 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 obtained resin composition can be reduced, and the molded product can be given a deep and clear color.

<Mixing method>
As a method of blending the above-mentioned various additives into the thermoplastic resin composition of the present invention, for example, the mixture is mixed with a tumbler, a V-type blender, a super mixer, a Nauter mixer, a Banbury mixer, a kneading roll, an extruder or the like. -There are a kneading method, a solution blending method in which the mixture is dissolved in a common good solvent such as methylene chloride, and the like, but this is not particularly limited, and any blending method that is usually used is used. Any method may be used.
The thermoplastic resin composition of the present invention thus obtained is added with various additives and the like, and is directly or once pelletized by a melt extruder, and then an extrusion molding method, an injection molding method, a compression molding method, etc. It can be molded into a desired shape by a commonly known molding method.

<Manufacturing method of polycarbonate resin composition>
In the embodiment of the present invention, only one of the two carbon atoms adjacent to the ultraviolet absorber, the light stabilizer, and the carbon atom having a phenolic hydroxyl group, which can be blended in the polycarbonate resin composition, is sterically hindered substituted. The mixing timing and mixing method of the antioxidant having a group are not particularly limited. As the mixing time, for example, when the 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. Further, regardless of the polymerization method, when the polycarbonate resin is in a molten state, such as during kneading of the polycarbonate resin and another compounding agent, the polycarbonate resin may be mixed using a kneading extruder or the like. Further, a mixture of a solid polycarbonate resin such as pellets or powder and a compounding agent may be further heated and mixed.

The polycarbonate resin composition of the present invention is produced by mixing the above-mentioned compounding components at the same time or in an arbitrary order by a mixer such as a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, or an extruder. Can be done.
As a mixing method, the above-mentioned compounding components may be directly mixed or kneaded with the polycarbonate resin, or a high-concentration masterbatch prepared in advance using a small amount of polycarbonate resin or other resin and the above-mentioned compounding components is prepared. However, the masterbatch can also be mixed with the polycarbonate resin according to the present invention.

[Reason why the present invention is effective]
The reason why the present invention is effective is not yet clear, but it is presumed as follows. That is, when the polycarbonate resin (A) is colored due to thermal deterioration during molding, aged deterioration due to the natural environment during use, etc., deterioration due to ultraviolet rays progresses. On the other hand, when the polycarbonate resin (A) is blended with an ultraviolet absorber, 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, an oxidative deterioration suppressing mechanism capable of capturing and inactivating active radicals generated by further blending a hindered phenol-based antioxidant or a hindered amine-based light stabilizer (HALS) in addition to an ultraviolet absorber. It has been known. On the other hand, in the present invention, by using an ultraviolet absorber, an antioxidant having a sterically-damaging radical only in one of two carbon atoms adjacent to a carbon atom having a phenolic hydroxyl group, and HALS in combination, by absorbing ultraviolet rays. Antioxidation of active radicals generated from UV absorbers, first of all, "antioxidation having a sterically damaging substituent on only one of the two carbon atoms adjacent to the carbon atom having a phenolic hydroxyl group, which has excellent radical catching properties with little steric damage. The agent "captures it, then deactivates the active radical in HALS by a radical exchange reaction with HALS, and regenerates it by radical exchange only in one of the two carbon atoms adjacent to the carbon atom having a phenolic hydroxyl group. By supplementing the active radicals of "antioxidants with sterically damaging substituents", the active radicals can be deactivated much more efficiently than the conventional oxidative deterioration suppression mechanism by the combined use of ultraviolet absorbers and antioxidants, resulting in excellent weather resistance. It is presumed that it shows sex. Further, 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 is less likely to cause deterioration in appearance, when an elastomer having a core-shell structure is blended, deterioration of the elastomer due to the natural environment is also suppressed. It should be possible to maintain excellent impact resistance.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.
In the following, the physical characteristics or properties of the polycarbonate resin composition, molded product, etc. were evaluated by the following methods.

[Method of preparing test pieces and various evaluations]
(1) Method for preparing test piece The pellet of the polycarbonate resin composition was dried at 90 to 100 ° C. for 10 hours in a nitrogen atmosphere. Next, pellets of the dried polycarbonate resin composition are supplied to an injection molding machine (J75EII type manufactured by Japan Steel Works, Ltd.), and the injection molded piece (width 60 mm × length) is provided under the conditions of a resin temperature of 240 ° C. and a molding cycle of 40 seconds. 60 mm x 2 mm thick) and an ISO test piece for evaluating mechanical properties were molded.
(2) Jet blackness (L ^* )
^{The color value L *} was measured by the D65 light source reflection method SCE (specular reflection removal) using a spectral color difference meter (CM-5 manufactured by Konica Minolta) in accordance with JIS Z8722.
The ^{smaller the L *} value, the better the jet blackness. In this embodiment, an L ^* value of 1.0 or less is defined as “◯”.

(3) Weather resistance (ΔE ^* )
The weather resistance was judged by comprehensively determining the results of ^{the color difference (ΔE *} ) and the gloss retention rate evaluated by the weather resistance test described in detail below.
[Weather resistance test]
The weather resistance test is performed by setting the discharge voltage to 50 V and the discharge current to 60 A with a sunshine carbon arc (4 pairs of ultra long life carbon) light source using a sunshine weather meter S60 manufactured by Suga Test Instruments Co., Ltd. in accordance with JIS B7753. 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 a black panel temperature of 63 ° C. and a relative humidity of 50% by surface spraying (rainfall). Was irradiated for 1000 hours. The surface spray (rainfall) time was 12 minutes / hour, and the glass filter was A type.

[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 conform to JIS Z8722, and the color values L *} , a ^* , b are measured by the D65 light source reflection method SCE (normal reflection removal) using a spectrocolorimeter (CM-5 manufactured by Konica Minolta). ^{* Was} measured, the values before the test were L ₀ ^* , a ₀ ^* , b ₀ ^* , and the values after the test were L ^* , a ^* , b ^* , and ΔE * was calculated from the following formula.
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 that the weather resistance is excellent without the color difference caused by the natural environment such as sunlight, rain and snow, and humidity. In this embodiment, the pass / fail judgment was made as follows.
ΔE ^* value of 1.0 or less: Judged as having excellent weather resistance, "○"
ΔE ^* value of 0.5 or less: Judged to be particularly excellent in weather resistance, "◎"
Those with a ΔE ^* value exceeding 1.0: Judged as not having excellent weather resistance, "x"

[Gloss retention rate]
Using an injection molded piece, measure the glossiness value (Gs60 °) with a spectrocolor difference meter VC-2000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z8741, and measure the glossiness before and after the weather resistance test in (3) above. The gloss retention rate was calculated from the values by the following formula.
Gloss retention rate (%) = {(gloss value after weathering test) / (gloss value before weathering test)} x 100
The larger the value of the gloss retention rate, the smaller the change in the gloss value before and after the weather resistance test, and the better the weather resistance without the change in the gloss of the surface appearance due to the natural environment such as sunlight, rain and snow, and humidity. Indicates that In this embodiment, pass / fail was determined as follows.
Those with a gloss retention rate of 90% or more: Judged as having excellent weather resistance, "○"
Those with a gloss retention rate of 98% or more: Judged to be particularly excellent in weather resistance, "◎"
Gloss retention rate less than 90%: Judged as not excellent in weather resistance, "x"

[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 performed as follows.
Both the color difference change (ΔE ^* ) and the gloss retention rate are “⊚”: It was judged that the weather resistance was extremely excellent.
One of the color difference change (ΔE ^* ) and the gloss retention rate was “⊚”, and the other was “◯”: It was judged that the weather resistance was particularly excellent.
Those in which both the color difference change (ΔE ^* ) and the gloss retention rate are “◯”: It was judged that the weather resistance was excellent.
If either the color difference change (ΔE ^* ) or the gloss retention rate is “x”: it was judged to be inferior in weather resistance.

(4) Appearance The appearance of the injection-molded piece after the above-mentioned (3) weather resistance (ΔE ^* ) test is visually confirmed, and the surface of the injection-molded piece with no cracks is marked with “○” and has cracks. Was set to "x". It has been confirmed that the injection molded piece used before the test has no cracks.

(5) Comprehensive evaluation As a result of the above test, the comprehensive evaluation was as follows. Even if the following acceptance criteria are satisfied, the one with a large number of ◎ is preferable.
Pass: Only 〇 or ◎ Fail: ×

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% copolymerized polycarbonate (manufactured by Mitsubishi Chemical Corporation: Durabio D7340R)
A-2: Isosorbide / 1,4-Cyclohexanedimethanol = 50/50 mol% copolymerized 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 ADEKA STAB LA-29
B-2: Benzophenone-based ADEKA ADEKA STAB LA-31
B-3: Triazine-based ADEKA ADEKA TAB LA-46

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

((D) Antioxidant having a sterically hindering substituent on only one of two carbon atoms adjacent to a carbon atom having a phenolic hydroxyl group)
D-1: 4,4', 4'-(1-methylpropynyl-3-iriden) Tris (6-tert-butyl-m-cresol) ADEKA ADEKA STAB AO-30
D-2: 6,6'-di-tert-butyl-4,4'-butylidene-m-cresol ADEKA ADEKA STAB AO-40

((E) Phosphite-based antioxidant)
F-1: ADEKA ADEKA STAB PEP-36A
F-2: BASF IRGAFOS PEP-Q

(Hindered phenolic antioxidants other than (D))
X-1: [3- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionoloxy] -2,2-bis [3- (3,5-di-tert-butyl) -4-Hydroxyphenyl) propanil] propionyloxy] propyl] 3- (3,5-di-tert
-Butyl-4-hydroxyphenyl) propionate 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

(Colorant)
・ Solvent Violet 36 Macrolex Violet 3R manufactured by LANXESS Co., Ltd.
・ Solvent Red 179 Lanxess Macrolex Red E2G ・ Solvent Green 3 Arimoto Chemical Industry Co., Ltd. Oil Green 5602
・ Solvent Blue 97 Macrolex Blue manufactured by LANXESS Co., Ltd.
RR

[Example 1]
Polycarbonate resin (A-1), ultraviolet absorber (B-1), light stabilizer (B-2), and two adjacent carbon atoms having phenolic hydroxyl groups so as to have the composition shown in Table-1. An antioxidant (D-1) having a steric hindrance substituent is mixed with only one of the carbon atoms, and an outlet is used using a twin-screw extruder (TEX-33) manufactured by Japan Steel Works, Ltd., which has one vent port. The resin was extruded into a strand shape so that the resin temperature of the resin was 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 of 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 of 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 of 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 of 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 of 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 of evaluating the obtained polycarbonate resin composition in the same manner as in Example 1.

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

The polycarbonate resin composition of the present invention is excellent not only in excellent transparency but also in good moldability, weather resistance, hue, heat resistance, moldability, and mechanical strength, and is used for electrical / electronic parts, automobile parts, etc. Injection molding field, film, sheet field, bottle, container field that requires heat resistance, lens applications such as camera lenses, finder lenses, CCD and CMOS lenses, phase difference used for liquid crystal and plasma displays, etc. It is possible to provide materials for a wide range of fields such as films such as films, diffusion sheets and polarizing films, sheets, optical disks, optical materials, optical components, dyes, binders for immobilizing charge transfer agents and the like.

Claims (8)

(A) A polycarbonate resin containing a structural unit derived from a dihydroxy compound represented by the following general formula (1), and
(B) Ri greens contain an antioxidant having two sterically hindered substituent on only one of the carbon atoms adjacent to the carbon atom having an ultraviolet absorber (C) a light stabilizer (D) a phenolic hydroxyl group ,
Aromatic dihi for the structural unit derived from all the dihydroxy compounds contained in (A).
The content of structural units derived from the droxy compound is 0 mol% or more and less than 40 mol%.
,
The above (D) is an antioxidant having a structure represented by the following formula (7).
Further, as an optional component, (E) an elastomer having a core-shell structure is contained, and
When the total of the above (A) and the above (E) is 100 parts by weight, the above (B) is 0.01 weight.
Contains more than 5 parts by weight and less than 5 parts by weight, and contains more than 0.01 parts by weight and less than 5 parts by weight of (C).
(D) is contained in an amount of 0.001 part by weight or more and 5 parts by weight or less.
Polycarbonate resin composition.

(In the above formula (7), n represents an integer of 1 to 4, R ¹ also have a hydrogen atom or a substituent represents an alkyl group having 1 to 5 carbon atoms. N is 1 If R ² is a hydrogen atom
Indicates an alkyl group having 1 to 5 carbon atoms which may have a substituent. When n is an integer of 2-4
, R ² has n-1 hydrogen atoms from an alkyl group having 1 to 5 carbon atoms which may have a substituent.
The n-valent group excluding is shown. ) Claim that the content of the elastomer having the core-shell structure (E) is 0.1 to 50 parts by weight when the total of (A) and (E) is 100 parts by weight in the polycarbonate resin composition. The polycarbonate resin composition according to 1. Polycarbonate resin composition, when a total of 100 parts by weight of the (A) and the (E), containing 0.01 to 5 parts by weight of (F) phosphite antioxidant, also claim 1
Is the polycarbonate resin composition according to 2. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the shell layer of the elastomer component (E) having the core-shell structure is made of alkyl (meth) acrylate. The polycarbonate resin composition according to claims 1 to 4 , wherein the light stabilizer (C) has a piperidine structure. The polycarbonate resin composition according to any one of claims 1 to 5 , wherein the color value L * measured by the D65 light source reflection method SCE (specular reflection removal) according to JIS Z8722 is 3 or less. A molded product containing the polycarbonate resin according to any one of claims 1 to 6. The molded product according to claim 7 , wherein the molded product is a part for an automobile.