JP2012197381A - Polycarbonate resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition excellent in thermal stability in heat molding, and excellent in the color hue after molding.SOLUTION: The polycarbonate resin composition contains at least a polycarbonate resin having a structural unit originated from a dihydroxy compound having a site represented by formula (1) as a part of the structure, and contains 0.001 to 0.5 pts.mass of a compound represented by formula (2) based on 100 pts.mass of the polycarbonate resin. Here, the case where the site represented by formula (1) is a part of -CH-O-H is excluded. In the formula (2), Ar, Arand Arare each independently a 6-20C aryl group, and may have a 1-10C alkyl group as a substituent.

Description

  The present invention relates to a polycarbonate resin composition excellent in light resistance, moldability, transparency, hue, heat resistance, thermal stability, and mechanical strength, and a molded product thereof.

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

  In order to solve such a problem, a method of adding a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, or a benzoxazine ultraviolet absorber to a polycarbonate resin is widely known (for example, Non-Patent Document 1).

Polycarbonate resins that use cyclic dihydroxy compounds with an ether bond in the molecule, such as aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and isosorbide obtained from biomass resources, as a monomer unit have heat resistance and mechanical strength. Due to its superiority, many studies have been made in recent years (for example, Patent Documents 1 to 7).

  In addition, a polycarbonate resin composition having an ether bond in the molecule such as isosorbide, isomannide, isoitide, etc. that does not have a benzene ring structure in the molecular skeleton, benzotriazole, benzophenone, It is known to add a cyanoacrylate system (Patent Document 8).

International Publication No. 04/111106 Pamphlet Japanese Patent Laid-Open No. 2006-232897 JP 2006-28441 A JP 2008-24919 A JP 2009-91404 A JP 2009-91417 A JP 2008-274007 A JP 2007-70391 A

Polycarbonate resin handbook (issued by Seiichi Honma, published by Nikkan Kogyo Shimbun, August 28, 1992)

  However, in order to prevent deterioration of hue and transparency when using the polycarbonate resin composition in a place where it is exposed to ultraviolet rays or visible light for a long time, when an ultraviolet absorber or the like is used, the hue after ultraviolet irradiation, etc. Although improvement of the above was recognized, there were problems such as affecting the hue, heat resistance and transparency of the resin in the first place, and volatilizing during molding to contaminate the mold. In particular, when a hindered amine light stabilizer (hereinafter sometimes abbreviated as HALS), which is a basic compound, is used in a polycarbonate resin, the polycarbonate is hydrolyzed by HALS, resulting in hue, transparency, mechanical properties. There was a problem that the mechanical strength was lowered. Moreover, there existed a subject that mold release property was bad at the time of melt molding, and it was difficult to use it for a transparent material, an optical material, etc.

  On the other hand, as polycarbonate resins, monomer units of aliphatic dihydroxy compounds that do not have an aromatic ring structure in the molecular skeleton, monomer units of alicyclic dihydroxy compounds, and cyclic dihydroxy compounds having an ether bond in the molecule such as isosorbide. If a polycarbonate resin containing a monomer unit is used, it is expected that the light resistance is improved in principle. However, cyclic dihydroxy compounds having an ether bond in the molecule, such as aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and isosorbide, do not have phenolic hydroxyl groups, and are widely known as methods for producing polycarbonate resins using bisphenol A as a raw material. It is difficult to polymerize by the conventional interface method, and it is usually produced by a method called a transesterification method or a melting method. In this method, the dihydroxy compound and a carbonic acid diester such as diphenyl carbonate are transesterified at a high temperature of 200 ° C. or higher in the presence of a basic catalyst, and the polymerization proceeds by removing by-product phenol and the like out of the system, A polycarbonate resin is obtained. However, the polycarbonate resin obtained by using the monomer having no phenolic hydroxyl group as described above is inferior in thermal stability to the polycarbonate resin obtained by using a monomer having a phenolic hydroxyl group such as bisphenol A. Therefore, there is a problem that coloring occurs during polymerization or molding that is exposed to a high temperature, and as a result, ultraviolet rays and visible light are absorbed to deteriorate light resistance.

Moreover, in the polycarbonate resin obtained using the monomer which does not have a phenolic hydroxyl group improved by points, such as a hue after ultraviolet irradiation, in polycarbonate resin obtained using the monomer which has phenolic hydroxyl groups, such as bisphenol A, Since the heat stability is inferior, coloring occurs during polymerization or molding that is exposed to a high temperature, and as a result, there is a problem in that the light resistance is reduced by absorbing ultraviolet rays and visible light. In particular, when a monomer having an ether bond in the molecule, such as isosorbide, is used, the influence on the hue is remarkable, and improvement has been demanded. Further, when it is used as various molded products, it is melt-molded at a high temperature. However, a material that has good thermal stability and is excellent in moldability and releasability at a high temperature has been demanded.
In addition, when an ultraviolet absorber is added to a polycarbonate resin composition using an ether bond in the molecule, there is a problem in that the hue, heat resistance, and weather resistance test of the resin itself deteriorate. .

  The object of the present invention is to eliminate the above-mentioned conventional problems, and is a resin having excellent transparency because of less coloring of the resin during polymerization, and also excellent in thermal stability during thermoforming, and to a hue after molding. An object of the present invention is to provide a polycarbonate resin composition excellent in mold release properties and a molded product thereof, which is excellent in melt molding.

  As a result of intensive studies to solve the above problems, the present inventor includes a polycarbonate resin containing at least a structural unit derived from a dihydroxy compound having a site represented by the following formula (1) in a part of the structure. It is a polycarbonate resin composition, and not only has excellent light resistance by containing 0.01 to 0.5 parts by mass of the compound represented by the following formula (2) with respect to 100 parts by mass of the polycarbonate resin. The present inventors have found that it has excellent moldability, transparency, hue, heat resistance, thermal stability, and mechanical strength, and reached the present invention.

That is, the gist of the present invention resides in the following [1] to [7].

（但し、式（１）で表される部位が−ＣＨ_２−Ｏ−Ｈの一部である場合を除く。）

（式（２）において、Ａｒ^１、Ａｒ^２、Ａｒ^３は、それぞれ独立に炭素数６〜２０のアリール基であり、炭素数１〜１０のアルキル基を置換基として有していてもよい。) [1] A polycarbonate resin composition comprising at least a polycarbonate resin having a structural unit derived from a dihydroxy compound having a site represented by the following formula (1) as part of the structure, represented by the following formula (2): A polycarbonate resin composition containing 0.001 to 0.5 parts by mass of the compound based on 100 parts by mass of the polycarbonate resin.

(Unless moiety represented by the formula (1) is part of _-CH 2 -O-H.)

(In Formula (2), Ar ¹ , Ar ² , and Ar ³ are each independently an aryl group having 6 to 20 carbon atoms, and may have an alkyl group having 1 to 10 carbon atoms as a substituent. )

（式（３）において、Ａ^１、Ａ^２は、置換基を有していてもよい炭素数１〜１８の脂肪族基、または置換基を有していてもよい芳香族基であり、Ａ^１とＡ^２は同一であっても異なっていてもよい。） [2] In the presence of a catalyst and a compound represented by the formula (2), a dihydroxy compound having a site represented by the formula (1) in a part of the structure and a carbonic acid diester represented by the following formula (3) The polycarbonate resin composition of Claim 1 obtained by polycondensation with.

(In the formula ^{(3), A 1, A} 2 is an aliphatic group or optionally substituted aromatic group, having 1 to 18 carbon atoms which may have a substituent, A ¹ and A ² may be the same or different.)

[3] The polycarbonate resin composition according to claim 1 or 2, wherein the dihydroxy compound having a site represented by the formula (1) is a compound represented by the following formula (4): .

[4] The method according to any one of claims 1 to 3, wherein the polycarbonate resin further includes a structural unit derived from at least one compound selected from the group consisting of aliphatic hydrocarbon dihydroxy compounds. Polycarbonate resin composition.

[5] Any one of claims 1 to 4, wherein the polycarbonate resin contains 90 mol% or less of a structural unit derived from a dihydroxy compound having a site represented by the formula (1) in a part of the structure. 2. The polycarbonate resin composition according to item 1.

[6] A polycarbonate resin molded product obtained by molding the polycarbonate resin composition according to any one of claims 1 to 5.

[7] A polycarbonate resin molded article obtained by injection molding the polycarbonate resin composition according to any one of claims 1 to 5.

  According to the present invention, not only has excellent light resistance, but also excellent moldability, transparency, hue, heat resistance, thermal stability, and mechanical strength, such as electrical / electronic parts, automotive parts, etc. Injection molding field, film, sheet field, bottle, container field, camera lens, viewfinder lens, lens application such as CCD and CMOS lens, retardation film used for liquid crystal and plasma display, diffusion sheet, polarized light To provide a polycarbonate resin composition and a molded article applicable to a wide range of fields such as a film such as a film, a sheet, an optical disk, an optical material, an optical component, a binder for fixing a dye and a charge transfer agent, and a building member. Polycarbonate resin composition suitable for applications exposed to light including ultraviolet rays, such as outdoors and lighting parts, and It is possible to provide a molded article.

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

(1) Polycarbonate resin composition The polycarbonate resin composition of the present invention includes a polycarbonate resin composition including at least a structural unit derived from a dihydroxy compound having a site represented by the following formula (1) in a part of the structure. It is a thing, Comprising: The compound represented by following formula (2) is contained 0.01-0.5 mass part with respect to 100 mass parts of this polycarbonate.

（但し、上記式（１）で表される部位が−ＣＨ_２−Ｏ−Ｈの一部である場合を除く。）

(However, the site represented by the above formula (1) unless it is part of _-CH 2 -O-H.)

（式（２）において、Ａｒ^１、Ａｒ^２、Ａｒ^３は、それぞれ独立に炭素数６〜２０のアリール基であり、炭素数１〜１０のアルキル基を置換基として有していてもよい。)

(In Formula (2), Ar ¹ , Ar ² , and Ar ³ are each independently an aryl group having 6 to 20 carbon atoms, and may have an alkyl group having 1 to 10 carbon atoms as a substituent. )

  The polycarbonate resin used in the present invention is a polycarbonate resin containing at least a structural unit derived from a dihydroxy compound having a site represented by the formula (1) in a part of the structure.

  Hereinafter, the method for producing the polycarbonate resin composition of the present invention will be described in detail.

(2) Manufacturing method of polycarbonate resin composition (2-1) Polycarbonate resin <Raw material>
(Dihydroxy compound)
The polycarbonate resin used in the present invention has a structural unit derived from a dihydroxy compound having a site represented by the following formula (1) in a part of the structure (hereinafter sometimes referred to as “the dihydroxy compound of the present invention”). Including at least. That is, the dihydroxy compound of the present invention refers to a compound containing at least two hydroxyl groups and at least a structural unit of the following formula (1).

（但し、上記式（１）で表される部位が−ＣＨ_２−Ｏ−Ｈの一部である場合を除く。）

(However, the site represented by the above formula (1) unless it is part of _-CH 2 -O-H.)

  The ratio of the structural unit derived from the dihydroxy compound having the site represented by the above formula (1) to the number of moles of the structural unit derived from all the dihydroxy compounds is preferably 90 mol% or less, more preferably 85 mol% or less, Especially preferably, it is 80 mol% or less. On the other hand, it is preferably at least 20 mol%, more preferably at least 30 mol%, particularly preferably at least 40 mol%.

When the proportion of the structural unit derived from the dihydroxy compound having the site represented by the above formula (1) is too large, irradiation using a sunshine carbon arc is performed on a polycarbonate resin molded product obtained by molding the polycarbonate resin composition of the present invention. After the treatment, the polycarbonate resin molded product may be cracked, and the transparency of the resin molded product may deteriorate and haze may increase. However, it is possible to prevent the polycarbonate resin molded product from cracking by incorporating a light-resistant stabilizer, which will be described later, preferably a light stabilizer, particularly a predetermined range of hindered amine, into the polycarbonate resin composition. The cause of cracking in the polycarbonate resin molded product is not clear, but if the proportion of structural units derived from the dihydroxy compound having the site represented by the above formula (1) is too large, the surface of the polycarbonate resin molded product is irradiated with ultraviolet rays. It is considered that the molecular weight of the resin molded product is lowered due to deterioration and hydrolysis.
However, as described above, it is possible to prevent cracking of the polycarbonate resin molded product by including the light-resistant stabilizer in the polycarbonate resin composition. The cause of this is not clear, but it is considered that the light-resistant stabilizer suppresses ultraviolet irradiation deterioration and hydrolysis on the surface of the polycarbonate resin molded product, and the molecular weight of the resin molded product is difficult to decrease.

On the other hand, if the proportion of the structural unit derived from the dihydroxy compound having the site represented by the formula (1) is too small, the heat resistance of the polycarbonate resin composition and its molded product may be lowered.
The dihydroxy compound of the present invention is not particularly limited as long as it has a site represented by the above formula (1) in a part of its structure. Specifically, diethylene glycol, triethylene glycol, tetra Oxyalkylene glycols such as ethylene glycol, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9, 9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-hydride) Xyloxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5 -Dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene 9,9-bis (4- (3-hydroxy-2,2- Compounds having an aromatic group in the side chain and an ether group bonded to the aromatic group in the main chain, such as phenyl-substituted fluorene such as dimethylpropoxy) phenyl) fluorene, a dihydroxy compound represented by the following formula (4), and Examples thereof include compounds having a cyclic ether structure such as spiroglycol represented by the following formula (5) and the following formula (6).
Among these dihydroxy compounds, oxyalkylene glycols such as diethylene glycol and triethylene glycol from the viewpoint of easy availability, ease of handling, reactivity during polymerization, and hue of the obtained polycarbonate resin and polycarbonate resin composition And a compound having a cyclic ether structure are preferred, and among the compounds having a cyclic ether structure, those having a plurality of ring structures are preferred.
Among these, from the viewpoint of heat resistance, compounds having a cyclic ether structure, represented by dihydroxy compounds represented by the following formulas (4), (5) and (6), are preferable, and have a cyclic ether structure. Among the compounds, those having a plurality of ring structures are preferable. Furthermore, anhydrous sugar alcohols represented by dihydroxy compounds represented by the following formula (4) are preferred.

  These may be used alone or in combination of two or more depending on the required performance of the polycarbonate resin and polycarbonate resin composition to be obtained.

Examples of the dihydroxy compound represented by the above formula (4) include isosorbide, isomannide and isoidet which are in a stereoisomeric relationship, and these may be used alone or in combination of two or more. May be.
Among these dihydroxy compounds, it is preferable to use a dihydroxy compound having no aromatic ring structure from the viewpoint of light resistance of the polycarbonate resin and the polycarbonate resin composition, and among them, it is abundant as a plant-derived resource and can be easily obtained. Isosorbide obtained by dehydrating condensation of sorbitol produced from various starches is most preferable from the viewpoints of availability and production, light resistance, optical properties, moldability, heat resistance, and carbon neutral.

  The polycarbonate resin used in the present invention may contain a structural unit derived from a dihydroxy compound other than the above-mentioned dihydroxy compound of the present invention (hereinafter may be referred to as “other dihydroxy compound”). Are ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6 -Hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecanedimethanol, 2,6-decalin dimethanol, 1, 5-decalindimethanol, 2,3-deca Dihydroxy compounds of aliphatic hydrocarbons such as 1,2-norbornanedimethanol, 2,5-norbornanedimethanol, 1,3-adamantanedimethanol, 2,2-bis (4-hydroxyphenyl) propane [= Bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis ( 4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4 '-Dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) Nyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) Sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dichlorodiphenyl ether, 9,9-bis (4 Aromatic bisphenols such as-(2-hydroxyethoxy-2-methyl) phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-2-methylphenyl) fluorene Among the dihydroxy compounds of aliphatic hydrocarbons, 1, 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, Dihydroxy compounds of alicyclic hydrocarbons such as 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, and 1,3-adamantane dimethanol are preferred.

  Among them, from the viewpoint of light resistance of the polycarbonate resin and the polycarbonate resin composition, a dihydroxy compound having no aromatic ring structure in the molecular structure, that is, an aliphatic hydrocarbon dihydroxy compound is preferable, and among them, an alicyclic hydrocarbon dihydroxy compound is preferable. Compounds are more preferred. As the aliphatic hydrocarbon dihydroxy compound, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, and tricyclodecane dimethanol are particularly preferable. As the dihydroxy compound of the formula hydrocarbon, 1,4-cyclohexanedimethanol and tricyclodecane dimethanol are particularly preferable.

By using these other dihydroxy compounds, it is possible to obtain effects such as improved flexibility, improved heat resistance, and improved moldability of the polycarbonate resin and the polycarbonate resin composition. When the content ratio of the derived structural unit is too large, the mechanical properties and heat resistance may be decreased. Therefore, the structural unit derived from the dihydroxy compound of the present invention with respect to the structural unit derived from all dihydroxy compounds. The ratio is usually 10 mol% or more, preferably 15 mol% or more, more preferably 20 mol% or more.
The dihydroxy compound of the present invention may contain a stabilizer such as a reducing agent, antioxidant, oxygen scavenger, light stabilizer, antacid, pH stabilizer, heat stabilizer, etc. Since the dihydroxy compound is easily altered, it is preferable to include a basic stabilizer. Basic stabilizers include group 1 or group 2 metal hydroxides, carbonates, phosphates, phosphites, hypophosphites in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). , Borate, fatty acid salt, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethyl Methylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium Basic ammonium compounds such as nium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide, 4-aminopyridine, 2-aminopyridine, N, N -Dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole And amine compounds such as aminoquinoline. Of these, Na or K phosphates and phosphites are preferred, and hydrogen phosphate 2Na and hydrogen phosphite 2Na are particularly preferred, because of their effects and ease of distillation removal described below.

  The content of these basic stabilizers in the dihydroxy compound of the present invention is not particularly limited. However, if the amount is too small, the effect of preventing alteration of the dihydroxy compound of the present invention may not be obtained. Since it may cause modification of the dihydroxy compound of the invention, it is usually 0.0001% by mass or more, preferably 0.001% by mass or more, and usually 1% by mass or less, preferably with respect to the dihydroxy compound of the invention. Is 0.1% by mass or less.

  Further, when the dihydroxy compound of the present invention containing these basic stabilizers is used as a raw material for the production of polycarbonate resin, the basic stabilizer itself becomes a polymerization catalyst, which makes it difficult to control the polymerization rate and quality, as well as the initial stage. In order to affect the hue and consequently affect the light resistance of the polycarbonate resin molded product, it is preferable to remove the basic stabilizer by ion exchange resin or distillation before using it as a raw material for producing the polycarbonate resin.

  When the dihydroxy compound of the present invention has a cyclic ether structure such as isosorbide, it is likely to be gradually oxidized by oxygen. It is important to use an oxygen agent or the like or handle it under a nitrogen atmosphere. When isosorbide is oxidized, decomposition products such as formic acid may be generated. For example, when isosorbide containing these decomposition products is used as a raw material for the production of a polycarbonate resin, there is a possibility that the resulting polycarbonate resin and further the polycarbonate resin composition may be colored, and that the physical properties may be significantly deteriorated. In some cases, the polymerization reaction is affected and a high molecular weight polymer cannot be obtained.

In order to obtain the dihydroxy compound of the present invention which does not contain the above oxidative decomposition product, and in order to remove the above basic stabilizer, it is preferable to carry out distillation purification. The distillation in this case may be simple distillation or continuous distillation, and is not particularly limited. As distillation conditions, it is preferable to carry out distillation under reduced pressure in an inert gas atmosphere such as argon or nitrogen. In order to suppress thermal denaturation, it is usually 250 ° C. or lower, preferably 200 ° C. or lower, especially It is preferable to carry out on the conditions of 180 degrees C or less.
By such distillation purification, the dihydroxy compound of the present invention is contained by setting the formic acid content in the dihydroxy compound of the present invention to 20 mass ppm or less, preferably 10 mass ppm or less, particularly preferably 5 mass ppm or less. When a dihydroxy compound is used as a raw material for producing a polycarbonate resin, it becomes possible to produce a polycarbonate resin and a polycarbonate resin composition excellent in hue and thermal stability without impairing polymerization reactivity. The formic acid content is measured by ion chromatography.

(Carbonated diester)
The polycarbonate resin used in the present invention can be obtained by polycondensation by a transesterification reaction using the above-mentioned dihydroxy compound containing the dihydroxy compound of the present invention and a carbonic acid diester as raw materials.
As a carbonic acid diester used, what is normally represented by following formula (3) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.

上記式（３）において、Ａ^１およびＡ^２は、それぞれ置換もしくは無置換の炭素数１〜１８の脂肪族基または置換もしくは無置換の芳香族基であり、Ａ^１とＡ^２とは同一であっても異なっていてもよい。

In the above formula (3), A ¹ and A ² are each a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic group, and A ¹ and A ² are the same. It may or may not be.

  Examples of the carbonic acid diester represented by the above formula (3) include substituted diphenyl carbonate such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, preferably diphenyl carbonate. Carbonates and substituted diphenyl carbonates, particularly preferably diphenyl carbonate. Carbonic acid diesters may contain impurities such as chloride ions, which may inhibit the polymerization reaction or affect the hue of the resulting polycarbonate resin and polycarbonate resin composition. It is preferable to use a product purified by distillation or the like.

(Transesterification reaction catalyst)
The polycarbonate resin used in the present invention is produced by transesterifying the dihydroxy compound containing the dihydroxy compound of the present invention and the carbonic acid diester represented by the above formula (3) as described above to produce a polycarbonate resin. More specifically, it can be obtained by transesterification and removing by-product monohydroxy compounds and the like out of the system. In this case, polycondensation is usually carried out by transesterification in the presence of a transesterification catalyst.

The transesterification reaction catalyst (hereinafter simply referred to as a catalyst or a polymerization catalyst) that can be used in the production of the polycarbonate resin used in the present invention has an influence on the light transmittance at a wavelength of 350 nm and the yellow index (YI) value. Can give.
As the catalyst used, any of the light resistance, transparency, hue, heat resistance, thermal stability, moldability, and mechanical strength of the manufactured polycarbonate resin composition can satisfy the light resistance. Without limitation, metal compounds, basic boron compounds, basic phosphorus compounds of Group 1 or Group 2 (hereinafter simply referred to as “Group 1” or “Group 2”) in the long-period periodic table, Examples include basic compounds such as basic ammonium compounds and amine compounds. Preferably, Group 1 metal compounds and / or Group 2 metal compounds are used. These may be used alone or in combination of two or more.

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

  The group 1 metal compound is a compound containing a group 1 metal such as lithium, potassium, and cesium, and more specifically, sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide. Sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, stearin Lithium acid, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium phenyl borohydride, potassium phenyl borohydride, lithium phenyl borohydride, cesium phenyl borohydride, benzoic acid Thorium, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenyl phosphate, dipotassium phenyl phosphate, Examples include dilithium phenylphosphate, dicesium phenylphosphate, sodium, potassium, lithium, cesium alcoholate, phenolate, disodium salt of bisphenol A, 2 potassium salt, 2 lithium salt, 2 cesium salt, etc. Lithium compounds are preferred.

  The group 2 metal compound is a compound containing a group 2 metal such as magnesium, calcium, strontium, and barium, and more specifically, calcium hydroxide, barium hydroxide, magnesium hydroxide, Strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate , Magnesium stearate, strontium stearate, etc., among which magnesium compounds, calcium compounds and barium compounds are preferred, and the polycarbonate resin composition obtained with polymerization activity is preferable. In terms of phase, more preferably a magnesium compound and / or calcium compound, most preferably a calcium compound.

  Examples of the basic boron compound include tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl. Examples include sodium, potassium, lithium, calcium, barium, magnesium, or strontium salts such as boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, etc. It is done.

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

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

  The amount of the polymerization catalyst used is usually 0.1 μmol or more, preferably 0.5 μmol or more, usually 300 μmol or less, preferably 100 μmol or less, per 1 mol of all dihydroxy compounds used in the polymerization. In particular, when using a compound containing at least one metal selected from the group consisting of lithium and Group 2 in the long-period periodic table, particularly when using a magnesium compound and / or a calcium compound, the amount of metal is The amount is usually 0.1 μmol or more, preferably 0.5 μmol or more, particularly preferably 0.7 μmol or more, per 1 mol of the dihydroxy compound. Further, the upper limit is usually 20 μmol, preferably 10 μmol, more preferably 3 μmol, particularly preferably 1.5 μmol, and most preferably 1.0 μmol.

  If the amount of the catalyst is too small, the polymerization rate is slowed down. As a result, when obtaining a polycarbonate resin having a desired molecular weight, the polymerization temperature has to be increased, and the hue of the obtained polycarbonate resin and polycarbonate resin composition is reduced. Or the light resistance, or the unreacted raw material is volatilized during the polymerization, and the molar ratio of the dihydroxy compound containing the dihydroxy compound of the present invention to the carbonic acid diester represented by the formula (3) collapses, and the desired molecular weight There is a possibility of not reaching. On the other hand, when there is too much usage-amount of a polymerization catalyst, there exists a possibility of affecting the hue and light resistance of the polycarbonate resin and polycarbonate resin composition which are obtained.

Further, when a group 1 metal, especially lithium, sodium, potassium, cesium, especially sodium, potassium, cesium, is contained in a large amount in the polycarbonate resin composition, the hue may be adversely affected, and the metal is a catalyst used. The total amount of these in the polycarbonate resin composition is usually 1 ppm by mass or less, preferably 0.8 ppm by mass or less, more preferably, as the amount of metal. Is 0.7 ppm by mass or less.
The amount of metal in the polycarbonate resin and the polycarbonate resin composition can be determined by recovering the metal in the polycarbonate resin composition by a method such as wet ashing, and then using a method such as atomic emission, atomic absorption, or inductively coupled plasma (ICP). Can be measured.

  Furthermore, when the polycarbonate resin used in the present invention is produced by using substituted diphenyl carbonate such as diphenyl carbonate and ditolyl carbonate as the carbonic acid diester represented by the formula (3), phenol and substituted phenol are by-produced to produce polycarbonate. It remains in the resin and is unavoidable to be contained in the polycarbonate resin composition, but since phenol and substituted phenol also have an aromatic ring, it not only absorbs ultraviolet rays but may affect light resistance. , It may cause odor during molding. The polycarbonate resin contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of 1000 mass ppm or more after a normal batch reaction, but from the viewpoint of light resistance and odor reduction, it is removed. Using a horizontal reactor excellent in volatility and an extruder with a vacuum vent, the aromatic monohydroxy compound in the polycarbonate resin is 700 ppm by mass or less, preferably 500 ppm by mass or less, particularly 300 ppm by mass or less. It is preferable. However, it is difficult to remove completely industrially, and the lower limit of the content of the aromatic monohydroxy compound is usually 1 ppm by mass.

  These aromatic monohydroxy compounds may naturally have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.

<Manufacturing method>
The polycarbonate resin used in the present invention and the polycarbonate resin composition of the present invention can be obtained by polycondensing the dihydroxy compound containing the dihydroxy compound of the present invention and the carbonic acid diester of the above formula (3) by a transesterification reaction. The raw material dihydroxy compound and carbonic acid diester are preferably mixed uniformly before the transesterification reaction.
The compound of the formula (2) in the present invention is prepared by mixing the polycarbonate resin and the compound of the formula (2) after producing the polycarbonate resin used in the present invention. However, when producing the polycarbonate resin used in the present invention, it is preferable to carry out a transesterification reaction in the presence of the compound of the formula (2) to obtain the polycarbonate resin composition of the present invention. . The compound of the formula (2) can be mixed in the reaction system at any timing during the transesterification reaction before the transesterification reaction, but from the viewpoint of suppressing thermal degradation of the dihydroxy compound, the compound of the formula (2) Is most preferably mixed at the same time as the mixing of the dihydroxy compound and carbonic acid diester. The compound of the formula (2) does not contribute to the reaction other than the raw material, which is mixed with the solid raw material among the carbonic acid diester and dihydroxy compound as raw materials and charged into the mixing tank, or dissolved or dispersed in the liquid raw material. It can be charged by a method such as uniformly dissolving or dispersing in a solvent.

  The mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, particularly preferably 100 ° C. or higher. The upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower, and particularly preferably 120 ° C. or lower. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, and this may often affect solidification and the like. If the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated, resulting in a change in the hue of the polycarbonate resin and the polycarbonate resin composition obtained, which may affect the light resistance.

  The operation of mixing the dihydroxy compound containing the dihydroxy compound of the present invention which is the raw material of the polycarbonate resin used in the present invention and the carbonic acid diester represented by the formula (3) is usually an oxygen concentration of 0.0001% by volume or more, Usually, it is preferably performed in an atmosphere of 10% by volume or less, preferably 5% by volume or less, particularly preferably 1% by volume or less, from the viewpoint of influence on the hue.

In order to obtain the polycarbonate resin used in the present invention, the carbonic acid diester represented by the formula (3) is usually 0.90 or more with respect to the dihydroxy compound containing the dihydroxy compound of the present invention used in the reaction, preferably, It is preferably used in a molar ratio of 0.95 or more, and usually used in a molar ratio of 1.20 or less, preferably 1.10 or less.
When this molar ratio decreases, the terminal hydroxyl group of the produced polycarbonate resin increases, which affects the thermal stability of the polymer, causing coloration during molding, reducing the rate of transesterification, and reducing the desired high Molecular weight may not be obtained.

Moreover, when this molar ratio becomes large, the rate of transesterification may decrease, or it may be difficult to produce a polycarbonate having a desired molecular weight. The decrease in the transesterification reaction rate increases the heat history during the polycondensation reaction, and may affect the hue and light resistance of the resulting polycarbonate resin and polycarbonate resin composition.
Furthermore, when the molar ratio of the carbonic acid diester represented by the formula (3) is increased with respect to the dihydroxy compound containing the dihydroxy compound of the present invention, the amount of residual carbonic acid diester in the obtained polycarbonate resin is increased, and the polycarbonate resin composition The carbonic acid diester content in the product also increases. These may absorb ultraviolet rays and affect the light resistance of the polycarbonate resin composition. The concentration of the carbonic acid diester in the polycarbonate resin composition of the present invention is preferably 60 ppm by mass or less, more preferably 40 ppm by mass or less, and particularly preferably 30 ppm by mass or less. Actually, the polycarbonate resin composition may contain an unreacted carbonic acid diester, and the lower limit of the concentration is usually 1 ppm by mass.

  In the present invention, the method of polycondensing a dihydroxy compound and a carbonic acid diester is usually carried out in multiple stages using a plurality of reactors in the presence of the above-mentioned catalyst. The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type. In the initial stage of the polycondensation reaction, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum, and in the latter stage of polymerization, it is preferable to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum. It is important from the viewpoints of hue and light resistance to appropriately select the jacket temperature and the internal temperature and the pressure in the reaction system. For example, if either the temperature or the pressure is changed too quickly before the polycondensation reaction reaches a predetermined value, the unreacted monomer will be distilled off, causing the molar ratio of the dihydroxy compound and the carbonic acid diester to change, resulting in a polycondensation rate. Or a polymer having a predetermined molecular weight or terminal group cannot be obtained, and as a result, the object of the present invention may not be achieved.

  Furthermore, it is effective to use a reflux condenser in the reactor for performing polycondensation in order to suppress the amount of the monomer to be distilled off. large. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected depending on the monomer used, but the temperature of the refrigerant introduced into the reflux condenser is usually 45 ° C. or more at the inlet of the reflux condenser. Preferably it is 80 degreeC or more, Most preferably, it is 100 degreeC or more, Usually, 180 degreeC or less, Preferably it is 150 degreeC or less, Most preferably, it is 130 degreeC or less. If the temperature of the refrigerant introduced into the reflux condenser is too high, the reflux amount is reduced and the effect is reduced. If it is too low, the distillation efficiency of the monohydroxy compound to be originally distilled tends to be reduced. As the refrigerant, hot water, steam, heat medium oil or the like is used, and steam or heat medium oil is preferable.

In order to maintain the polycondensation rate appropriately and suppress the distillation of the monomer, while maintaining the hue, thermal stability, light resistance, etc. of the final polycarbonate resin composition, The selection of the quantity is important.
The polycarbonate resin used in the present invention is preferably produced by polycondensation in multiple stages using a plurality of reactors using a catalyst. The reason for carrying out polycondensation in a plurality of reactors is the polycondensation reaction. In the initial stage, since there are many monomers in the reaction solution, it is important to suppress the volatilization of the monomers while maintaining the necessary polycondensation reaction rate. In the latter stage of the polycondensation reaction, the equilibrium is polycondensed. This is because it is important to sufficiently distill off the by-produced monohydroxy compound for shifting to the side. Thus, in order to set different polycondensation reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of polycondensation reactors arranged in series.

As described above, the reactor used in the method for producing the polycarbonate resin used in the present invention may be at least two or more, but from the viewpoint of production efficiency, preferably three or more, more preferably 3 to 5, particularly preferably 4.
In the present invention, if there are two or more reactors, a plurality of reaction stages having different conditions may be provided in the reactor, or the temperature and pressure may be continuously changed.

In the present invention, the catalyst used for polycondensation can be mixed in the raw material preparation tank and the raw material storage tank, or can be directly mixed in the polycondensation reaction tank, but from the viewpoint of supply stability and control of the polycondensation reaction. Is provided with a catalyst supply line in the middle of the raw material line before being supplied to the polycondensation reaction tank, and preferably supplied as an aqueous solution.
If the temperature of the polycondensation reaction is too low, the productivity will decrease and the thermal history of the product will increase, and if it is too high, not only will the monomer be volatilized, but it will also promote the decomposition and coloring of the polycarbonate resin and polycarbonate resin composition. there's a possibility that.

  Specifically, in the first stage reaction, the maximum internal temperature of the polycondensation reactor is usually 140 ° C. or higher, preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and usually 270 ° C. or lower, preferably Is 240 ° C. or lower, more preferably 230 ° C. or lower, usually 1 kPa or higher, preferably 5 kPa or higher, more preferably 10 kPa or higher, usually 110 kPa or lower, preferably 70 kPa or lower, more preferably 30 kPa or lower (absolute pressure). The reaction is usually performed for 0.1 hour or longer, preferably 0.5 hours or longer, usually 10 hours or shorter, preferably 3 hours or shorter, while distilling off the generated monohydroxy compound to the outside of the reaction system.

  In the second and subsequent stages, the pressure in the reaction system is gradually reduced from the pressure in the first stage, and the monohydroxy compound that is subsequently generated is removed from the reaction system. The maximum internal temperature is usually 210 ° C. or higher, preferably 220 ° C. or higher, usually 270 ° C. or lower, preferably 250 ° C. or lower, usually 0.1 hours or longer, preferably 0.5 hours. As mentioned above, it is performed for 1 hour or more, usually 10 hours or less, preferably 6 hours or less, particularly preferably 3 hours or less.

  In particular, in order to suppress the coloration and thermal deterioration of the polycarbonate resin and the polycarbonate resin composition and obtain a polycarbonate resin and a polycarbonate resin composition having good hue and light resistance, the maximum internal temperature in all reaction stages is less than 250 ° C., In particular, the temperature is preferably 225 ° C to 245 ° C. In order to prevent the polycondensation reaction rate from decreasing in the latter half of the polycondensation reaction and minimize deterioration due to thermal history, a horizontal reactor with excellent plug flow and interface renewability is used at the final stage of polymerization. It is preferable to do.

If the polycondensation temperature is increased and the polycondensation time is too long in order to obtain a polycarbonate resin having a predetermined molecular weight, the ultraviolet transmittance tends to decrease and the YI value tends to increase.
The monohydroxy compound produced as a by-product is preferably reused as a raw material for diphenyl carbonate, bisphenol A, etc. after purification as necessary from the viewpoint of effective utilization of resources.
The polycarbonate resin used in the present invention is usually cooled and solidified after polycondensation as described above, and pelletized with a rotary cutter or the like.

  The method of pelletization is not limited, but it is extracted from the final polycondensation reactor in a molten state, cooled and solidified in the form of a strand and pelletized, uniaxial or biaxial in the molten state from the final polycondensation reactor. The resin is supplied to the extruder, melt-extruded, cooled and solidified into pellets, or extracted from the final polycondensation reactor in a molten state, cooled and solidified in the form of strands, and once pelletized Examples thereof include a method in which a resin is again supplied to a single-screw or twin-screw extruder, melt-extruded, and then cooled and solidified to be pelletized.

At that time, in the extruder, the residual monomer under reduced pressure devolatilization, and generally known heat stabilizer, neutralizer, light stabilizer, mold release agent, colorant, antistatic agent, lubricant, lubricant, A plasticizer, a compatibilizer, a flame retardant, etc. can be added and kneaded.
The melt kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the polycarbonate resin, but is usually 150 ° C. or higher, preferably 200 ° C. or higher, more preferably 230 ° C. or higher, and usually 300 ° C. or lower, preferably It is 270 degrees C or less, More preferably, it is 260 degrees C or less. When the melt-kneading temperature is lower than 150 ° C., the melt viscosity of the polycarbonate resin is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 300 ° C., the thermal deterioration of the polycarbonate becomes severe, resulting in a decrease in mechanical strength due to a decrease in molecular weight, coloring, and gas generation.

  When the polycarbonate resin used in the present invention is produced, it is desirable to install a filter in order to prevent foreign substances from entering. The filter installation position is preferably on the downstream side of the extruder, and the filter foreign matter removal size (opening) is usually preferably 100 μm or less as 99% removal filtration accuracy. In particular, in the case of disagreeing with the entry of minute foreign matters for film applications, 40 μm or less is preferable, and 10 μm or less is more preferable.

Extrusion of the polycarbonate resin used in the present invention is preferably performed in a class 7 defined in JIS B 9920 (2002), more preferably in a clean room having a higher cleanliness than class 6 in order to prevent foreign matter from being mixed after extrusion. It is desirable to implement.
Moreover, when cooling the extruded polycarbonate resin into chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign substances in the air. When water cooling is used, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. The opening of the filter to be used is preferably 10 μm to 0.45 μm as 99% removal filtration accuracy.

The molecular weight of the polycarbonate resin of the present invention thus obtained can be expressed by a reduced viscosity, and the reduced viscosity is usually 0.30 dL / g or more, preferably 0.35 dL / g or more, The upper limit is more preferably 1.20 dL / g or less and 1.00 dL / g or less, and still more preferably 0.80 dL / g or less.
If the reduced viscosity of the polycarbonate resin is too low, the mechanical strength of the molded product may be small. If it is too large, the fluidity at the time of molding tends to decrease, and the productivity and moldability tend to decrease.

The reduced viscosity is measured using a Ubbelohde viscometer tube at a temperature of 20.0 ° C. ± 0.1 ° C., using methylene chloride as a solvent and adjusting the concentration of the polycarbonate solution to 0.6 g / dL.
Further, the lower limit amount of the terminal group concentration (terminal phenyl group concentration) represented by the following formula (7) in the polycarbonate resin of the present invention is preferably 20 μeq / g, more preferably 40 μeq / g, and particularly preferably 50 μeq / g. The upper limit is preferably 160 μeq / g, more preferably 140 μeq / g, and particularly preferably 100 μeq / g.

In the polycarbonate resin used in the present invention, if the concentration of the end group represented by the following formula (7) is too high, the hue after exposure to ultraviolet rays may be affected even if the hue immediately after polycondensation or molding is good. On the other hand, if it is too low, the thermal stability may be lowered.
In order to control the concentration of the terminal group represented by the following formula (7), the molar ratio between the dihydroxy compound containing the dihydroxy compound of the present invention as the raw material and the carbonic acid diester represented by the formula (3) is controlled. And the type and amount of the catalyst during the transesterification reaction, a method for controlling the pressure and temperature during the polycondensation reaction, and the like.

Further, when the mole number of H bonded to the aromatic ring in the polycarbonate resin of the present invention is (A) and the mole number of H bonded to other than the aromatic ring is (B), the number of moles of H bonded to the aromatic ring. The ratio of the total H to the number of moles is represented by A / (A + B). However, since the aromatic ring having an ultraviolet absorbing ability may affect the light resistance as described above, A / (A + B) is preferably 0.05 or less, more preferably 0.04 or less, particularly preferably 0.02 or less, and preferably 0.01 or less. A / (A + B) can be quantified by ¹ H-NMR.

(2-2) Compound Represented by Formula (2) In the polycarbonate resin composition of the present invention, the compound represented by the following formula (2) is added in an amount of 0.001 to 0.00 with respect to 100 parts by mass of the polycarbonate resin. Contains 5 parts by mass.

In the above formula (2), Ar ¹ , Ar ² , and Ar ³ are aryl groups having 6 to 20 carbon atoms, and each may have an alkyl group having 1 to 10 carbon atoms as a substituent.
The aryl group represented by Ar ¹ , Ar ² , and Ar ³ may be any group as long as it has an aromatic attribute. More specifically, examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a chrysenyl group, a pyrenyl group, a benzopyrenyl group, and a perylenyl group. As carbon number of an aryl group, 6-14 are still more preferable, and especially a phenyl group is preferable. Ar ¹ , Ar ² , and Ar ³ may be the same or different from each other.
Examples of the substituent that the aryl group represented by Ar ¹ , Ar ² , or Ar ³ may have include an alkyl group having 1 to 10 carbon atoms, which may be linear or branched. It may be present, but preferably has a branched structure. Further, the number of carbon atoms is preferably 3 or more, particularly preferably 4 or more, more preferably 8 or less, and particularly preferably 6 or less. Of these, a tert-butyl group is particularly preferred.

Examples of the compound represented by the formula (2) include triphenyl phosphite, tris (2-isobutylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris (2- t-pentylphenyl) phosphite, tris (2-cyclohexylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2,6-di-t-butylphenyl) phosphite, And tris (2-t-butyl-6-methylphenyl) phosphite. Among them, tris (2-t-butyl-6-methylphenyl) phosphite, tris (2,4-di-t-butylphenyl) Phosphites are preferred.
Although there is no restriction | limiting in particular in the molecular weight of the compound part represented by Formula (2), Usually 300 or more are used, Preferably it is 400 or more, Especially preferably, it is 550 or more, Usually 1200 or less, Preferably it is 1000 or less, Especially preferably, it is 750 or less. Moreover, you may use together multiple types of compounds represented by Formula (2).

  In the polycarbonate resin composition of the present invention, the compound represented by the formula (2) is usually 0.001 part by mass or more, preferably 0.002 part by mass or more, particularly preferably 0 with respect to 100 parts by mass of the polycarbonate resin. 0.005 parts by mass or more, usually 0.5 parts by mass or less, preferably 0.3 parts by mass or less, particularly preferably 0.1 parts by mass or less. When the content of the compound represented by the formula (2) is within the above range, a polycarbonate resin composition excellent in transparency and excellent in hue after molding and a molded product thereof are obtained by suppressing coloring during molding. It becomes possible. On the other hand, when the content of the compound represented by the formula (2) is less than 0.001 part by mass, the coloring suppression effect at the time of molding may be insufficient. On the other hand, if the amount exceeds 0.5 parts by mass, the amount of deposits on the mold at the time of injection molding increases or the amount of deposits on the roll increases when the film is formed by extrusion molding. The surface appearance may be impaired.

  The polycarbonate resin composition of the present invention contains the compound represented by the formula (2), but the polycarbonate resin and the compound represented by the formula (2) may be mixed by any method. The polycarbonate resin may be obtained by mixing the compound represented by the formula (2), or when the polycarbonate resin is produced by polycondensation, for example, put into a reactor together with raw material monomers, You may mix in the process in the middle. In particular, from the viewpoint of preventing deterioration of the polycarbonate resin during the polycondensation reaction, it is preferable to mix in a step in the middle of producing the polycarbonate resin by polycondensation.

(2-3) Other ingredients (Bluing agent)
The polycarbonate resin composition of the present invention can contain a bluing agent as long as the object of the present invention is not impaired. The content of the bluing agent is preferably 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, particularly preferably 0.01 parts by mass or more, and most preferably 0 with respect to 100 parts by mass of the polycarbonate resin. 0.05 parts by mass or more, preferably 1 part by mass or less, more preferably 0.8 parts by mass or less, particularly preferably 0.5 parts by mass or less, and most preferably 0.15 parts by mass or less. As the bluing agent, known ones such as oil-soluble dyes typified by anthraquinone compounds can be used.

(Light stabilizer)
The polycarbonate resin composition of the present invention can contain a light-resistant stabilizer as long as the object of the present invention is not impaired. By including a light-resistant stabilizer in the polycarbonate resin composition, the difference in haze before and after the irradiation treatment using the sunshine carbon arc can be reduced, and a polycarbonate resin molded article excellent in transparency without being clouded. Obtainable. The light stabilizer content is preferably 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, particularly preferably 0.01 parts by mass or more, and most preferably 0, based on 100 parts by mass of the polycarbonate resin. 0.05 parts by mass or more, preferably 1 part by mass or less, more preferably 0.8 parts by mass or less, particularly preferably 0.5 parts by mass or less, and most preferably 0.15 parts by mass or less. When the content of the light stabilizer is too much, there is a tendency to color, whereas when it is too little, there is a tendency that a sufficient improvement effect for the weather resistance test cannot be obtained. The light-resistant stabilizer mainly has an action of preventing deterioration of a resin due to light such as ultraviolet rays and improving stability to light. Examples of the light-resistant stabilizer include an ultraviolet absorber that absorbs ultraviolet rays and a light stabilizer that has a radical scavenging action. As the light stabilizer, hindered amine is preferred.

(Release agent)
The polycarbonate resin composition of the present invention preferably further contains a release agent in order to further improve the releasability from the mold during melt molding. Release agents include higher fatty acids, higher fatty acid esters of mono- or polyhydric alcohols, natural animal waxes such as beeswax, natural plant waxes such as carnauba wax, natural petroleum waxes such as paraffin wax, and montan wax. Natural coal wax, olefin wax, silicone oil, organopolysiloxane and the like can be mentioned, and higher fatty acid and higher fatty acid ester of monohydric or polyhydric alcohol are particularly preferable.

  The higher fatty acid ester is preferably a partial ester or a total ester of a substituted or unsubstituted monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms. . Such partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbite, stearyl stearate, behenic acid monoglyceride, behenyl behenate, Pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate Sorbitan monostearate, 2-ethylhexyl stearate and the like. Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used.

  As the higher fatty acid, a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms is preferable. Examples of such saturated fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like. One of these release agents may be used alone, or two or more thereof may be mixed and used. The content of the release agent is preferably 0.0001 parts by mass or more, more preferably 0.01 parts by mass or more, particularly preferably 0.1 parts by mass or more, on the other hand, preferably 100 parts by mass of the polycarbonate resin. 1 part by mass or less, more preferably 0.7 part by mass or less, and particularly preferably 0.5 part by mass or less.

  In the present embodiment, the mixing timing and mixing method of the release agent to be blended with the polycarbonate resin are not particularly limited. As the mixing time, for example, when the polycarbonate resin is produced by the transesterification method, at the end of the polymerization reaction; and regardless of the polymerization method, the polycarbonate resin in the middle of kneading the polycarbonate resin and other compounding agents is melted A case where it is blended and kneaded with a polycarbonate resin in a solid state such as pellets or powder using an extruder or the like. As a mixing method, a method of directly mixing or kneading the release agent with a polycarbonate resin; a high-concentration masterbatch prepared by using a small amount of a polycarbonate resin or other resin and the release agent can also be mixed. .

(Antioxidant)
The polycarbonate resin composition of the present invention may contain an antioxidant other than the compound represented by the formula (2). In this case, an antioxidant different from the compound represented by the formula (2) is used. If it is different from the compound represented by formula (2), it may be a phosphorus-based antioxidant, and preferably a phosphite-based antioxidant, a phenol-based antioxidant, and a sulfur-based antioxidant. Can be mentioned.

Phosphite-based antioxidants As phosphite-based antioxidants, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, Monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylene bis (4,6 -Di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Distearyl pentaerythritol diphosphite etc. are mentioned.

  Among these, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite are preferably used. . These compounds can be used alone or in combination of two or more.

Here, the content of the phosphite antioxidant is preferably 0.0001 parts by mass or more, more preferably 0.0002 parts by mass or more, and particularly preferably 0.0003 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin. On the other hand, it is preferably 1 part by mass or less, more preferably 0.1 part by mass or less, and particularly preferably 0.01 part by mass or less.
If the content is too small, the effect of suppressing coloring during molding may be insufficient. Moreover, if the content is excessively large, the amount of deposits on the mold at the time of injection molding increases or the amount of deposits on the roll increases when the film is formed by extrusion molding. The surface appearance may be impaired.
The polycarbonate resin composition of the present invention preferably further contains a phenolic antioxidant.

-Phenol antioxidants Examples of phenol antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, Triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, 1 , 3,5-trimethyl-2,4,6-tris (3,5-di-tert-bul-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl- 4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4 , 4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane.

  Among these compounds, an aromatic monohydroxy compound substituted with one or more alkyl groups having 5 or more carbon atoms is preferable. Specifically, octadecyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the like, preferably pentaerythris Lithyl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate is more preferred.

Here, the content of the phenolic antioxidant is preferably 0.0001 parts by mass or more, more preferably 0.0002 parts by mass or more, and particularly preferably 0.0003 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin. On the other hand, it is preferably 1 part by mass or less, more preferably 0.1 part by mass or less, and particularly preferably 0.01 part by mass or less.
If the content is too small, the effect of suppressing coloring during molding may be insufficient. Moreover, if the content is excessively large, the amount of deposits on the mold at the time of injection molding increases or the amount of deposits on the roll increases when the film is formed by extrusion molding. The surface appearance may be impaired.

Sulfur-based antioxidants Examples of sulfur-based antioxidants include dilauryl-3,3′-thiodipropionic acid ester, ditridecyl-3,3′-thiodipropionic acid ester, and dimyristyl-3,3′-thiol. Dipropionate, distearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), bis [2- Methyl-4- (3-laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) Etc. Among the above, pentaerythritol tetrakis (3-lauryl thiopropionate) is preferable.

Here, the content of the sulfur-based antioxidant is preferably 0.0001 parts by mass or more, more preferably 0.0002 parts by mass or more, particularly preferably 0.0003 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin. On the other hand, it is preferably 1 part by mass or less, more preferably 0.1 part by mass or less, and particularly preferably 0.01 part by mass or less.
If the content is too small, the effect of suppressing coloring during molding may be insufficient. Moreover, if the content is excessively large, the amount of deposits on the mold at the time of injection molding increases or the amount of deposits on the roll increases when the film is formed by extrusion molding. The surface appearance may be impaired.

In the present embodiment, the mixing timing and mixing method of the antioxidant blended in the polycarbonate resin are not particularly limited. As the mixing time, for example, when the polycarbonate resin is produced by the transesterification method, at the end of the polymerization reaction; and regardless of the polymerization method, the polycarbonate resin in the middle of kneading the polycarbonate resin and other compounding agents is melted A case where it is blended and kneaded with a polycarbonate resin in a solid state such as pellets or powder using an extruder or the like. As a mixing method, a method of directly mixing or kneading the acid value inhibitor with a polycarbonate resin; a high-concentration master batch prepared using a small amount of a polycarbonate resin or other resin and the antioxidant may be mixed. it can.

(Acidic compounds)
The polycarbonate resin composition of the present invention may further contain an acidic compound.
The compounding amount of the acidic compound is preferably 0.00001 parts by mass or more, more preferably 0.0001 parts by mass or more, particularly preferably 0.0002 parts by mass with respect to 100 parts by mass of the polycarbonate resin. On the other hand, it is preferably 0.1 parts by mass or less, more preferably 0.01 parts by mass or less, and particularly preferably 0.001 parts by mass or less.
If the blending amount of the acidic compound is excessively small, it may not be possible to sufficiently suppress coloring when the residence time of the polycarbonate resin composition in the injection molding machine becomes long during injection molding. Moreover, when there are too many compounding quantities of an acidic compound, the hydrolysis resistance of a polycarbonate resin composition may fall remarkably.

  Examples of acidic compounds include hydrochloric acid, nitric acid, boric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, adipic acid, ascorbic acid, aspartic acid, azelaic acid, adenosine phosphoric acid, benzoic acid Acid, formic acid, valeric acid, citric acid, glycolic acid, glutamic acid, glutaric acid, cinnamic acid, succinic acid, acetic acid, tartaric acid, oxalic acid, p-toluenesulfinic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, nicotinic acid , Bronsted acids such as picric acid, picolinic acid, phthalic acid, terephthalic acid, propionic acid, benzenesulfinic acid, benzenesulfonic acid, malonic acid, maleic acid, and esters thereof. Among these acidic compounds or derivatives thereof, sulfonic acids or esters thereof are preferable, and p-toluenesulfonic acid, methyl p-toluenesulfonate, and butyl p-toluenesulfonate are particularly preferable.

These acidic compounds can be mixed in the manufacturing process of a polycarbonate resin composition as a compound which neutralizes the basic transesterification catalyst used in the polycondensation reaction of the polycarbonate resin mentioned above.
The polycarbonate resin composition of the present invention can contain an antistatic agent as long as the object of the present invention is not impaired.

Moreover, the polycarbonate resin composition of the present invention may contain an inorganic filler. The compounding quantity of an inorganic filler is normally 1 mass part or more with respect to 100 mass parts of polycarbonate resin, Preferably it is 3 mass parts or more, and is 100 mass parts or less normally, Preferably it is 50 mass parts or less. When the blending amount of the inorganic filler is excessively small, the reinforcing effect is small, and when it is excessively large, the appearance tends to deteriorate.
Examples of the inorganic filler include glass fiber, glass milled fiber, glass flake, glass bead, carbon fiber, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whisker, barium sulfate, talc, mica, and wallast. Calcium silicate such as knight; carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, potassium titanate fiber, whisker, etc. It is done. Among these, glass fiber filler, glass powder filler, glass flake filler; carbon fiber filler, carbon powder filler, carbon flake filler; various whiskers, mica Talc is preferred. More preferably, glass fiber, glass flake, glass milled fiber, carbon fiber, wollastonite, mica and talc are mentioned.

(2-4) Mixing method of compounding material In the polycarbonate resin composition of the present invention, the above components are mixed at the same time or in any order in a tumbler, V-type blender, Nauter mixer, Banbury mixer, kneading roll, extruder, etc. It can be produced by mixing with a machine. Furthermore, a nucleating agent, a flame retardant, an inorganic filler, an impact modifier, a foaming agent, a dye / pigment and the like that are usually used in the resin composition may be contained within a range not impairing the object of the present invention.

(3) Polycarbonate resin molded product In the present embodiment, a polycarbonate resin molded product obtained by molding the above-described polycarbonate resin composition is obtained. The method for molding the polycarbonate resin molded product is not particularly limited, but the injection molding method is preferable. Moreover, since the polycarbonate resin molded article of the present invention is excellent in light resistance and transparency, it can be used for road sound insulation walls, arcade ceiling sheets, arcade ceiling plates, facility roofs, facility wall materials, and the like.

  In addition, the polycarbonate resin composition of the present invention includes, for example, aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, ABS, AS and other synthetic resins, polylactic acid, polybutylene succin It can also be used as a polymer alloy by kneading with one or more of biodegradable resins such as nate and rubber.

  ADVANTAGE OF THE INVENTION According to this invention, the polycarbonate resin composition excellent in light resistance, transparency, a hue, heat resistance, heat stability, a moldability, and mechanical strength, and its molded article can be provided.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.
In the following, evaluation of physical properties or characteristics of polycarbonate resin, polycarbonate resin composition, molded article and the like was performed by the following method.

(1) Measurement of reduced viscosity A sample of a polycarbonate resin composition was dissolved using a mixed solution of phenol / 1,1,2,2-tetrachloroethane in a mass ratio of 1: 1 as a solvent, and 1.0 g / dL A concentrated polycarbonate solution was prepared. Using an Ubbelohde type viscosity tube, measurement was performed at a temperature of 30.0 ° C. ± 0.1 ° C., and a relative viscosity ηrel was obtained from the following equation from the solvent passage time t ₀ and the solution passage time t.
ηrel = t / t ₀
From the relative viscosity, the specific viscosity ηsp was determined from the following formula.

ηsp = (η−η ₀ ) / η ₀ = ηrel−1
The reduced viscosity ηsp / c was determined by dividing the specific viscosity by the concentration c (g / dL). The higher this value, the higher the molecular weight.

(2) Hue Measurement Using a spectral color difference meter (SE2000 manufactured by Nippon Denshoku Industries Co., Ltd.), the yellow index (YI) value of the pellets obtained in the following examples was measured by the C light source transmission method. The smaller the YI value, the better the quality without yellowness.

(3) Injection molding The pellets of the polycarbonate resin composition were dried at 90 ° C for 10 hours in a nitrogen atmosphere. Next, the pellets of the dried polycarbonate resin composition are supplied to an injection molding machine (J75EII type manufactured by Nippon Steel Co., Ltd.), and injection molded pieces (width 60 mm × length) under the conditions of a resin temperature of 220 ° C. and a molding cycle of 23 seconds. 60 mm × thickness 3 mm). Further, the molded piece was allowed to stand for 2 weeks under the condition of 50 ° C. × 50 RH%, and then the moldability was visually evaluated to confirm the presence or absence of bleed-out on the surface of the test piece.

The abbreviations of the compounds used in the description of the following examples are as follows.
ISB: Isosorbide (Rocket Fleure, trade name POLYSORB)
CHDM: 1,4-cyclohexanedimethanol (manufactured by Nippon Nippon Kayaku)
DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)
Irgafos 168: Tris (2,4-di-t-butylphenyl) phosphite (manufactured by BASF Japan Ltd.)

[Example 1]
ISB 77.54 parts by mass, CHDM 32.79 parts by mass, DPC 162.38 parts by mass, calcium acetate 1.50 × 10 ⁻⁴ parts by mass, and Irgafos 168 6.50 × 10 ⁻² parts by mass into a reaction vessel, nitrogen Under the atmosphere, the heating bath temperature was set to 210 ° C., and the raw materials were dissolved while stirring as necessary (about 10 minutes). After dissolution, the reaction was carried out at normal pressure for 60 minutes as the first step of the reaction. Next, the pressure was reduced from normal pressure to 13.3 KPa over 90 minutes, held at 13.3 KPa for 30 minutes, and the generated phenol was extracted out of the reaction vessel.
Next, as the second step of the reaction, while raising the temperature of the heating tank to 220 ° C. over 30 minutes, the pressure was reduced to 0.10 KPa or less over 60 minutes, and the generated phenol was extracted out of the reaction vessel. After reaching a predetermined torque, the reaction was terminated, and the produced polymer was extruded into water to obtain pellets of a polycarbonate resin composition. About the obtained polycarbonate resin composition, the synthetic amount of the polycarbonate resin theoretically obtained from the usage-amount of a raw material was calculated, and also content of Irgafos 168 with respect to 100 mass parts of polycarbonate resins was computed. Moreover, reduced viscosity, YI, and moldability were evaluated by the evaluation method described above. The obtained results are shown in Table 1.
The amount of polycarbonate resin synthesized was calculated by excluding the amount of phenol removed outside the reaction system from the total amount of raw materials used.

[Example 2]
A pellet of the polycarbonate resin composition was obtained in the same manner as in Example 1 except that the amount of Irgafos 168 used in Example 1 was changed to 2.50 × 10 ⁻² parts by mass. Various physical properties of the obtained polycarbonate resin composition were evaluated in the same manner as in Example 1. The obtained results are shown in Table 1.

[Comparative Example 1]
A polycarbonate resin pellet was obtained in the same manner as in Example 1 except that Irgafos 168 used in Example 1 was not used. Various physical properties of the obtained polycarbonate resin were evaluated in the same manner as in Example 1. The obtained results are shown in Table 1.
[Comparative Example 2]
A pellet of the polycarbonate resin composition was obtained in the same manner as in Example 1 except that the amount of Irgafos 168 used in Example 1 was 7.00 × 10 ⁻¹ parts by mass. Various physical properties of the obtained polycarbonate resin composition were evaluated in the same manner as in Example 1. The obtained results are shown in Table 1.

上記表１において、「−」はその材料を使用していないことを表す。

In the said Table 1, "-" represents that the material is not used.

  As is clear from the results in Table 1, the polycarbonate resin compositions of the present invention (Examples 1 and 2) have a suitable reduced viscosity, and further, both the hue and the moldability are compared with Comparative Examples 1 and 2. It was excellent. Also, no bleed out was seen.

  The polycarbonate resin composition of the present invention is not only excellent in transparency, but also excellent in hue, heat resistance, moldability, and mechanical strength, in the field of injection molding such as electrical / electronic parts and automotive parts, film, Sheet field, bottles and container fields that require heat resistance, and lens applications such as camera lenses, finder lenses, CCD and CMOS lenses, retardation films used in liquid crystals and plasma displays, diffusion sheets, polarized light Materials such as films, sheets, optical disks, optical materials, optical components, dyes, charge transfer agents and the like can be provided for a wide range of fields such as binder applications.

Claims (7)

A polycarbonate resin composition comprising at least a polycarbonate resin having a structural unit derived from a dihydroxy compound having a site represented by the following formula (1) in a part of the structure, the compound represented by the following formula (2): The polycarbonate resin composition which contains 0.001-0.5 mass part with respect to 100 mass parts of polycarbonate resin.

(Unless moiety represented by the formula (1) is part of _-CH 2 -O-H.)

(In Formula (2), Ar ¹ , Ar ² , and Ar ³ are each independently an aryl group having 6 to 20 carbon atoms, and may have an alkyl group having 1 to 10 carbon atoms as a substituent. ) In the presence of a catalyst and a compound represented by the formula (2), a combination of a dihydroxy compound having a site represented by the formula (1) in a part of the structure and a carbonic acid diester represented by the following formula (3) The polycarbonate resin composition according to claim 1 obtained by condensation.

(In the formula ^{(3), A 1, A} 2 is an aliphatic group or optionally substituted aromatic group, having 1 to 18 carbon atoms which may have a substituent, A ¹ and A ² may be the same or different.) The polycarbonate resin composition according to claim 1 or 2, wherein the dihydroxy compound having a site represented by the formula (1) is a compound represented by the following formula (4).

  The polycarbonate resin composition according to any one of claims 1 to 3, wherein the polycarbonate resin further comprises a structural unit derived from at least one compound selected from the group consisting of aliphatic hydrocarbon dihydroxy compounds. object.   5. The method according to claim 1, wherein the polycarbonate resin contains 90 mol% or less of a structural unit derived from a dihydroxy compound having a site represented by the formula (1) in a part of the structure. The polycarbonate resin composition as described.   A polycarbonate resin molded article obtained by molding the polycarbonate resin composition according to any one of claims 1 to 5.   The polycarbonate resin molded product formed by injection-molding the polycarbonate resin composition of any one of Claims 1-5.