JP2015189917A - Polycarbonate resin composition and molded article using the same, film, plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition which is provided with antistatic properties and has excellent haze, yellow index values (YI) or the like.SOLUTION: There is provided a polycarbonate resin composition which comprises 0.05 pts.wt. or more and less than 1 pt.wt. of an alkanesulfonic acid salt, based on 100 pts.mass of a polycarbonate resin which contains a structural unit derived from a dihydroxy compound having a cyclic ether structure and is produced by using at least one metal compound selected from a magnesium compound and a calcium compound as a transesterification catalyst.

Description

  The present invention relates to a polycarbonate resin composition excellent in haze, yellow index value (YI) and the like and imparted with antistatic properties, and a molded article, film and plate formed by molding the same.

  Polycarbonate is generally produced using raw materials derived from petroleum resources. However, in recent years, there is a concern about the exhaustion of petroleum resources, and there is a demand for providing polycarbonate using raw materials obtained from biomass resources such as plants. In addition, it is feared that global warming due to the increase and accumulation of carbon dioxide emissions will lead to climate change, etc., so that carbon-neutral plant-derived monomers are used as raw materials even after disposal after use. There is a need to develop polycarbonate. Among them, there is a demand for a polycarbonate resin that is imparted with antistatic properties and excellent in haze, yellow index value (YI) and the like for use in the building material field, electrical / electronic field, automobile field, optical part field, and the like.

Conventionally, various polycarbonates using plant-derived monomers as raw materials have been developed.
For example, it has been proposed to use isosorbide as a plant-derived monomer and obtain a polycarbonate by transesterification with diphenyl carbonate (see, for example, Patent Document 1). Moreover, by copolymerizing isosorbide and an aliphatic diol (for example, refer to Patent Document 2) or polymerizing 1,4-cyclohexanedimethanol which is an alicyclic dihydroxy compound (for example, refer to Patent Document 3), Attempts have been made to improve the physical properties of homopolycarbonate resins comprising isosorbide. Further, it has been proposed to improve the haze, yellow index value (YI), etc. of polycarbonate using isosorbide as a raw material by considering the polymerization temperature and catalyst of the polycarbonate, or containing a bluing agent (for example, (See Patent Document 4).
On the other hand, the polycarbonate which can prevent electrification by containing an antistatic agent with respect to aromatic polycarbonate resin is proposed (for example, refer to patent documents 5).
Furthermore, it is described that a sulfonic acid metal salt flame retardant is added to a polycarbonate using isosorbide as a raw material (see, for example, Patent Document 6).

British Patent No. 1079686 International Publication No. 04/111106 Pamphlet JP 2008-024919 A JP 2012-214665 A JP 2002-020609 A JP 2011-021171 A

However, in the inventions described in Cited Documents 1 to 4, no attention has been paid to the antistatic property of the polycarbonate using isosorbide as a raw material, and no measures are taken to improve the antistatic property. However, it is not satisfactory from the viewpoint of antistatic properties.
Further, with respect to the cited document 5, attention is not paid to the polycarbonate using isosorbide as a raw material. Furthermore, although Cited Document 6 suggests adding a sulfonic acid metal salt-based flame retardant to a polycarbonate made from isosorbide as a raw material, its effect is also different. As described above, the optimum content and production method capable of obtaining an antistatic effect while improving the haze, yellow index value (YI), and the like of polycarbonate using isosorbide as a raw material are substantially disclosed. Absent.

  The object of the present invention is to eliminate the above-mentioned conventional problems and to be used in the building material field, the electric / electronic field, the automobile field, the optical part field, etc., so that antistatic properties are imparted, and haze, yellow index value (YI), etc. It is in providing the polycarbonate resin composition which is excellent in this, and the molded article, film, and plate which shape | mold this.

  As a result of investigations by the present inventors, a specific ratio of a polycarbonate resin containing a structural unit derived from a dihydroxy compound having a specific site and an alkane sulfonate produced using a specific transesterification catalyst is used. If it is a polycarbonate resin composition, it is excellent in haze, yellow index value (YI), etc., which can be suitably used in the building material field, electrical / electronic field, automobile field, optical part field, etc. It discovered that the polycarbonate resin composition to which the preventive property was provided was realizable, and came to complete this invention.

That is, the gist of the present invention resides in the following [1] to [11].
[1] comprising a structural unit derived from a dihydroxy compound having a cyclic ether structure,
0.05 parts by weight or more of alkane sulfonates with respect to 100 parts by weight of a polycarbonate resin produced using at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds as a transesterification reaction catalyst A polycarbonate resin composition containing less than parts by weight.
[2] 100 parts by mass of a polycarbonate resin containing a structural unit derived from a dihydroxy compound having a cyclic ether structure, containing 0.05 part by weight or more and less than 1 part by weight of an alkane sulfonate, and molded from the polycarbonate resin composition The polycarbonate resin composition according to the above [1], wherein the molded product having a thickness of 2 mm has a total light transmittance of 60% or more.
[3] The polycarbonate resin composition according to the above [1] or [2], which contains a release agent.
[4] The polycarbonate resin composition according to any one of [1] to [3], which contains an antioxidant.
[5] The polycarbonate resin composition according to any one of [1] to [4], which contains a phosphite compound as an antioxidant.
[6] The polycarbonate resin composition according to any one of [1] to [5], wherein the dihydroxy compound having a cyclic ether structure is a dihydroxy compound having a structure represented by the following formula (1).
[7] The polycarbonate resin composition according to any one of [1] to [6], wherein the polycarbonate resin includes a structural unit derived from an aliphatic dihydroxy compound.
[8] A polycarbonate resin molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [7].
[9] The polycarbonate resin molded product according to [8], wherein the polycarbonate resin molded product is obtained by molding by an injection molding method.
[10] A film obtained by molding the polycarbonate resin composition according to any one of [1] to [7].
[11] A plate obtained by molding the polycarbonate resin composition according to any one of [1] to [7].

  According to the present invention, the charging property is improved, the material has excellent properties such as haze and yellow index value (YI), and is preferably used in the building material field, the electric / electronic field, the automobile field, the optical part field, and the like. Can be provided, and a molded article, a film, and a plate formed by molding the polycarbonate resin composition.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. However, the description of constituent elements described below is an example (representative example) of an embodiment of the present invention, and the aspect of the present invention does not exceed the gist thereof. However, the present invention is not limited to the following contents. In the present specification, “to” is used as an expression including numerical values or physical quantities before and after. In addition, when the expression “substituent” is used in the present specification, the type of the substituent is not limited unless otherwise specified, and it means one having a molecular weight of up to 200.

[Polycarbonate resin composition]
The polycarbonate resin composition of the present invention includes a structural unit derived from a dihydroxy compound having a cyclic ether structure, and uses at least one metal compound selected from the group consisting of a magnesium compound and a calcium compound as a transesterification reaction catalyst. This is a polycarbonate resin composition containing 0.05 part by weight or more and less than 1 part by weight of alkanesulfonate with respect to 100 parts by weight of the produced polycarbonate resin.

The polycarbonate resin composition having such a structure is imparted with antistatic properties and has excellent physical properties such as haze and yellow index value (YI), so that it is in the building material field, electrical / electronic field, automotive field, optical component field. It can use suitably in uses, such as.
When the alkanesulfonic acid salt is less than 0.05 parts by weight, or when it is 1 part by weight or more, the polycarbonate resin composition is charged so that it is out of the predetermined reference range. This causes a decrease in the yield of subsequent processes such as hard coating, and cannot be used suitably for the above-mentioned applications.
Here, the “antistatic property of the polycarbonate resin composition” can be evaluated by measuring the surface potential of the molded article of the target polycarbonate resin composition. A specific evaluation method will be described in Examples described later.

  In the polycarbonate resin composition of the present invention, the total light transmittance of a 2 mm-thick molded product molded from the polycarbonate resin composition is preferably 60% or more.

  The total light transmittance can be controlled by adjusting the molar ratio of the dihydroxy compound in the polycarbonate resin composition, the type or content of the antistatic agent, and the like.

Hereinafter, the details of the polycarbonate resin composition of the present invention will be described.
<Dihydroxy compound having a cyclic ether structure>
The polycarbonate resin which is the raw material of the polycarbonate resin composition of the present invention (hereinafter sometimes referred to as “the polycarbonate resin of the present invention”) is a structural unit derived from a dihydroxy compound having a cyclic ether structure as part of its structure. including.
Examples of the dihydroxy compound having a cyclic ether structure include anhydrous sugar alcohols typified by the dihydroxy compound represented by the following general formula (1), spiroglycol represented by the following general formula (2), and the like.
Examples of the dihydroxy compound represented by the following general formula (1) include isosorbide, isomannide and isoidet which are in a stereoisomeric relationship.
Moreover, as a dihydroxy compound represented by the following general formula (2), 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) ) Undecane (common name: spiroglycol), 3,9-bis (1,1-diethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane, 3,9- And bis (1,1-dipropyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane. These may be used alone or in combination of two or more.

(In the general formula (2), R _{1 to} R ₄ are each independently an alkyl group having 1 to 3 carbon atoms.)

  Among the dihydroxy compounds having a cyclic ether structure, it is most preferable to use isosorbide which is industrially easily available and is derived from plant raw materials, and these may be used alone or in combination of two or more.

  In addition, the dihydroxy compound which has the said cyclic ether structure in a part of structure represented by isosorbide is easy to be gradually oxidized with oxygen. For this reason, when storing or handling during production, it is important to prevent moisture from being mixed, to use an oxygen scavenger, or to be in a nitrogen atmosphere in order to prevent decomposition by oxygen. When isosorbide is oxidized, decomposition products such as formic acid are generated. For example, when a polycarbonate resin is produced using isosorbide containing these decomposition products, the resulting polycarbonate resin is colored or causes a significant deterioration in physical properties. Moreover, it may affect the polymerization reaction, and a high molecular weight polymer may not be obtained. In addition, when a stabilizer for preventing the generation of formic acid is added, depending on the type of the stabilizer, coloring may occur in the obtained polycarbonate resin, or the physical properties may be significantly deteriorated.

  Therefore, it is preferable to use a stabilizer for the dihydroxy compound having a cyclic ether structure. 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. Since it is easy, it is preferable to contain a basic stabilizer. Among these, examples of the reducing agent include sodium borohydride and lithium borohydride, and examples of the antacid include alkalis such as sodium hydroxide. Addition of such an alkali metal salt is not preferable because an alkali metal may serve as a polymerization catalyst, and if it is added excessively, the polymerization reaction cannot be controlled.

  Basic stabilizers include group 1 or group 2 metal hydroxides, carbonates, phosphates, phosphites, hypophosphorous acid in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). Salts, borates, fatty acid salts, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium Basic ammonium compounds such as monium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide, 4-aminopyridine, 2-aminopyridine, N, N -Dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole And amine compounds such as aminoquinoline. Of these, sodium or potassium phosphates and phosphites are preferable, and disodium hydrogen phosphate and disodium hydrogen phosphite are particularly preferable because of their effects and ease of distillation removal described later.

  The content of these basic stabilizers in the dihydroxy compound is not particularly limited, but if it is too small, the effect of preventing the alteration of the dihydroxy compound may not be obtained, and if it is too large, the modification of the dihydroxy compound may be caused. Therefore, 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.

  In addition, when dihydroxy compounds containing these basic stabilizers are used as raw materials for the production of polycarbonate resin, the basic stabilizer itself becomes a polymerization catalyst, which not only makes it difficult to control the polymerization rate and quality, but also deteriorates the initial hue. Therefore, 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, in order to deteriorate the light resistance of the resulting polycarbonate resin molded product.

  In order to obtain a dihydroxy compound that 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 of the dihydroxy compound. The distillation in this case may be simple distillation or continuous distillation, and is not particularly limited. As distillation conditions, it is preferable to carry out distillation under reduced pressure in an inert gas atmosphere such as argon or nitrogen. In order to suppress thermal denaturation, it is 250 ° C. or lower, preferably 200 ° C. or lower, particularly 180 °. It is preferable to carry out under the conditions of ℃ or less.

  By such distillation purification, the formic acid content in the dihydroxy compound is 20 ppm by weight or less, preferably 10 ppm by weight or less, particularly preferably 5 ppm by weight or less, thereby impairing the polymerization reactivity during the production of the polycarbonate resin. In addition, it is possible to produce a polycarbonate resin excellent in hue and thermal stability. Formic acid content is measured using ion chromatography according to the following procedure. In the following procedure, isosorbide is taken as an example of a typical dihydroxy compound.

About 0.5 g of isosorbide is precisely weighed and collected in a 50 ml volumetric flask and made up to volume with pure water. A sodium formate aqueous solution is used as a standard sample, and the peak having the same retention time as that of the standard sample is defined as formic acid, and quantified by an absolute calibration curve method from the peak area.
As the ion chromatograph, DX-500 type manufactured by Dionex was used, and an electric conductivity detector was used as a detector. As a measurement column, AG-15 is used for a guard column manufactured by Dionex, and AS-15 is used for a separation column. A measurement sample is injected into a 100 μl sample loop, and 10 mM NaOH is used as an eluent, and the measurement is performed at a flow rate of 1.2 ml / min and a thermostat temperature of 35 ° C. A membrane suppressor is used as the suppressor, and a 12.5 mM-H ₂ SO ₄ aqueous solution is used as the regenerating solution.

  Further, the polycarbonate resin of the present invention is a structural unit derived from a dihydroxy compound having a cyclic ether structure in order to obtain a surface impact resistance improving effect and an impact resistance improving effect when the polycarbonate resin composition of the present invention is used. In addition, it is preferable to include a structural unit derived from an aliphatic dihydroxy compound (a dihydroxy compound composed of an aliphatic hydrocarbon other than two hydroxy groups). In order to introduce a structural unit derived from an aliphatic dihydroxy compound in the polycarbonate resin, it may be copolymerized using an aliphatic dihydroxy compound as a raw material for the polycarbonate resin, similarly to the dihydroxy compound having the cyclic ether structure.

  Examples of the aliphatic dihydroxy compound include a linear aliphatic dihydroxy compound, a branched aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and the like. Among these, an alicyclic dihydroxy compound is preferable.

  Specific examples of the aliphatic dihydroxy compound that can be used in the present invention are given below, but the following aliphatic dihydroxy compounds can be used alone or in combination of two or more.

  Examples of the linear aliphatic dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5 -Heptanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol and the like. Examples of the branched aliphatic dihydroxy compound include neopentyl glycol and hexylene glycol.

  An alicyclic dihydroxy compound is a compound having a cyclic structure hydrocarbon skeleton and two hydroxy groups, and the hydroxy group may be directly bonded to the cyclic structure or via a substituent such as an alkylene group. You may couple | bond with the cyclic structure. The cyclic structure may be monocyclic or polycyclic. As a suitable thing of an alicyclic dihydroxy compound, the alicyclic dihydroxy compound which has the 5-membered ring structure mentioned below, the alicyclic dihydroxy compound which has a 6-membered ring structure, etc. are mentioned. As an alicyclic dihydroxy compound, an alicyclic dihydroxy compound having a 5-membered ring structure or an alicyclic dihydroxy compound having a 6-membered ring structure is used, and a structural unit derived therefrom is introduced into a polycarbonate resin. The heat resistance of the polycarbonate resin can be increased.

  The carbon number of the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, more preferably 30 or less. The higher the number of carbon atoms, the higher the heat resistance of the obtained polycarbonate resin. However, the synthesis of the polycarbonate resin becomes difficult, the purification becomes difficult, and the cost may increase. On the other hand, the smaller the carbon number of the alicyclic dihydroxy compound, the easier the purification and the easier the raw material procurement.

  Examples of alicyclic dihydroxy compounds having a 5-membered ring structure include decycloline diols such as tricyclodecanediols, pentacyclopentadecanediols, 2,6-decalindiol, 1,5-decalindiol, and 2,3-decalindiol. , Tricyclotetradecanediols, tricyclodecane dimethanols, pentacyclopentadecane dimethanols and the like.

  Examples of alicyclic dihydroxy compounds having a 6-membered ring structure include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, 2-methyl- Cyclohexanediols such as 1,4-cyclohexanediol, cyclohexenediols such as 4-cyclohexene-1,2-diol, norbornanediols such as 2,3-norbornanediol, 2,5-norbornanediol, Adamantanediols such as 3-adamantanediol and 2,2-adamantanediol, cyclohexanedimethanols such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, 4 -Cyclohexene-1, -Cyclohexene dimethanol such as diol, norbornane dimethanol such as 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, adamantane diol such as 1,3-adamantanedimethanol, 2,2-adamantanedimethanol Methanol etc. are mentioned.

  Among the alicyclic dihydroxy compounds listed above, cyclohexane dimethanols, tricyclodecane dimethanols, adamantane diols, and pentacyclopentadecane dimethanol are preferable, and cyclohexane dimethanols and tricyclodecane dimethanol are particularly preferable. .

  When cyclohexanedimethanols and / or tricyclodecanedimethanols are used, the surface impact resistance of the resulting polycarbonate resin composition is excellent. Among cyclohexanedimethanols, 1,4-cyclohexanedimethanol is preferable.

  The polycarbonate resin contains both a structural unit derived from a dihydroxy compound having a cyclic ether structure and a structural unit derived from an aliphatic dihydroxy compound such as an alicyclic dihydroxy compound, thereby enabling transparency and impact resistance of the polycarbonate resin. In addition to improving the properties, it is also possible to obtain the effect of improving various physical properties such as flexibility, heat resistance and moldability.

  When the proportion of structural units derived from aliphatic dihydroxy compounds such as alicyclic dihydroxy compounds in the polycarbonate resin of the present invention is too small, the dispersibility of the impact strength modifier in the polycarbonate resin when the polycarbonate resin composition is obtained On the other hand, if the amount is too large, the reduced viscosity of the polycarbonate resin increases, the fluidity during molding decreases, and the productivity and moldability deteriorate. There is a risk. In particular, when the structural unit derived from the aliphatic dihydroxy compound relative to the structural unit derived from all the dihydroxy compounds in the polycarbonate resin is 20 mol% or more, the impact resistance when the polycarbonate resin composition is obtained is excellent. . The ratio of the structural unit derived from the aliphatic dihydroxy compound such as the alicyclic dihydroxy compound to the structural unit derived from the entire dihydroxy compound in the polycarbonate resin is more than 40 mol%, preferably 45 mol% or more. On the other hand, the structural unit derived from an aliphatic dihydroxy compound such as an alicyclic dihydroxy compound relative to the structural unit derived from all dihydroxy compounds in the polycarbonate resin is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol. % Or less.

  The aliphatic dihydroxy compound is the same stabilizer as the above-mentioned dihydroxy compound having a cyclic ether structure, such as a reducing agent, antioxidant, oxygen scavenger, light stabilizer, antacid, pH stabilizer, heat stabilizer and the like. May be included.

  The polycarbonate resin of the present invention may contain a structural unit derived from a dihydroxy compound having a cyclic ether structure and a dihydroxy compound other than the aliphatic dihydroxy compound (hereinafter sometimes referred to as “other dihydroxy compounds”). .

  More specifically, as other dihydroxy compounds, 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) 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 Aromatic bisphenols such as -3,3'-dichlorodiphenyl ether, 9,9-bis (4-hydroxyphenyl) fluorene, and 9,9-bis (4-hydroxy-2-methylphenyl) fluorene. However, from the viewpoint of the light resistance of the polycarbonate resin, as the other dihydroxy compounds, those having no aromatic ring structure in the molecular structure are preferable. These other dihydroxy compounds may be used alone or in combination of two or more according to the required performance of the obtained polycarbonate resin.

  When the polycarbonate resin of the present invention contains structural units derived from other dihydroxy compounds, the ratio of the structural units derived from other dihydroxy compounds to the structural units derived from all dihydroxy compounds in the polycarbonate resin is 0 mol% or more and Less than 1 mol% is preferable, 0 mol% or more and less than 0.8 mol% is more preferable, and 0 mol% or more and less than 0.5 mol% is still more preferable. When there is too much content of the structural unit derived from other dihydroxy compounds, such as a bisphenol compound, there exists a possibility that coloring may become remarkable.

  In addition, other dihydroxy compounds are stabilizers such as reducing agents, antioxidants, oxygen scavengers, light stabilizers, antacids, pH stabilizers, heat stabilizers and the like similar to the above-mentioned dihydroxy compounds having a cyclic ether structure. May be included.

(Carbonated diester)
The polycarbonate resin of the present invention can be produced by a generally used polymerization method, and the polymerization method may be any of an interfacial polymerization method using phosgene and a melt polymerization method in which a transesterification reaction with a carbonic acid diester is performed. A melt polymerization method in which a dihydroxy compound is reacted with a diester carbonate having lower toxicity to the environment in the presence of a polymerization catalyst is preferred.
The polycarbonate resin can be obtained by a melt polymerization method in which the above-described dihydroxy compound containing the dihydroxy compound of the present invention and a carbonic acid diester are transesterified.
As a carbonic acid diester used, what is normally represented by following General formula (3) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.

In the general formula (3), A ₁ and A ₂ are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic group.
Examples of the carbonic acid diester represented by the general formula (3) include substituted diphenyl carbonate such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. Carbonic acid diesters may contain impurities such as chloride ions, which may hinder the polymerization reaction or worsen the hue of the resulting polycarbonate resin. It is preferable to use what was done.

The carbonic acid diester is preferably used in a molar ratio of 0.90 to 1.20, more preferably in a molar ratio of 0.95 to 1.10, based on all dihydroxy compounds used in the melt polymerization. It is even more preferable to use at a molar ratio of .96 to 1.10, and particularly preferable to use at a molar ratio of 0.98 to 1.04.
When this molar ratio is less than 0.90, the terminal hydroxyl group of the produced polycarbonate resin is increased, the thermal stability of the polymer is deteriorated, and when the polycarbonate resin composition is molded, coloring or transesterification is caused. There is a possibility that the reaction rate decreases or a desired high molecular weight product cannot be obtained.
On the other hand, when the molar ratio is greater than 1.20, the rate of transesterification reaction decreases under the same conditions, and it becomes difficult to produce a polycarbonate resin having a desired molecular weight. The amount of diester is increased, and this residual carbonic acid diester may be unfavorable at the time of molding or causing the odor of the molded product, increasing the heat history during the polymerization reaction, resulting in the hue and There is a possibility of worsening the weather resistance.

  Furthermore, when the molar ratio of carbonic acid diester to the total dihydroxy compound is increased, the amount of residual carbonic acid diester in the obtained polycarbonate resin is increased, which may deteriorate the light resistance of the polycarbonate resin by absorbing ultraviolet rays. It is not preferable. The concentration of the carbonic acid diester remaining in the polycarbonate resin of the present invention is preferably 200 ppm by weight or less, more preferably 100 ppm by weight or less, particularly preferably 60 ppm by weight or less, and particularly preferably 30 ppm by weight or less. However, actually, the polycarbonate resin may contain unreacted carbonic acid diester, and the lower limit value of the unreacted carbonic acid diester concentration in the polycarbonate resin is usually 1 ppm by weight.

<Transesterification reaction catalyst>
The polycarbonate resin can be produced by transesterifying the dihydroxy compound containing the dihydroxy compound having the cyclic ether structure described above with the carbonic acid diester represented by the general formula (3). More specifically, it can be obtained by transesterification to remove by-product monohydroxy compounds and the like out of the system. In this case, melt polymerization is usually carried out by transesterification in the presence of a transesterification catalyst.

The transesterification catalyst (hereinafter sometimes referred to as “catalyst”) used in the production of the polycarbonate resin of the present invention includes at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds. . By using such a catalyst, the transparency, hue and light resistance of the polycarbonate resin can be made particularly excellent.
As a form of magnesium compound or calcium compound used as a catalyst, it is usually used in the form of a salt such as a hydroxide or carbonate, carboxylate, or phenol salt. Hydroxides, carbonates and acetates are preferred, and acetates are preferred from the viewpoint of hue and polymerization activity.

  The amount of catalyst used in the case of using a magnesium compound and / or a calcium compound is preferably 0.1 μmol or more, more preferably 0.5 μmol or more, particularly preferably 0.7 μmol or more, per 1 mol of the total dihydroxy compound as a metal equivalent amount. And The upper limit is preferably 20 μmol, more preferably 10 μmol, particularly preferably 3 μmol, and most preferably 2.0 μmol.

  If the amount of the catalyst used is too small, the polymerization activity necessary for producing a polycarbonate resin having a desired molecular weight may not be obtained, and sufficient breaking energy may not be obtained. On the other hand, if the amount of the catalyst used is too large, not only the hue of the resulting polycarbonate resin will deteriorate, but also by-products will be generated, resulting in a decrease in fluidity and the occurrence of gels, which causes brittle fracture. In some cases, it may be difficult to produce a polycarbonate resin having a target quality.

<Production method of polycarbonate resin>
The polycarbonate resin is obtained by melt-polymerizing a dihydroxy compound containing the dihydroxy compound of the present invention and a carbonic acid diester by an ester exchange reaction. The raw material dihydroxy compound and the carbonic acid diester are uniformly mixed before the ester exchange reaction. It is preferable to do.
The mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and the upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. Among these, 100 ° C. or higher and 120 ° C. or lower is preferable. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often causing problems such as solidification, and if the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated. The hue of the polycarbonate resin thus obtained may deteriorate, which may adversely affect light resistance.

  The operation of mixing a dihydroxy compound containing a dihydroxy compound having a cyclic ether structure and the carbonic acid diester represented by the formula (3) is performed at an oxygen concentration of 10% by volume or less, more preferably 0.0001% by volume to 10% by volume. In particular, it is preferable to perform in an atmosphere of 0.0001% by volume to 5% by volume, particularly 0.0001% by volume to 1% by volume, from the viewpoint of preventing hue deterioration of the obtained polycarbonate resin.

  The polycarbonate resin is preferably produced by melt polymerization in multiple stages using a plurality of reactors using a catalyst, but the reason for carrying out melt polymerization in a plurality of reactors is the initial stage of the melt polymerization reaction. Because there are many monomers contained in the reaction solution, it is important to suppress the volatilization of the monomers while maintaining the necessary polymerization rate. This is because it is important to sufficiently distill off the monohydroxy compound produced as a by-product. Thus, in order to set different polymerization reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of reactors arranged in series. As described above, the number of the reactors may be at least two, but from the viewpoint of production efficiency, the number of reactors is three or more, preferably 3 to 5, and particularly preferably four. The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.

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

  In order to maintain the polymerization rate appropriately and suppress the distillation of the monomer, while keeping the hue, thermal stability, light resistance, etc. of the finally obtained polycarbonate resin, The selection of the quantity is important.

  In the production of the polycarbonate resin, 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. Good.

  In the production of the polycarbonate resin, the catalyst can be added to the raw material preparation tank, 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, the reactor A catalyst supply line is installed in the middle of the raw material line before being supplied to, and is preferably supplied as an aqueous solution.

  As the polymerization conditions, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum in the initial stage of polymerization and to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum in the late stage of polymerization. Appropriate selection of the jacket temperature and internal temperature at the stage and the pressure in the reaction system is important from the viewpoint of the hue and light resistance of the resulting polycarbonate resin. For example, if either the temperature or the pressure is changed too quickly before the polymerization reaction reaches a predetermined value, the unreacted monomer will be distilled, causing the molar ratio of the dihydroxy compound and the carbonic acid diester to change, resulting in a decrease in the polymerization rate. Or a polymer having a predetermined molecular weight or terminal group may not be obtained, and as a result, the object of the present invention may not be achieved.

  If the temperature of the transesterification reaction is too low, it may lead to a decrease in productivity and an increase in the thermal history of the product, and if it is too high, it may not only cause vaporization of the monomer but also promote the decomposition and coloring of the polycarbonate resin. .

  In the production of the polycarbonate resin, a method of transesterifying a dihydroxy compound containing a dihydroxy compound having the cyclic ether structure as a part of the structure with a carbonic acid diester in the presence of a catalyst is usually a multistage process of two or more stages. To be implemented. Specifically, the first stage transesterification reaction temperature (hereinafter sometimes referred to as “internal temperature”) is preferably 140 ° C. or higher, more preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and even more. Preferably it is 200 degreeC or more. Further, the transesterification temperature in the first stage is preferably 270 ° C. or lower, more preferably 240 ° C. or lower, further preferably 230 ° C. or lower, and even more preferably 220 ° C. or lower. The residence time in the first stage transesterification reaction is usually 0.1 hours to 10 hours, preferably 0.5 hours to 3 hours. The first stage transesterification reaction involves reacting the generated monohydroxy compound. It is carried out while distilling out of the system. In the second and subsequent stages, the transesterification reaction temperature is increased, and the transesterification reaction is usually carried out at a temperature of 210 ° C. to 270 ° C., preferably 220 ° C. to 250 ° C., and simultaneously generated monohydroxy compounds are removed from the reaction system. While removing the pressure of the reaction system gradually from the pressure of the first stage, the pressure of the reaction system is finally 200 Pa or less, usually 0.1 hours to 10 hours, preferably 0.5 hours to 6 hours, Particularly preferably, the polycondensation reaction is performed for 1 hour to 3 hours. When the transesterification reaction temperature is excessively high, the hue is deteriorated when formed into a molded product, which may easily cause brittle fracture. When the transesterification reaction temperature is too low, the target molecular weight does not increase, the molecular weight distribution becomes wide, and the impact strength may be inferior. Further, if the residence time of the transesterification reaction is excessively long, brittle fracture may occur easily. If the residence time is too short, the target molecular weight may not increase and the impact strength may be inferior.

  The by-produced monohydroxy compound is preferably reused as a raw material for carbonic acid diesters and various bisphenol compounds after purification as necessary from the viewpoint of effective utilization of resources.

  In particular, in order to obtain a good polycarbonate resin having a high impact strength by suppressing the coloration, thermal deterioration or burning of the polycarbonate resin, the maximum internal temperature in all reaction stages is less than 255 ° C., more preferably 250 ° C. or less, especially 225 It is preferable that it is a C-245 degreeC. In addition, a horizontal reactor with excellent plug flow and interface renewability is used at the final stage of the reaction in order to suppress a decrease in the polymerization rate in the latter half of the polymerization reaction and to minimize thermal degradation of the polycarbonate resin due to thermal history. It is preferable to do.

  In addition, in order to obtain a polycarbonate resin with high impact strength and to obtain a polycarbonate resin with high molecular weight, the polymerization temperature may be increased as much as possible, and the polymerization time may be lengthened. It tends to break down. Therefore, in order to satisfy both the high impact strength and the difficulty of brittle fracture, the polymerization temperature must be kept low, the use of a highly active catalyst for shortening the polymerization time, and the appropriate reaction system pressure. Is preferable. Furthermore, it is preferable to remove foreign matters or burns generated in the reaction system by a filter or the like in the middle of the reaction or at the end of the reaction in order to make brittle fracture difficult.

  When a polycarbonate resin is produced using a substituted diphenyl carbonate such as diphenyl carbonate or ditolyl carbonate as the carbonic acid diester represented by the formula (3), phenol and substituted phenol are by-produced, and the polycarbonate resin Although it cannot be avoided, phenol and substituted phenols also have an aromatic ring, which absorbs ultraviolet rays and may cause deterioration of light resistance, and may also cause odor during molding. . The polycarbonate resin contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of 1000 ppm by weight or more after a normal batch reaction, but from the viewpoint of light resistance and odor reduction, it is devolatilized. Using a horizontal reactor excellent in performance or an extruder with a vacuum vent, the content of the aromatic monohydroxy compound in the polycarbonate resin is preferably 700 ppm by weight or less, more preferably 500 ppm by weight or less, and particularly 300 weights. It is preferable to make it ppm or less. However, it is difficult to remove completely industrially, and the lower limit of the content of the aromatic monohydroxy compound in the polycarbonate resin is usually 1 ppm by weight. In addition, these aromatic monohydroxy compounds may naturally have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.

  In addition, Group 1 metals, especially lithium, sodium, potassium, cesium, especially sodium, potassium, cesium, may be mixed from raw materials or reactors. Since there is a possibility of adverse effects, the total amount of these compounds in the polycarbonate resin of the present invention is preferably small, and the amount of metal in the polycarbonate resin is usually 1 ppm by weight or less, preferably 0.8 ppm by weight. Below, more preferably 0.7 ppm by weight or less.

  The amount of metal in the polycarbonate resin can be measured by various conventionally known methods. After recovering the metal in the polycarbonate resin by a method such as wet ashing, atomic emission, atomic absorption, Inductively Coupled Plasma (ICP) It can measure using the method of these.

The polycarbonate resin is usually cooled and solidified after melt polymerization as described above, and pelletized with a rotary cutter or the like.
The method of pelletization is not limited, but the polycarbonate resin is drawn out from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand, and pelletized, or the molten state from the final polymerization reactor is uniaxial or biaxial. After supplying resin to the extruder of the shaft and melt-extruding, cooling and solidifying to pelletize, or after extracting from the final polymerization reactor in a molten state, cooling and solidifying in the form of strands and once pelletizing 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 is devolatilized under reduced pressure, and generally known heat stabilizers, neutralizers, UV absorbers, mold release agents, colorants, lubricants, lubricants, plasticizers, phases. A solubilizer, 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 to 300 ° C, preferably 200 ° C to 270 ° C, more preferably 230 ° C to 260 ° C. 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 degradation of the polycarbonate becomes severe, which causes a decrease in mechanical strength due to a decrease in molecular weight, coloring, generation of gas, generation of foreign matters, and further generation of burns. It is preferable to install a filter for removing the foreign matters and burns in the extruder or at the outlet of the extruder.

The size of the filter for removing foreign matter (aperture) is usually 400 μm or less, preferably 200 μm or less, particularly preferably 100 μm or less, with the goal of filtering accuracy of removing 99% or more of foreign matter. If the opening of the filter is excessively large, leakage may occur in the removal of foreign matters and burns, and when polycarbonate resin is molded, brittle fracture may occur. Moreover, the opening of the said filter can be adjusted according to the use of the said polycarbonate resin composition. For example, when applied to film applications, the aperture of the filter is preferably 40 μm or less and more preferably 10 μm or less because of the requirement to eliminate defects.
Further, a plurality of the filters may be used in series, or a filtration device in which a plurality of leaf disk polymer filters are stacked may be used.

  When the extruded polycarbonate resin is cooled to form chips, it is preferable to use a cooling method such as air cooling or water cooling. The air used for air cooling should be air from which foreign substances in the air have been removed in advance with a HEPA filter (a filter specified in JIS Z8112), etc., to prevent reattachment of foreign substances in the air. desirable. More preferably, it is preferably carried out in a clean room having a higher degree of cleanliness than class 7, as defined in JIS B 9920 (2002), and more preferably higher than class 6. When using water cooling, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. There are various openings of the filter to be used, but those having a filter of 10 to 0.45 μm are preferable.

The glass transition temperature (Tg) of the polycarbonate resin is preferably less than 145 ° C. If this range is exceeded and the glass transition temperature is too high, there is a risk of fading. In this case, it is necessary to set the mold temperature high when transferring the shape of the mold surface to the molded product during molding. For this reason, the temperature controller that can be selected may be limited, or the transferability of the mold surface may be deteriorated.
The glass transition temperature of the polycarbonate resin is more preferably less than 140 ° C, and still more preferably less than 135 ° C.
The glass transition temperature of the polycarbonate resin is usually 90 ° C. or higher, preferably 95 ° C. or higher.

  As a method of setting the glass transition temperature of the polycarbonate resin to less than 145 ° C., the proportion of the structural unit derived from the dihydroxy compound having the cyclic ether structure in a part of the structure is reduced, or the alicyclic dihydroxy having low heat resistance. Examples thereof include a method of selecting a compound and reducing the proportion of structural units derived from an aromatic dihydroxy compound such as a bisphenol compound.

  The degree of polymerization of the polycarbonate resin was determined by precisely adjusting the polycarbonate concentration to 1.00 g / dl by using a mixed solvent of phenol and 1,1,2,2, -tetrachloroethane in a weight ratio of 1: 1 as a solvent. The reduced viscosity measured at 30.0 ° C. ± 0.1 ° C. (hereinafter sometimes simply referred to as “reduced viscosity”) is preferably 0.40 dl / g or more, more preferably 0.42 dl / g or more, Particularly preferably, it is 0.45 dl / g or more, but depending on the use of the polycarbonate resin composition, 0.60 dl / g or more, further 0.85 dl / g or more may be suitably used. Further, it is preferably 2.0 dl / g or less, more preferably 1.7 dl / g or less, and particularly preferably 1.4 dl / g or less. If the reduced viscosity of the polycarbonate resin is excessively low, the mechanical strength may be weakened. If the reduced viscosity of the polycarbonate resin is excessively high, the fluidity at the time of molding is reduced, the cycle characteristics are reduced, and the molded product is reduced. Tends to be deformed by heat.

  When the polycarbonate resin is produced by a melt polymerization method, one or more of a phosphoric acid compound and a phosphorous acid compound can be added during polymerization for the purpose of preventing coloring.

  As the phosphoric acid compound, one or more of trialkyl phosphates such as trimethyl phosphate and triethyl phosphate are preferably used. These are preferably added in an amount of 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less, based on the total hydroxy compound components. When the addition amount of the phosphorus compound is less than the lower limit, the effect of preventing coloring is small, and when the addition amount is more than the upper limit, the transparency is lowered, or conversely, the coloring is promoted or the heat resistance is lowered.

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

  The phosphoric acid compound and the phosphorous acid compound can be added in combination, but the addition amount in that case is the total amount of the phosphoric acid compound and the phosphorous acid compound, and the total hydroxy compound component described above, It is preferable to set it as 0.0001 mol% or more and 0.005 mol% or less, More preferably, it is 0.0003 mol% or more and 0.003 mol% or less. If this addition amount is less than the lower limit, the effect of preventing coloring is small, and if it is more than the upper limit, it may cause a decrease in transparency, or conversely promote coloring or reduce heat resistance. .

  In addition, the polycarbonate resin produced in this way may be blended with one or more thermal stabilizers in order to prevent a decrease in molecular weight and a deterioration in hue at the time of molding or the like.

  Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris ( 2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl Diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di) -Tert Butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, Trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), dimethylbenzenephosphonate, Examples include diethyl benzenephosphonate and dipropyl benzenephosphonate. Among them, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and dimethyl benzenephosphonate are preferably used.

  Such a heat stabilizer can be further added in addition to the addition amount added at the time of melt polymerization. That is, after blending an appropriate amount of a phosphorous acid compound or phosphoric acid compound to obtain a polycarbonate resin, if a phosphorous acid compound is further blended by a blending method described later, transparency during polymerization is reduced, coloring Further, it is possible to blend more heat stabilizers while avoiding a decrease in heat resistance, and it is possible to prevent deterioration of hue.

  The content of these heat stabilizers is preferably 0.0001 parts by weight to 1 part by weight, more preferably 0.0005 parts by weight to 0.5 parts by weight, and 0.001 parts by weight with respect to 100 parts by weight of the polycarbonate resin. Part to 0.2 parts by weight is more preferable.

<Alkanesulfonate>
The polycarbonate resin composition of the present invention contains the polycarbonate resin and an alkane sulfonate.

Examples of the alkane sulfonate include aliphatic sulfonate and perfluoroalkane-sulfonate. Examples of these salts include ammonium salts and metal salts. Preferred examples of metals used as metal salts include metals of Group 1 of the periodic table and metals of Group 2 of the periodic table. Specifically, alkali metals such as lithium, sodium, potassium, rubidium and cesium; alkaline earth metals such as calcium, strontium and barium; beryllium and magnesium. Among these metal salts, alkali metals are preferable from the viewpoint of transparency, and sodium and potassium are particularly preferable.
As the alkane sulfonate, an alkane sulfonate having an alkyl group having 4 to 8 carbon atoms is preferable.

  Specific examples of the alkane-sulfonic acid metal salt include, for example, sodium butane-sulfonate, potassium butane-sulfonate, sodium pentane-sulfonate, potassium pentane-sulfonate, sodium octane-sulfonate, potassium octane-sulfonate, Examples include tetraethylammonium salt of butane-sulfonic acid.

  The compounding quantity of alkane sulfonate is 0.05 weight part or more and less than 1 weight part with respect to 100 weight part of polycarbonate. When the blending amount of the alkane-sulfonic acid metal salt is excessively small, it is difficult to obtain a sufficient antistatic effect, and when it is excessively large, the haze is deteriorated. Therefore, 0.05 parts by weight or more is preferable, 0.06 parts by weight or more is preferable, 0.07 parts by weight or more is more preferable, and 0.08 parts by weight or more is particularly preferable. Moreover, less than 1 weight part is preferable, 0.9 weight part or less is preferable, 0.8 weight part or less is further more preferable, and 0.7 weight part or less is especially preferable.

The polycarbonate resin composition can be produced by mixing the polycarbonate resin and the alkane sulfonate.
Specifically, for example, the polycarbonate resin composition and the alkane sulfonate are mixed using an extruder, extruded into a strand, and cut into a pellet using a rotary cutter or the like. Can be obtained.

  The chargeability of the polycarbonate resin composition can be controlled by adjusting the molecular weight, the molar ratio of the dihydroxy compound, the type or content of the alkanesulfonic acid metal salt, and the like in the polycarbonate resin composition.

The polycarbonate resin composition preferably has a melt viscosity of 300 Pa · s or more. If the melt viscosity is too low outside the above range, the mechanical strength will be insufficient, the molded product will crack when taken out from the mold after molding such as injection molding, or cracks will occur when using the molded product There is a risk. The polycarbonate resin composition preferably has a melt viscosity of 450 Pa · s or more, more preferably 500 Pa · s or more.
The polycarbonate resin composition preferably has a melt viscosity of 800 Pa · s or less. When the melt viscosity is too high outside the above range, it may be difficult to industrially produce a polycarbonate resin composition having high strength. Further, in this case, there is a possibility that the fluidity is deteriorated, coloring due to an increase in molding temperature, molecular weight reduction, generation of decomposition gas, etc. are likely to occur. The polycarbonate resin composition preferably has a melt viscosity of 700 Pa · s or less, more preferably 640 Pa · s or less.

At the time of mixing the polycarbonate resin and the alkane sulfonate, additives such as the following antioxidant and mold release agent can be appropriately added as necessary.
In the polycarbonate resin composition, one or more kinds of antioxidants generally known for the purpose of antioxidant can be blended.

  When an antioxidant is used, it is usually 0.0001 part by weight or more and 1 part by weight or less, preferably 0.001 part by weight or more, more preferably 0.01 part by weight or more with respect to 100 parts by weight of the polycarbonate resin. In addition, it is usually 1 part by weight or less, preferably 0.5 part by weight or less, more preferably 0.3 part by weight or less.

  When the content of the antioxidant is above the above lower limit with respect to the entire polycarbonate resin composition, there is a tendency that the coloring suppression effect during molding tends to be good, but the content of the antioxidant is relative to the entire polycarbonate resin composition. If the amount is larger than the above upper limit, the surface appearance of the product is impaired by increasing the amount of deposits on the mold during injection molding or increasing the amount of deposits on the roll when forming a film by extrusion molding. There is a fear.

  The antioxidant is preferably at least one selected from the group consisting of phenolic antioxidants, phosphate antioxidants and sulfur antioxidants, and phenolic antioxidants and / or phosphate oxidations. An inhibitor is further preferred, and it is more preferred to contain a phosphate-based antioxidant.

  Examples of the phenolic antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, triethylene glycol-bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] , Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1 , 3,5-trimethyl-2 4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 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} And compounds such as -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, pentaerythritol-tetrakis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the like, preferably pentaerythritol- Tetrakis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is more preferred .

  Examples of the phosphate antioxidant include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tri Octadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert -Butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaeri Li diphosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, and distearyl pentaerythritol phosphite.

  Among these, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferred, and tris (2,4-di-tert-butylphenyl) phosphite is more preferred.

  Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, diester Stearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), bis [2-methyl-4- (3 -Laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) and the like. Among the above, pentaerythritol tetrakis (3-lauryl thiopropionate) is preferable.

  In addition, the polycarbonate resin composition has a range that does not impair the purpose of the present invention in order to further improve the release from the cooling roll during sheet molding or the mold release from the mold during injection molding. A release agent may be blended.

  Such release agents include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefinic waxes, olefinic waxes containing carboxy groups and / or carboxylic anhydride groups, silicone oils, Examples include organopolysiloxane. A mold release agent may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  The higher fatty acid ester is preferably a partial ester or a total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a 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. A stearic acid ester is more preferable as a mold release agent from the viewpoints of mold release and transparency.

  As the stearic acid ester, a partial or total ester of a substituted or unsubstituted monovalent or polyhydric alcohol having 1 to 20 carbon atoms and stearic acid is preferable. Such partial esters or total esters of monohydric or polyhydric alcohols and stearic acid include ethylene glycol distearate, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, stearyl stearate, pentaerythritol. More preferred are monostearate, pentaerythritol tetrastearate, propylene glycol monostearate, stearyl stearate, butyl stearate, sorbitan monostearate, 2-ethylhexyl stearate and the like. Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate and stearyl stearate are more preferred, and ethylene glycol distearate and stearic acid monoglyceride are particularly preferred.

  As the higher fatty acid, a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms is preferable. Of these, unsubstituted saturated fatty acids having 10 to 30 carbon atoms are more preferable, and examples of such higher fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid. A saturated fatty acid having 16 to 18 carbon atoms is more preferable, and examples of such saturated fatty acid include palmitic acid and stearic acid, and stearic acid is particularly preferable.

  When a release agent is used, the blending amount is usually 0.001 part by weight or more, preferably 0.01 part by weight or more, more preferably 0.1 part by weight or more, relative to 100 parts by weight of the polycarbonate resin. Moreover, it is 2 weight part or less normally, Preferably it is 1 weight part or less, More preferably, it is 0.5 weight part or less. If the content of the release agent is excessively large, the amount of deposits on the mold may increase during molding, and if molding is carried out in large quantities, there is a possibility that labor may be required for mold maintenance. There is a possibility that the appearance will be defective. When the content of the release agent in the polycarbonate resin composition is not less than the above lower limit, there is an advantage that the molded product can be easily released from the mold at the time of molding, and the molded product can be easily obtained.

  Further, the polycarbonate resin composition is significantly less discolored by ultraviolet rays than the conventional polycarbonate resin, but for the purpose of further improvement, it does not impair the purpose of the present invention. Seeds or two or more species may be blended.

  Here, the ultraviolet absorber is not particularly limited as long as it is a compound having ultraviolet absorbing ability. Examples of the compound having ultraviolet absorbing ability include organic compounds and inorganic compounds. Of these, organic compounds are preferred because they are easy to ensure affinity with the polycarbonate resin and are easily dispersed uniformly.

  The molecular weight of the organic compound having ultraviolet absorbing ability is not particularly limited, but is usually 200 or more, preferably 250 or more. Also. Usually, it is 600 or less, preferably 450 or less, more preferably 400 or less. If the molecular weight is too small, there is a possibility of causing a decrease in UV resistance performance after long-term use. When the molecular weight is excessively large, there is a possibility that the transparency of the resin composition is lowered after long-term use.

  Preferred ultraviolet absorbers include benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, salicylic acid phenyl ester compounds, cyanoacrylate compounds, malonic acid ester compounds, oxalic acid anilide compounds, and the like. . Of these, benzotriazole compounds, hydroxybenzophenone compounds, and malonic ester compounds are preferably used. These may be used alone or in combination of two or more.

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

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

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

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

  Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenyl acrylate, 2'-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like.

  Examples of the oxalic acid anilide compound include 2-ethyl-2'-ethoxy-oxalanilide (manufactured by Clariant, Sanduvor VSU).

  The content of the ultraviolet absorber and the light stabilizer can be appropriately selected according to the type of the ultraviolet absorber, but the ultraviolet absorber is added in an amount of 0.001% by weight to the entire polycarbonate resin composition. It is preferable to contain 5 weight%, and 0.01 to 2 weight part is preferable with respect to 100 weight part of polycarbonate.

  The polycarbonate resin composition may be blended with one or more blueing agents in order to counteract yellowishness. Any bluing agent can be used without any problem as long as it is used in conventional polycarbonate resins. In general, anthraquinone dyes are preferred because they are readily available.

  As a specific bluing agent, for example, the general name Solvent Violet 13 [CA. (Color Index No.) 60725], generic name Solvent Violet 31 [CA. 68210], general name Solvent Violet 33 [CA. 60725], generic name Solvent Blue 94 [CA. 61500], generic name Solvent Violet 36 [CA. 68210], generic name Solvent Blue 97 [manufactured by Bayer, "Macrolex Violet RR"], and generic name Solvent Blue 45 [CA. 61110] and the like are typical examples.

Usually, the content of these bluing agents is preferably 0.1 × 10 ⁻⁴ parts by weight to 2 × 10 ⁻⁴ parts by weight with respect to 100 parts by weight of the polycarbonate resin.

  In addition to the above-mentioned additives, the polycarbonate resin composition may be any of various known additives, for example, a flame retardant, a flame retardant aid, a hydrolysis inhibitor, and a foaming agent, as long as the object of the present invention is not impaired. In addition, a resin composition containing a dye or pigment may be used. Also, for example, a resin composition in which a synthetic resin such as aromatic polycarbonate, aromatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, or the like, or a biodegradable resin such as polylactic acid or polybutylene succinate is mixed. May be.

  As a blending method of the above-mentioned polycarbonate resin composition and various additives as described above, for example, mixing and kneading with a tumbler, V-type blender, super mixer, nauter mixer, Banbury mixer, kneading roll, extruder, etc. Or a solution blending method in which the mixture is dissolved in a common good solvent such as methylene chloride. However, this is not particularly limited, and any blending method that is usually used can be used. Various methods may be used.

  Various additives are added to the polycarbonate resin thus obtained, and it is generally known such as an extrusion molding method, an injection molding method, a compression molding method, etc. directly or after being once pelletized by a melt extruder. It can be formed into a desired shape by a forming method.

[Polycarbonate resin molded product]
A polycarbonate resin molded product can be obtained by molding the polycarbonate resin composition as described above.
Preferably, the polycarbonate resin molded product is molded by an injection molding method.
In this case, the polycarbonate resin molded product having a complicated shape can be produced. And if it shape | molds in a complicated shape, it will become easy to generate | occur | produce a stress concentration part, but since the modification effect of impact strength is acquired as mentioned above in the said polycarbonate resin composition, the fracture | rupture by stress concentration can be suppressed.

  The haze measured based on JIS K7105 (1981) when the resin composition of the present invention is molded to a thickness of 0.1 mm is preferably 10% or less, more preferably 8% or less, and more preferably 5%. More preferably, it is as follows. When the haze is within such a range, it can be widely used in various applications that require transparency.

<Use of resin composition>
The resin composition of the present invention can be molded into a film, a plate, an injection molded product or the like. Specifically, the polycarbonate resin of the present invention, alkane sulfonate and, if necessary, raw materials such as other resins and additives are directly mixed, and are then put into an extruder or an injection molding machine for molding, or The raw material is melt-mixed using a twin screw extruder, extruded into a strand shape to form pellets, and then the pellets are put into an extruder or an injection molding machine to be molded. In any method, it is necessary to consider a decrease in molecular weight due to hydrolysis of the polycarbonate-based resin, and the latter is preferably selected for uniform mixing. Therefore, the latter manufacturing method will be described below.

  The polycarbonate resin of the present invention, alkane sulfonate, and other resins and additives as necessary are sufficiently dried to remove moisture, then melt mixed using a twin screw extruder, and extruded into a strand shape. Create pellets. At this time, it is preferable to appropriately select the melt extrusion temperature in consideration of the viscosity changing depending on the composition ratio and blending ratio of each raw material. Specifically, the molding temperature is preferably 200 ° C. or higher and 260 ° C. or lower, more preferably 210 ° C. or higher and 250 ° C. or lower, and further preferably 220 ° C. or higher and 240 ° C.

  After the pellets produced by the above method are sufficiently dried to remove moisture, a film, a plate, or an injection molded product can be molded by the following method.

  As a method for forming a film and a plate, in addition to a roll stretching method, a tenter stretching method, a tubular method, and an inflation method, a general T die casting method, a pressing method, or the like can be employed as a film or plate forming method.

  In general, "film" is a thin flat product whose thickness is extremely small compared to the length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll. (JIS K6900) In general, the term “sheet” refers to a product that is thin according to the definition in JIS, and whose thickness is small for the length and width but flat. However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of words, in the present invention, the term “film” includes both “sheet” and “sheet”. Including "film".

  The molding method of the injection-molded body is not particularly limited, and for example, an injection molding method such as a general injection molding method for a thermoplastic resin, a gas assist molding method, and an injection compression molding method can be employed. In addition to the above-described methods, an in-mold molding method, a gas press molding method, a two-color molding method, a sandwich molding method, or the like can also be employed according to other purposes.

  Since the film, plate, or injection-molded product obtained from the resin composition of the present invention is excellent in transparency, heat resistance, and impact resistance, the use of the resin composition of the present invention is not particularly limited. However, for example, building materials, interior parts, transparent films, films for resin-coated metal plates, films for molding (vacuum and pressure forming, hot press molding, etc.), colored plates, transparent plates, shrink films, shrink labels, shrink tubes, It can be used for automobile interior materials, home appliance housings, various parts, OA equipment parts and other injection molded products.

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

(1) Preparation method of test piece The pellet of the polycarbonate resin composition was dried at 90 ° C. for 6 hours using a hot air dryer. 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 the injection molded plate is subjected to a resin temperature of 240 ° C., a mold temperature of 60 ° C., and a molding cycle of 40 seconds. (Width 100 mm × length 100 mm × thickness 2 mm) was molded.

(2) Surface potential measurement After the injection-molded plate obtained in (1) above was placed on a wooden desk with the mold fixing side up, a surface potential meter (SMC IZH10) was used to form the sensor and molding. The surface potential on the upper surface of the molded plate was measured with the distance from the plate fixed at 100 mm. The surface potential was determined to be -1 kV or more and +1 kV or less.

(3) Total light transmittance and haze measurement After the injection molded plate obtained in (1) was cut into four equal parts (width 50 mm x length 50 mm x thickness 2 mm), it conforms to JIS K7105 (1981). Then, using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance and haze of the test piece were measured with a D65 light source. The total light transmittance was 80% or more, and haze was 10% or less.

(4) Hue measurement According to JIS K7105 (1981), the injection-molded plate obtained in the above (3) is subjected to the C light source transmission method using a spectral color difference meter (SE2000 manufactured by Nippon Denshoku Industries Co., Ltd.). The yellow index (YI) value of the test piece was measured. The smaller the YI value, the better the quality without yellowness, and 30 or less was accepted.

Moreover, the symbol of the compound used by the following example and the comparative example is as follows.
ISB: Isosorbide (Rocket Fleure, trade name POLYSORB)
CHDM: 1,4-cyclohexanedimethanol (Eastman)
DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)
<Alkanesulfonate>
Electro stripper PC-3: mixture of sodium alkane sulfonate and silicon dioxide (manufactured by Kao Corporation)
Electro stripper PC: Sodium alkanesulfonate (manufactured by Kao Corporation)

Other additives are as follows.
<Antioxidant>
ADK STAB 2112: Phosphite antioxidant (manufactured by ADEKA)
Irganox 1010: Phenolic antioxidant (manufactured by BASF Japan)
<Release agent>
Unistar E-275: Distearate glycol (manufactured by NOF Corporation)

[Example 1]
In a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C., ISB and CHDM, DPC and calcium acetate monohydrate having a chloride ion concentration of 10 ppb or less by purification by distillation, a molar ratio In ISB / CHDM / DPC / calcium acetate monohydrate = 0.70 / 0.30 / 1.00 / 1.3 × 10 ⁻⁶ and sufficiently purged with nitrogen (oxygen concentration 0.0005) ~ 0.001 vol%).

  Subsequently, heating was performed with a heating medium, and stirring was started when the internal temperature reached 100 ° C., and the contents were melted and made uniform while controlling the internal temperature to be 100 ° C. After that, temperature increase was started, the internal temperature was adjusted to 210 ° C. in 40 minutes, and when the internal temperature reached 210 ° C., control was performed so as to maintain this temperature, and at the same time, pressure reduction was started and the temperature reached 210 ° C. After 90 minutes, the pressure was changed to 13.3 kPa (absolute pressure, the same applies hereinafter), and the pressure was maintained for another 60 minutes.

  The phenol vapor produced as a by-product with the polymerization reaction is led to a reflux condenser using a steam controlled at 100 ° C. as the inlet temperature to the reflux condenser, and a monomer component contained in the phenol vapor in a slight amount is introduced into the polymerization reactor. Then, the phenol vapor that did not condense was recovered by guiding it to a condenser using 45 ° C. warm water as a refrigerant.

  After the contents thus oligomerized are once restored to atmospheric pressure, they are transferred to another polymerization reaction apparatus equipped with a stirring blade and a reflux condenser controlled in the same manner as described above. The internal temperature was set to 220 ° C. and the pressure was set to 200 Pa in 60 minutes. Thereafter, the internal temperature was set to 230 ° C. and the pressure was set to 133 Pa or less over 20 minutes. When the predetermined stirring power was reached, the pressure was restored, the contents were extracted in the form of strands, and pelletized (polycarbonate resin 1) with a rotary cutter.

  Next, pellets of the obtained polycarbonate resin 1, and electrostripper PC-3 as an alkane sulfonate so as to have the composition shown in Table 1 below, Unistar E-275 as a release agent, and further an antioxidant Extruded Irganox 1010 and Adeka Stub 2112 in a strand form using a twin-screw extruder (LABOTEX30HSS-32) manufactured by Nippon Steel Works having two vents so that the resin temperature at the extruder outlet is 250 ° C. After cooling and solidifying with water, it was 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 evaluation results of the obtained pellet-like polycarbonate resin composition according to the above method are shown in Table 1 described later.

[Example 2]
A polycarbonate resin was prepared in the same manner as in Example 1 except that the electrostripper PC was used as the antistatic agent instead of the electrostripper PC-3 as the alkane sulfonate, and the composition shown in Table 1 below was used. The composition was manufactured and evaluated, and the results are shown in Table 1.

[Comparative Example 1]
The same procedure as in Example 1 was carried out except that the composition shown in Table 1 below was used without using an alkane sulfonate, and a polycarbonate resin composition was produced and evaluated. The results are shown in Table 1. It was.

[Comparative Examples 2-3]
Production and evaluation of a polycarbonate resin composition were carried out in the same manner as in Example 1 except that electrostripper PC-3 was used as the alkane sulfonate and the addition amount was changed to the composition shown in Table 1 below. The results are shown in Table 1.

[Comparative Examples 4 to 5]
Using an electrostripper PC as the alkane sulfonate, the same procedure as in Example 2 was conducted, except that the amount added was changed to the composition shown in Table 1, and the production and evaluation of the polycarbonate resin composition were conducted. The results are shown in Table 1.

  As is clear from Table 1, the polycarbonate resin composition of the present invention had a lower surface potential than the polycarbonate resin composition of the comparative example, and exhibited a high total light transmittance, a low haze and a low YI. Therefore, the polycarbonate resin molded article of the present invention imparts antistatic properties, has good transparency and color tone such as haze and yellow index value (YI), and is in the building material field, electrical / electronic field, automobile field, optical field. It can be seen that it can be suitably used in the parts field and the like.

  According to the present invention, the charging property is improved, the material has excellent properties such as haze and yellow index value (YI), and is preferably used in the building material field, the electric / electronic field, the automobile field, the optical part field, and the like. Can be obtained, and can be suitably used in the building material field, the electric / electronic field, the automobile field, the optical part field, and the like.

Claims (11)

Including a structural unit derived from a dihydroxy compound having a cyclic ether structure,
0.05 parts by weight or more of alkane sulfonate with respect to 100 parts by weight of polycarbonate resin produced using at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds as a transesterification reaction catalyst A polycarbonate resin composition containing less than parts by weight.   A thickness of 0.05 to 1 part by weight of an alkane sulfonate, which is formed from the polycarbonate resin composition, with respect to 100 parts by weight of a polycarbonate resin containing a structural unit derived from a dihydroxy compound having a cyclic ether structure. The polycarbonate resin composition according to claim 1, wherein a 2 mm-thick molded article has a total light transmittance of 60% or more.   The polycarbonate resin composition of Claim 1 or 2 containing a mold release agent.   The polycarbonate resin composition according to any one of claims 1 to 3, comprising an antioxidant.   The polycarbonate resin composition according to any one of claims 1 to 4, comprising a phosphite compound as an antioxidant. The polycarbonate resin composition according to any one of claims 1 to 5, wherein the dihydroxy compound having a cyclic ether structure is a dihydroxy compound having a structure represented by the following formula (1).
  The polycarbonate resin composition according to any one of claims 1 to 6, wherein the polycarbonate resin contains a structural unit derived from an aliphatic dihydroxy compound.   A polycarbonate resin molded article obtained by molding the polycarbonate resin composition according to any one of claims 1 to 7.   The polycarbonate resin molded product according to claim 8, wherein the polycarbonate resin molded product is obtained by molding by an injection molding method.   A film obtained by molding the polycarbonate resin composition according to any one of claims 1 to 7.   A plate obtained by molding the polycarbonate resin composition according to claim 1.