JPWO2016039370A1 - Polycarbonate resin composition - Google Patents

Abstract

Provided is a polycarbonate resin composition having a high hardness which is transparent with few foreign matters, excellent in flame retardancy, excellent in fluidity and excellent in moldability with a thin wall. Polycarbonate resin (A1) having a structural unit derived from an aromatic dihydroxy compound represented by the following general formula (1) having a viscosity average molecular weight of less than 30,000, 50 to 98% by mass, and a viscosity average molecular weight of 50,000 to Polycarbonate resin (A3) having a viscosity average molecular weight of 10,000 to 30,000 having a polymer structure different from that of polycarbonate resin (A2) of 95,000 and 2 to 30% by mass of 95,000 (however, And 100 parts by mass of the polycarbonate resin (A) containing at least 100% by mass of the polycarbonate resin (A), and 0.01 to 1 part by mass of the organic sulfonic acid metal salt (B). A polycarbonate resin composition. [Chemical 1]

Description

  The present invention relates to a polycarbonate resin composition, and in particular, relates to a polycarbonate resin composition with high hardness, which has few foreign matters, is transparent and excellent in flame retardancy, has good fluidity and is excellent in thin-wall moldability. .

  Polycarbonate resins are excellent in mechanical strength, electrical characteristics, transparency, and the like, and are widely used as engineering plastics in various fields such as electrical and electronic equipment fields and automobile fields. In recent years, in these fields of use, molding products have become thinner, smaller, and lighter, and further improvements in the performance of molding materials have been demanded. Among them, the development of polycarbonate resins with high hardness has become desirable. Some suggestions have been made.

  For example, a method for producing a polycarbonate or copolycarbonate having an excellent surface hardness using an aromatic dihydroxy compound having a specific structure different from conventional bisphenol A such as bisphenol C (Patent Document 1, Patent Document 2), dimethylbisphenolcyclohexane A method using a blend of a polycarbonate of a type and a polycarbonate of a bisphenol A type (Patent Document 3) is known.

  Furthermore, for members of electrical and electronic devices, liquid crystal display devices, etc., it is desired to develop a polycarbonate resin that has not only high hardness but also excellent flame retardancy. For example, a polycarbonate resin having a specific structure and a flame retardant are combined. A method has been proposed (Patent Document 4).

JP-A-64-069625 Japanese Patent Laid-Open No. 08-183852 International Publication No. 2009/083933 Pamphlet JP 2011-225862 A

  However, with these methods, it is possible to achieve both surface hardness and flame retardancy, but in order to achieve high flame retardance with a thin wall, it is necessary to increase the molecular weight of the polycarbonate resin, which lowers the fluidity. However, in some thin product shapes, molding may be difficult. In addition, when a high molecular weight is used to impart flame retardancy or a polycarbonate resin having a specific structure is used, the resin is likely to be thermally deteriorated during the resin composition production or molding process, The present inventors have found that there is a problem that a large amount of foreign matter is generated.

  Under such circumstances, the object (problem) of the present invention is to provide a polycarbonate resin composition having few foreign matters, excellent surface hardness, flame retardancy and transparency, good fluidity and excellent moldability with a thin wall. There is to do.

  As a result of intensive research to solve the above problems, the present inventor has obtained a polycarbonate resin containing a specific molecular weight polycarbonate resin having a specific structural unit and a high molecular weight polycarbonate resin and an organic sulfonic acid metal salt. The present inventors have found that the composition solves the above problems, and have reached the present invention.

The present invention relates to the following inventions.
[1] Polycarbonate resin (A1) having a structural unit derived from an aromatic dihydroxy compound represented by the following general formula (1) having a viscosity average molecular weight of less than 30,000, 50 to 98% by mass, and a viscosity average molecular weight of 50 Polycarbonate resin (A3) of 2 to 30% by mass of 1,000 to 95,000 and a polycarbonate resin (A3) of 30 to 30 mass% having a viscosity average molecular weight different from that of the polycarbonate resin (A1). % (However, the total amount of the polycarbonate resin (A) is 100% by mass) and 100 parts by mass of the polycarbonate resin (A) contains 0.01 to 1 part by mass of the organic sulfonic acid metal salt (B). A polycarbonate resin composition characterized by the above.
(In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and X is
R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is a C 6-12 fat which may be bonded to a carbon atom (C) to have a substituent. The group which forms a cyclic hydrocarbon is shown. )

[2] The polycarbonate resin composition according to the above [1], wherein the organic sulfonic acid metal salt (B) is a fluorine-containing organic sulfonic acid alkali metal salt.
[3] The polycarbonate resin composition according to the above [1] or [2], wherein the polycarbonate resin (A1) has a viscosity average molecular weight of 24,000 to 29,000.
[4] The polycarbonate resin composition according to any one of [1] to [3], wherein the polycarbonate resin (A2) has a viscosity average molecular weight of 60,000 to 85,000.
[5] The polycarbonate resin composition according to any one of [1] to [4], wherein the content of the polycarbonate resin (A3) in the polycarbonate resin (A) is 2 to 25% by mass.
[6] The polycarbonate resin composition according to any one of [1] to [5], wherein the aromatic dihydroxy compound represented by the general formula (1) is a bisphenol compound represented by the following formula (1a).
[7] The polycarbonate resin composition according to any one of [1] to [6], wherein the polycarbonate resin (A2) is a polycarbonate resin having a structural unit derived from bisphenol A.
[8] The polycarbonate resin composition according to any one of [1] to [7], wherein the polycarbonate resin (A3) is a polycarbonate resin having a structural unit derived from bisphenol A.
[9] The polycarbonate resin composition according to any one of the above [1] to [8], wherein the amount of terminal hydroxy groups of the polycarbonate resin (A) is 10 to 700 ppm by mass.
[10] The polycarbonate resin composition according to any one of [1] to [9] above, wherein the amount of terminal hydroxy groups of the polycarbonate resin (A1) is 10 to 800 ppm by mass.
[11] The polycarbonate resin composition according to any one of [1] to [10], wherein the structural viscosity index N1 of the polycarbonate resin (A1) and the structural viscosity index N2 of the polycarbonate resin (A2) are N1 <N2.
[12] The polycarbonate resin composition according to any one of [1] to [11], wherein the structural viscosity index N1 of the polycarbonate resin (A1) is 1.0 to 1.4.
[13] The polycarbonate resin composition according to any one of the above [1] to [12], wherein the structural viscosity index N2 of the polycarbonate resin (A2) is 1.2 to 1.9.

[14] Any of [1] to [13] above, wherein the content of the structural unit derived from the compound represented by the following general formula (2) in the polycarbonate resin composition is 10 to 4,000 mass ppm. The polycarbonate resin composition described in 1.
(In the general formula (2), R ¹ , R ² and X have the same meaning as in the general formula (1).)
[15] Any of the above [1] to [14], wherein the content of the structural unit derived from the compound represented by the general formula (2) in the polycarbonate resin (A1) is 60 to 6,000 mass ppm. The polycarbonate resin composition described in 1.
[16] The polycarbonate resin composition according to any one of [1] to [15] above, wherein the UL94 flame retardancy of a molded article having a thickness of 1.0 mm obtained by injection molding the polycarbonate resin composition is V-0. .
[17] A method for producing the polycarbonate resin composition according to any one of [1] to [16] above by melt kneading using an extruder, wherein an inert gas is supplied to a raw material inlet of the extruder as a unit. The ratio of the raw material amount F [kg / hr] and the inert gas amount G [L / min] of the polycarbonate resin composition supplied to the extruder per hour is 0.005 ≦ G / F ≦ 0.2. A method for producing a polycarbonate resin composition, which is kneaded while being introduced into the process.

  The polycarbonate resin composition of the present invention has few foreign matters, high surface hardness, excellent flame retardancy and transparency, good fluidity, and excellent moldability with a thin wall.

It is a schematic sectional drawing which shows an example of a structure of the extruder suitable for manufacture of the resin composition of this invention.

Hereinafter, the present invention will be described in detail with reference to examples and the like, but the present invention is not limited to the following examples and the like, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
In addition, in this-application specification, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit unless there is particular notice.

  The polycarbonate resin composition of the present invention comprises 50 to 98% by mass of a polycarbonate resin (A1) having a structural unit derived from the aromatic dihydroxy compound represented by the general formula (1) and having a viscosity average molecular weight of less than 30,000. Polycarbonate resin (A2) having a viscosity average molecular weight of 50,000 to 95,000 and 2 to 30% by mass and a polycarbonate resin having a viscosity average molecular weight of 10,000 to 30,000 having a polymer structure different from that of the polycarbonate resin (A1) ( A3) 0 to 30% by mass (however, the polycarbonate resin (A) as a whole is 100% by mass) and at least 100 parts by mass of the polycarbonate resin (A), the organic sulfonic acid alkali metal salt (B) 0.01 to It contains 1 part by mass.

Hereafter, each component etc. which comprise the polycarbonate resin composition of this invention are demonstrated in detail.
[Polycarbonate resin (A)]
The polycarbonate resin (A) contained in the polycarbonate resin composition of the present invention is a polycarbonate resin having a structural unit derived from the aromatic dihydroxy compound represented by the general formula (1) and having a viscosity average molecular weight of less than 30,000 ( A1) and a polycarbonate resin (A2) having a viscosity average molecular weight of 50,000 to 95,000 are contained at least.

[Polycarbonate resin (A1)]
The polycarbonate resin (A1) is a polycarbonate resin having a structural unit derived from an aromatic dihydroxy compound represented by the following general formula (1) and having a viscosity average molecular weight of less than 30,000.
(In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and X is
R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is a C 6-12 fat which may be bonded to a carbon atom (C) to have a substituent. The group which forms a cyclic hydrocarbon is shown. )

In the general formula (1), examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R ¹ and R ² include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, etc., substituted or unsubstituted Examples of the aryl group include a phenyl group, a benzyl group, a tolyl group, a 4-methylphenyl group, and a naphthyl group.

Among these, R ¹ and R ² are preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or a 4-methylphenyl group, and particularly preferably a hydrogen atom.

In addition, the bonding position of R ¹ and R ² in the general formula (1) is preferably the 5-position with respect to X.

In the general formula (1), R ³ and R ⁴ in X each independently represent a hydrogen atom or a methyl group, preferably a methyl group, and particularly an isopropylidene group in which R ³ and R ⁴ are a methyl group. Is preferred.

  Z is bonded to a carbon atom bonded to two phenyl groups in the general formula (1) to form a substituted or unsubstituted divalent alicyclic hydrocarbon having 6 to 12 carbon atoms. Examples of the divalent alicyclic carbocycle include cycloalkylidene groups such as cyclopentylidene group, cyclohexylidene group, cycloheptiline group, cyclododecylidene group, and adamantylidene group (preferably having a carbon number of 4 to Examples of the substituted group include those having these methyl substituents and ethyl substituents. Among these, a cyclohexylidene group, a methyl-substituted cyclohexylidene group, and a cyclododecylidene group are preferable.

  Preferred examples of the compound represented by the general formula (1) include bisphenol compounds such as the following formulas (1a) and (1b).

  Among these, bisphenol C represented by the formula (1a) (hereinafter sometimes referred to as “BPC”) is particularly preferable.

  The polycarbonate resin (A1) preferably contains a structural unit derived from a compound represented by the following general formula (2). Including a branched structure generated from a structural unit derived from the compound represented by the general formula (2) increases the viscosity in the low shear region, suppresses combustion droplets in the combustion test, and improves flame retardancy. Tend.

(In the general formula (2), R ¹ , R ² and X have the same meaning as in the general formula (1).)

  The content of the structural unit derived from the compound represented by the general formula (2) is preferably 10 to 6,000 mass ppm in the polycarbonate resin (A1), and preferably 60 to 5,000 mass ppm. More preferably, 120 to 4,000 mass ppm is more preferable, and 600 to 3,500 mass ppm is most preferable. If the content of the compound represented by the general formula (2) is too small, the flame retardancy may be lowered, and if it is too much, the amount of foreign matter may be increased. In the present invention, the structural unit derived from the compound represented by the general formula (2) may be referred to as a “branched structure”. The amount of branched structure can be measured by the method described in Examples described later.

  An example of the compound represented by the general formula (2) is a case where the general formula (1) is 2,2-bis (3-methyl-4-hydroxyphenyl) propane represented by the formula (1a). And a compound represented by the following formula (2 ′).

The polycarbonate resin (A1) is a structural unit derived from a dihydroxy compound other than the structural unit derived from the compound represented by the general formula (1) (hereinafter referred to as “other structural unit”) within a range not impairing the object of the present invention. It may also be a copolymer polycarbonate resin. As other structural units, for example, derived from an aromatic dihydroxy compound represented by the following general formula (3) (for example, a structural unit derived from bisphenol A), or derived from another dihydroxy compound as described later The structural unit to be mentioned.
(In general formula (3), X has the same meaning as X in general formula (1).)

  A preferable specific example of the structural unit derived from the aromatic dihydroxy compound represented by the general formula (3) is 2,2-bis (4-hydroxyphenyl) propane, that is, a carbonate structural unit derived from bisphenol A. .

  When the polycarbonate resin (A1) is a copolymer polycarbonate resin having a structural unit derived from the general formulas (1) and (3), the inclusion of the structural unit derived from the aromatic dihydroxy compound represented by the general formula (3) The proportion in the polycarbonate resin (A1) is usually less than 50% by mass, preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably 10% by mass or less. Most preferably, it is 5 mass% or less.

  The polycarbonate resin (A1) may have other structural units other than the structural units represented by the general formulas (1) to (3).

Examples of other structural units other than the structural units represented by the general formulas (1) to (3) include the following structural units derived from dihydroxy compounds.
For example, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxy-3- (1-methylethyl) phenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3- (1) -Methylpropyl) phenyl) propane, 2,2-bis (4-hydroxy-3-cyclohexylphenyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 1,1-bis (4- Hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenyl ester , Bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxy-3- (1-methylethyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) ) Cyclohexane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexane, 1,1-bis (4- Hydroxy-3-phenylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) -1- Phenylethane, 1,1-bis (4-hydroxy-3- (1-methylethyl) phenyl) -1-phenylethane 1,1-bis (4-hydroxy-3-tert-butylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) -1-phenylethane, , 1-bis (4-hydroxy-3-cyclohexylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy) Phenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 4,4 ′-(1,3-phenylenediisopropylidene) bisphenol, 4,4 ′-(1,4-phenylenediisopropylidene) ) Bisphenol, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluor Len, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxyphenyl ether, 4,4′-dihydroxybiphenyl, 1,1-bis (4-hydroxyphenyl) -3,3-5-trimethylcyclohexane, 1, 1-bis (4-hydroxy-6-methyl-3-tert-butylphenyl) butane and the like can be mentioned.

  The content ratio of other structural units other than the structural units represented by the general formulas (1) to (3) of the polycarbonate resin (A1) is usually less than 50% by mass, preferably 40% by mass in the polycarbonate resin (A1). Hereinafter, it is more preferably 30% by mass or less, further preferably 20% by mass or less, particularly preferably 10% by mass or less, and most preferably 5% by mass or less.

<Physical properties of polycarbonate resin (A1)>
The viscosity average molecular weight (Mv) of the polycarbonate resin (A1) is less than 30,000. The viscosity average molecular weight is preferably 18,000 to 29,000, more preferably 20,000 to 28,000, further preferably 22,000 to 28,000, and 25,000 to 27,000. Is particularly preferred. When the viscosity average molecular weight is 30,000 or more, the fluidity is lowered, the moldability is deteriorated, and the number of foreign matters is increased. Even if the viscosity average molecular weight is too low, flame retardancy and mechanical properties are lowered.
In addition, the measuring method of a viscosity average molecular weight is as the below-mentioned Example.

In the polycarbonate resin (A1), the amount of terminal hydroxy groups greatly affects thermal stability, hydrolysis stability, color tone, etc., and also reduces foreign matters derived from gels during the production and molding of resin compositions. From this point, the amount of terminal hydroxy groups of the polycarbonate resin (A1) is usually 10 ppm by mass or more, preferably 50 ppm by mass or more, more preferably 100 ppm by mass or more, and further preferably 200 masses. ppm or more, particularly preferably 300 mass ppm or more, and most preferably 500 mass ppm or more. The terminal hydroxy amount is usually 1,200 mass ppm or less, preferably 1,000 mass ppm or less, more preferably 800 mass ppm or less, still more preferably 700 ppm or less, and most preferably 650 mass ppm or less. If the amount of terminal hydroxy groups of the polycarbonate resin (A1) is excessively small, the initial hue at the time of molding tends to deteriorate. When the amount of terminal hydroxy groups is excessively large, the residence heat stability and moist heat resistance are lowered, and there is a tendency that gel-derived foreign matter is likely to be generated.
In the present invention, the amount of the terminal hydroxy group of the polycarbonate resin is the mass of the terminal hydroxy group with respect to the mass of the polycarbonate resin expressed in ppm, and the titanium tetrachloride / acetic acid method (Macromol. Chem. 88, 215 (1965). This is a value measured by colorimetric determination in accordance with (see)).

  Polycarbonate resin (A1) has a ratio (Mw / Mn) of polystyrene-equivalent weight average molecular weight Mw and number average molecular weight Mn measured by gel permeation chromatography (GPC) of 3.0 or more and 5.0 or less. A range is preferable. Further, Mw / Mn is more preferably in the range of 3.0 or more and 4.0 or less. When Mw / Mn is too small, the fluidity in the molten state increases and the moldability tends to decrease. On the other hand, if Mw / Mn is excessively large, the melt viscosity tends to increase and molding becomes difficult.

  The polycarbonate resin (A1) preferably has a pencil hardness of HB or higher in accordance with JIS K5600-5-4 (1999). The pencil hardness of the polycarbonate resin is more preferably F or higher, still more preferably H or higher, and most preferably 2H or higher. However, it is usually 3H or less. A polycarbonate resin having a pencil hardness of less than HB tends to scratch the surface, and a conventional bisphenol A type polycarbonate resin has an insufficient pencil hardness of 2B. In the present invention, the pencil hardness is a value measured for a molded body having a thickness of 3 mm obtained by injection molding of a polycarbonate resin.

The polycarbonate resin (A1) has a glass transition temperature of preferably 140 ° C. or lower, more preferably 135 ° C. or lower, more preferably 110 ° C. or higher, and more preferably 115 ° C. or higher. . It is preferable that the glass transition temperature be in such a range because the fluidity tends to be improved.
In the present invention, the glass transition temperature refers to the temperature at the inflection point when the temperature is raised from room temperature at a rate of 10 ° C./min under a nitrogen stream using differential scanning calorimetry (DSC). Say.

  The polycarbonate resin (A1) is preferably obtained by a melt polymerization method of an aromatic dihydroxy compound and a carbonic acid diester.

  The polycarbonate resin (A1) has a structural feature that the two benzene ring positions of the bisphenol skeleton are substituted with methyl groups, and the resin is easily gelled during the production and molding of the resin composition. It has been clarified for the first time by the present inventors that foreign matter is likely to be generated. And it became clear for the first time by examination of the present inventors that the generation of foreign substances derived from the gelled product is effectively suppressed by adjusting the terminal hydroxy group of the polycarbonate resin (A1) to a specific amount or less. It is a surprising effect.

[Polycarbonate resin (A2)]
The polycarbonate resin (A2) is an aromatic polycarbonate resin having a viscosity average molecular weight of 50,000 to 95,000.

  There is no limitation on the polymer structure of the polycarbonate resin (A2), and it may have the same polymer structure as the polycarbonate resin (A1) or may have a polymer structure different from that of the polycarbonate resin (A1). The polycarbonate resin (A1) is preferably a polycarbonate resin having a different polymer structure, more preferably a polycarbonate resin having a structural unit represented by the general formula (3).

  A preferred specific example of the polycarbonate structural unit represented by the general formula (3) is 2,2-bis (4-hydroxyphenyl) propane, that is, a carbonate structural unit derived from bisphenol A. It is preferable to use bisphenol A as a monomer raw material because the high molecular weight of the polycarbonate resin (A2) becomes easier.

As polycarbonate resin (A2), you may have other structural units other than the structural unit represented by the said General formula (3).
The content in the case of having other structural units other than the structural unit represented by the general formula (3) is usually less than 50% by mass, preferably 40% by mass or less, more preferably 30% by mass in the polycarbonate resin (A2). % Or less, more preferably 20% by mass or less, particularly preferably 10% by mass or less, and most preferably 5% by mass or less.

Examples of other structural units other than the structural unit represented by the general formula (3) include the following structural units derived from dihydroxy compounds.
For example, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2 , 2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3- (1-methylpropyl) phenyl) propane, 2,2-bis (4-hydroxy-) 3-cyclohexylphenyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) phenylmethane, 1,1- (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3- (1-methylethyl) Phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-phenylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) -1-phenylethane, 1,1 Bis (4-hydroxy-3- (1-methylethyl) phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) -1-phenylethane, 1,1-bis (4- Hydroxy-3-phenylphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 4,4 ′-(1,3 -Phenylenediisopropylidene) bisphenol, 4,4 '-(1,4-phenylenediisopropylidene) bisphenol, 9,9-bis (4-hydroxy) Phenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxyphenyl ether, 4,4′-dihydroxybiphenyl, 1,1- Bis (4-hydroxyphenyl) -3,3-5-trimethylcyclohexane, 1,1-bis (4-hydroxy-6-methyl-3-tert-butylphenyl) butane and the like can be mentioned.

<Physical properties of polycarbonate resin (A2)>
The viscosity average molecular weight (Mv) of the polycarbonate resin (A2) is 50,000 to 95,000 as described above. By setting it as such a high viscosity average molecular weight, a flame retardance and a mechanical physical property improve. When the viscosity average molecular weight exceeds 95,000 and is too high, fluidity is lowered and the amount of foreign matter is increased.

  The polycarbonate resin (A2) has a glass transition temperature of preferably 160 ° C. or lower, more preferably 155 ° C. or lower, further preferably 150 ° C. or lower, and preferably 130 ° C. or higher. 140 ° C. or higher is more preferable, and 145 ° C. or higher is further preferable. By setting the glass transition temperature in such a range, a resin composition having excellent heat resistance and fluidity tends to be obtained, which is preferable.

  The polycarbonate resin (A2) is preferably obtained by an interfacial polymerization method.

[Polycarbonate resin (A3)]
The polycarbonate resin composition of the present invention comprises a polycarbonate resin (A1) having a structural unit derived from the aromatic dihydroxy compound represented by the general formula (1) and having a viscosity average molecular weight of less than 30,000 and a viscosity average molecular weight of 50. In addition to the polycarbonate resin (A2) of 1,000,000 to 95,000, it may further contain a polycarbonate resin (A3) having a viscosity average molecular weight of 10,000 to 30,000 having a polymer structure different from that of the polycarbonate resin (A1). preferable.

  The polycarbonate resin (A3) includes the same polycarbonate resin as the polycarbonate resin (A2) except that the viscosity average molecular weight is in the range of 10,000 to 30,000, and the structural unit derived from bisphenol A is A polycarbonate resin is preferred.

  In the polycarbonate resin (A3), the amount of terminal hydroxy groups greatly affects thermal stability, hydrolysis stability, color tone, etc., so the amount of terminal hydroxy groups in the polycarbonate resin (A3) is usually 10 mass ppm or more. Yes, it is preferably 30 mass ppm or more, more preferably 50 mass ppm or more, still more preferably 100 mass ppm or more, and particularly preferably 150 mass ppm or more. The terminal hydroxy amount is usually 1,000 ppm by mass or less, preferably 800 ppm by mass or less, more preferably 500 ppm by mass or less, and further preferably 300 ppm or less. If the amount of terminal hydroxy groups of the polycarbonate resin (A3) is too small, the initial hue at the time of molding tends to deteriorate, and the production of the polycarbonate resin (A3) itself tends to be difficult. When the amount of terminal hydroxy groups is excessively large, the residence heat stability and the heat and humidity resistance tend to decrease.

  The polycarbonate resin (A3) is preferably obtained by an interfacial polymerization method.

<Method for Producing Polycarbonate Resins (A1) to (A3)>
The method for producing the polycarbonate resin used in the present invention is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt polymerization method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
Hereinafter, a particularly preferable one of these methods will be specifically described.

-Interfacial polymerization method First, the case where a polycarbonate resin is manufactured by the interfacial polymerization method will be described.
In the interfacial polymerization method, the aromatic dihydroxy compound represented by the general formulas (1) and (3) and the carbonate precursor are usually maintained in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, and the pH is usually kept at 9 or higher. After reacting with a body (preferably phosgene), a polycarbonate resin is obtained by performing interfacial polymerization in the presence of a polymerization catalyst. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present if necessary, and an antioxidant may be present for the purpose of preventing oxidation of the dihydroxy compound.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate. Among them, sodium hydroxide and Potassium hydroxide is preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. In particular, it is preferably set to 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride Pyridine; guanine; guanidine salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the molecular weight regulator include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides, and the like. Among them, aromatic phenols are preferable.
Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-oxinebenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a polycarbonate resin composition can be improved. Moreover, a terminal hydroxy group can also be arbitrarily adjusted by adjusting the usage-amount of a molecular weight modifier.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator can be mixed at any time as long as it is between the reaction (phosgenation) of the dihydroxy compound and phosgene and the start of the polymerization reaction.
In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

-Melt polymerization method Next, the case where a polycarbonate resin is manufactured by the melt polymerization method (melt transesterification method) is demonstrated. In the melt polymerization exchange method, an ester exchange reaction between an aromatic dihydroxy compound and a carbonic acid diester is performed.

The aromatic dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diaryl carbonates such as diphenyl carbonate; and substituted diphenyl carbonates such as ditolyl carbonate. Of these, diaryl carbonate is preferable, and diphenyl carbonate is particularly preferable. In addition, 1 type may be used for carbonic acid diester, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the aromatic dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound. It is more preferable to use the above. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxy groups can be adjusted to a suitable range.

  In the polycarbonate resin, the amount of terminal hydroxy groups tends to have a great influence on thermal stability, hydrolysis stability, color tone and the like. For this reason, you may adjust the amount of terminal hydroxy groups as needed by arbitrary well-known methods. In the transesterification reaction, a polycarbonate resin in which the amount of terminal hydroxy groups is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

When adjusting the amount of terminal hydroxy groups by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among these, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  In the melt polymerization method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less (267 Pa or less). As a specific operation, a melt polycondensation reaction may be performed under the conditions in this range while removing by-products such as hydroxy compounds.

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. In the case of a batch system, the order of mixing the reaction substrate, reaction medium, catalyst, additive, etc. is arbitrary as long as the desired polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. However, in view of the stability of the polycarbonate resin and the polycarbonate resin composition, the melt polycondensation reaction is preferably carried out continuously.

In the melt polymerization method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 mass ppm or more normally with respect to polycarbonate resin, and is 100 mass ppm or less normally, Preferably it is 20 mass ppm or less.

[Polycarbonate resin (A)]
As described above, the polycarbonate resin (A) contained in the polycarbonate resin composition of the present invention contains the polycarbonate resins (A1) and (A2) as essential components, but the content ratio thereof is the entire polycarbonate resin (A). As 100 mass%, the quantity of polycarbonate resin (A1) is 50-98 mass%, Preferably it is 60-94 mass%, More preferably, it is 70-90 mass%. The amount of the polycarbonate resin (A2) is 2 to 30% by mass, preferably 3 to 20% by mass, more preferably 4 to 15% by mass, and particularly preferably 5 to 13% by mass.
Further, when the polycarbonate resin (A3) having a viscosity average molecular weight of 10,000 to 30,000 having a polymer structure different from that of the polycarbonate resin (A1) is contained, a preferable content is 100 mass of the whole polycarbonate resin (A). % Is 2 to 30% by mass, preferably 3 to 20% by mass, and more preferably 5 to 15% by mass.
By containing the polycarbonate resin (A) in such a ratio and further containing the organic sulfonic acid metal salt (B), it is transparent and excellent in flame retardancy, has a small amount of foreign matters, and has a high hardness. It is possible to achieve a polycarbonate resin composition having good properties and excellent moldability with a thin wall.

  The polycarbonate resin (A) preferably contains a structural unit derived from the compound represented by the general formula (2). When the branched structure generated from the structural unit derived from the compound represented by the general formula (2) is included, the viscosity in the low shear region is increased, combustion drops are suppressed in the combustion test, and flame retardancy is improved. Conceivable.

  The content of the structural unit derived from the compound represented by the general formula (2) is preferably 10 to 5,000 mass ppm in the polycarbonate resin (A), and preferably 50 to 4,000 mass ppm. More preferably, 100 to 3,500 ppm by mass is further preferable, and 500 to 3,000 ppm by mass is most preferable. If the content of the compound represented by the general formula (2) is too small, the flame retardancy may be lowered, and if it is too much, the amount of foreign matter may be increased.

  When the polycarbonate resin (A) contains a structural unit derived from the compound represented by the general formula (2), the amount of the branched structure may be adjusted according to the above-described method for producing a polycarbonate resin. In particular, by appropriately adjusting the reaction temperature of the polymerization reaction, the reaction time, the resin temperature in the extruder, the residence time, and the like, a polycarbonate resin having a branched structure amount within a desired range can be easily obtained.

<Physical properties of polycarbonate resin (A)>
In the polycarbonate resin (A), the amount of terminal hydroxy groups greatly affects thermal stability, hydrolysis stability, color tone, etc., and also reduces foreign matters derived from gels during the production and molding of resin compositions. From this point, the amount of terminal hydroxy groups of the polycarbonate resin (A) is usually 10 ppm by mass or more, preferably 40 ppm by mass or more, more preferably 80 ppm by mass or more, and further preferably 150 masses. ppm or more, particularly preferably 300 mass ppm or more, and most preferably 400 mass ppm or more. The amount of terminal hydroxy is usually 1,000 ppm by mass or less, preferably 800 ppm by mass or less, more preferably 700 ppm by mass or less, further preferably 650 ppm or less, and most preferably 600 ppm by mass or less. When the amount of terminal hydroxyl groups of the polycarbonate resin (A) is excessively small, the initial hue at the time of molding tends to deteriorate. When the amount of terminal hydroxy groups is excessively large, the residence heat stability and moist heat resistance are lowered, and there is a tendency that gel-derived foreign matter is likely to be generated.
In addition, the amount of terminal hydroxyl groups of polycarbonate resin (A) can be adjusted by adjusting each terminal hydroxyl group of polycarbonate resin (A1)-(A3) and each compounding ratio suitably.

In the present invention, the polycarbonate resin (A) preferably includes a polycarbonate resin having a structural viscosity index N in a predetermined range.
The structural viscosity index N is an index for evaluating the flow characteristics of the melt. Usually, the melting characteristics of polycarbonate resin can be expressed by the formula: γ = a · σ ^N , and a and N are obtained from the intercept and slope of the logarithmic plot of γ and σ (Log γ = Loga + NLogσ). In the formula, γ: shear rate, a: constant, σ: stress, N: structural viscosity index.
In the above formula, when N = 1, Newtonian fluidity is shown, and as the value of N increases, non-Newtonian fluidity increases. That is, the flow characteristics of the melt are evaluated by the magnitude of the structural viscosity index N. In general, a polycarbonate resin having a large structural viscosity index N tends to have a high melt viscosity in a low shear region. For this reason, when a polycarbonate resin having a large structural viscosity index N is mixed with another polycarbonate resin, dripping at the time of combustion of the obtained polycarbonate resin composition can be suppressed, and flame retardancy can be improved.

The structural viscosity index N is expressed by Log η _a = [(1-N) / N] × Log γ + C derived from the above formula, as described in, for example, JP-A-2005-232442. Is also possible. In the formula, N: structural viscosity index, γ: shear rate, C: constant, η _a : apparent viscosity. As can be seen from this equation, the N value can also be evaluated from γ and ηa in _a low shear region in which the viscosity behavior is greatly different. For example, the N value can be determined from η _a at γ = 12.16 sec ⁻¹ and γ = 24.32 sec ⁻¹ .

  The polycarbonate resin (A) has a structural viscosity index N of preferably 1.1 or more, more preferably 1.2 or more, particularly 1.25 or more, more preferably 1.28 or more, and usually 1.8 or less. From the viewpoint of flame retardancy, it is preferable that a polycarbonate resin having a ratio of 1.7 or less is contained. The polycarbonate resin (A) contains a polycarbonate resin having a structural viscosity index N in the predetermined range, preferably 3% by mass or more, more preferably 5% by mass or more, and further 10% by mass or more in the polycarbonate resin (A). It is preferable to do. When the polycarbonate resin (A) contains a polycarbonate resin having a structural viscosity index N in the above predetermined range, and further contains an organic sulfonic acid metal salt (B), a synergistic effect can be remarkably exhibited.

  Furthermore, it is preferable that the structural viscosity index N1 of the polycarbonate resin (A1) and the structural viscosity index N2 of the polycarbonate resin (A2) satisfy N1 <N2. By setting it as such a structural viscosity index, it tends to be easy to obtain a polycarbonate resin composition with less foreign matter and excellent surface hardness, fluidity, transparency and flame retardancy.

  The structural viscosity index N1 of the polycarbonate resin (A1) is preferably 1.0 or more, more preferably 1.1 or more, particularly 1.15 or more, still more preferably 1.2 or more, and preferably 1.4 or less. More preferably, it is 1.35 or less, More preferably, it is 1.3 or less, Most preferably, it is 1.25 or less. As described above, in general, a polycarbonate resin having a larger structural viscosity index N suppresses dripping at the time of combustion of a polycarbonate resin composition that can increase the melt viscosity in a low shear region, and improves flame retardancy. However, in the polycarbonate resin (A1), when the structural viscosity index N1 is too high, foreign substances are increased and the color tone may be deteriorated by the inventors' investigation. Therefore, the structural viscosity index N1 of the polycarbonate resin (A1) is not preferably too high as the structural viscosity index N2 of the polycarbonate resin (A2). In the present invention, the structural viscosity index is more preferably N1 <N2. .

In addition, it is generally known to improve the flame retardancy of the resin composition by increasing the viscosity average molecular weight of the polycarbonate resin. In the polycarbonate resin (A1), it was also clarified by the present inventors that the amount of foreign matter may increase.
However, surprisingly, in the polycarbonate resin composition of the present invention, the polycarbonate resin (A1) having a specific structure can be obtained without excessively increasing the structural viscosity index N1 and the viscosity average molecular weight of the polycarbonate resin (A1). Adopted, preferably by adjusting the structural viscosity index N1 and the branched structure amount derived from the general formula (2) to a specific range, there is less problem of foreign matter and color tone, and more without sacrificing fluidity It became possible to achieve high flame retardancy.

  In addition, the lower limit of the structural viscosity index N1 of the polycarbonate resin (A1) is as described above. However, if the structural viscosity index N1 is too low, the melt viscosity of the polycarbonate resin (A) is too low, so that dripping occurs during ignition. It is not preferable because it may occur and flame retardancy may be reduced.

  The structural viscosity index N2 of the polycarbonate resin (A2) is preferably 1.2 or more, more preferably 1.25 or more, particularly 1.3 or more, still more preferably 1.4 or more, and preferably 1.9. Below, more preferably 1.8 or less, still more preferably 1.7 or less, and particularly preferably 1.6 or less. If the structural viscosity index N2 of the polycarbonate resin (A2) is too high, the melt viscosity becomes too high, the fluidity is lowered, and the moldability may be deteriorated. Also. If the structural viscosity index N2 of the polycarbonate resin (A2) is too low, the melt viscosity of the polycarbonate resin (A) is too low, so that dripping may occur during ignition and flame retardancy may be reduced, which is not preferable.

  As the polycarbonate resin (A3), the structural viscosity index N is preferably 1.1 or more, more preferably 1.2 or more, particularly 1.25 or more, more preferably 1.28 or more, and usually 1.8 or less. From the viewpoint of flame retardancy, it is preferable that a polycarbonate resin having a ratio of 1.7 or less is contained. When the polycarbonate resin (A3) includes a polycarbonate resin having a structural viscosity index N in the specific range, the content thereof is preferably 10% by mass or more, more preferably 20% by mass or more in the polycarbonate resin (A3). More preferably, it is 40% by mass or more, and particularly preferably 60% by mass or more. By including a polycarbonate resin having a high structural viscosity index N in this way, dripping during combustion of the polycarbonate resin composition of the present invention can be suppressed, and flame retardancy can be further improved.

  When a polycarbonate resin having a structural viscosity index N in the predetermined range is manufactured, the polycarbonate resin may be manufactured according to the above-described method for manufacturing a polycarbonate resin. At this time, it is preferable to produce a polycarbonate resin having a branched structure (hereinafter, referred to as “branched polycarbonate resin” as appropriate) because a polycarbonate resin having a structural viscosity index N within a predetermined range is easily obtained. This is because the branched polycarbonate resin tends to have a high structural viscosity index N.

  Examples of the method for producing the branched polycarbonate resin include the methods described in JP-A-8-259687, JP-A-8-245782, and the like. In the methods described in these documents, when the dihydroxy compound and the carbonic acid diester are reacted by the melt transesterification method, the structural viscosity index can be obtained without using a branching agent by selecting the catalyst conditions or production conditions. A polycarbonate resin which is high and excellent in hydrolysis stability can be obtained.

  As another method for producing a branched polycarbonate resin, an interfacial polymerization method using a trifunctional or higher polyfunctional compound (branching agent) in addition to the dihydroxy compound and the carbonate precursor, which are the raw materials of the polycarbonate resin described above. Or the method of copolymerizing these by a melt transesterification method is mentioned.

  Examples of the trifunctional or higher functional compound include 1,3,5-trihydroxybenzene (phloroglucin), 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4 , 6-Dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri Polyhydroxy compounds such as (4-hydroxyphenyl) benzene and 1,1,1-tri (4-hydroxyphenyl) ethane;

  3,3-bis (4-hydroxyaryl) oxyindole (that is, isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferable.

  The polyfunctional compound can be used by substituting a part of the dihydroxy compound. The amount of the polyfunctional aromatic compound used is usually 0.01 mol% or more, preferably 0.1 mol% or more, and usually 10 mol% or less, preferably 3 mol% or less, relative to the dihydroxy compound. It is. In addition, 1 type may be used for a polyfunctional compound and it may use 2 or more types together by arbitrary combinations and a ratio.

[Organic sulfonic acid metal salt (B)]
The polycarbonate resin composition of the present invention contains an organic sulfonic acid metal salt (B). By containing the organic sulfonic acid metal salt (B) together with the polycarbonate resins (A1) and (A2) described above, flame retardancy is effectively prevented without impairing the transparency of the polycarbonate resin composition of the present invention. Thus, a polycarbonate resin composition having a high hardness and excellent moldability with a thin wall can be obtained.
As the organic sulfonic acid metal salt (B), an organic sulfonic acid alkali metal salt is preferable, and examples thereof include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts. Among them, aromatic sulfonic acid metal salts, perfluoro Fluorine-containing organic sulfonic acid metal salts represented by alkanesulfonic acid metal salts are more preferred, and fluorine-containing sulfonic acid alkali metal salts are particularly preferred.

  The metal possessed by the organic sulfonic acid metal salt (B) is preferably an alkali metal or alkaline earth metal, and the type thereof is an alkali metal such as lithium, sodium, potassium, rubidium or cesium, or an alkaline earth such as calcium or barium. Examples of the metal include sodium, potassium, and cesium, and potassium and sodium are particularly preferable.

The aromatic sulfonesulfonic acid metal salt is preferably an aromatic sulfonesulfonic acid alkali metal salt, an aromatic sulfonesulfonic acid alkaline earth metal salt, or the like. The acid alkaline earth metal salt may be a polymer. Specific examples of the aromatic sulfonesulfonic acid metal salt include sodium salt of diphenylsulfone-3-sulfonic acid, potassium salt of diphenylsulfone-3-sulfonic acid, and sodium of 4,4′-dibromodiphenyl-sulfone-3-sulfone. Salt, potassium salt of 4,4′-dibromodiphenylsulfone-3-sulfone, calcium salt of 4-chloro-4′-nitrodiphenylsulfone-3-sulfonic acid, diphenylsulfone-3,3′-disulfonic acid di Examples thereof include sodium salts and dipotassium salts of diphenylsulfone-3,3′-disulfonic acid.

As the fluorine-containing organic sulfonic acid metal salt, a fluorine-containing organic sulfonic acid alkali metal salt is preferable, and examples of preferable ones include a fluorine-containing aliphatic sulfonic acid alkali metal salt and a fluorine-containing aromatic sulfonic acid alkali metal salt. .
Among them, specific examples of preferable ones include potassium perfluorobutanesulfonate, lithium perfluorobutanesulfonate, sodium perfluorobutanesulfonate,
At least one C—F in the molecule, such as cesium perfluorobutane sulfonate, lithium trifluoromethane sulfonate, sodium trifluoromethane sulfonate, potassium trifluoromethane sulfonate, potassium perfluoroethane sulfonate, potassium perfluoropropane sulfonate, etc. An alkali metal salt of a fluorine-containing aliphatic sulfonic acid having a bond;

  Disodium perfluoromethane disulfonate, dipotassium perfluoromethane disulfonate, disodium perfluoroethane disulfonate, dipotassium perfluoroethane disulfonate, dipotassium perfluoropropane disulfonate, dipotassium perfluoroisopropane disulfonate, perfluorobutane disulfonate Fluorine-containing aliphatic sulfone such as disodium, dipotassium perfluorobutane disulfonate, dipotassium perfluorooctane disulfonate, alkali metal salts of fluorine-containing aliphatic disulfonic acid having at least one C—F bond in the molecule; Examples include alkali metal salts of acids.

  Examples of the fluorine-containing aromatic sulfonic acid alkali metal salt include dipotassium diphenylsulfone-3,3′-disulfonate, potassium diphenylsulfone-3-sulfonate, sodium benzenesulfonate, sodium (poly) styrenesulfonate, paratoluenesulfonic acid. Sodium, (branched) sodium dodecylbenzenesulfonate, sodium trichlorobenzenesulfonate, potassium benzenesulfonate, potassium styrenesulfonate, potassium (poly) styrenesulfonate, potassium paratoluenesulfonate, (branched) potassium dodecylbenzenesulfonate, Potassium trichlorobenzenesulfonate, cesium benzenesulfonate, cesium (poly) styrenesulfonate, cesium p-toluenesulfonate, (branched) dodecylbenzenesulfone Cesium, such as trichlorobenzene sulfonate, cesium, alkali metal salts of aromatic sulfonic acids and the like having at least one aromatic group in the molecule.

  The alkali metal salt of fluorine-containing organic sulfonic acid may be an alkali metal salt of fluorine aliphatic sulfonic acid imide. For example, bis (perfluoropropanesulfonyl) imide lithium, bis (perfluoropropanesulfonyl) imide sodium, bis (perfluoropropanesulfonyl) imide potassium, bis (perfluorobutanesulfonyl) imide lithium, bis (perfluorobutanesulfonyl) imide Sodium, potassium bis (perfluorobutanesulfonyl) imide, potassium trifluoromethane (pentafluoroethane) sulfonylimide, sodium trifluoromethane (nonafluorobutane) sulfonylimide, potassium trifluoromethane (nonafluorobutane) sulfonylimide, trifluoromethane, An alkali metal salt of a fluorinated aliphatic disulfonic imide having at least one C—F bond in the molecule;

Cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide lithium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide sodium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide potassium An alkali metal salt of a cyclic fluorinated aliphatic sulfonimide having at least one C—F bond in the molecule, such as an alkali metal salt of a fluorinated aliphatic sulfonic imide, such as;
Etc.

Among the above-mentioned, fluorine-containing aliphatic sulfonic acid alkali metal salts are particularly preferable.
The alkali metal salt of a fluorinated aliphatic sulfonic acid is particularly preferably an alkali metal salt of perfluoroalkanesulfonic acid, specifically, potassium perfluorobutanesulfonate or sodium perfluoroethanesulfonate.

The purity of the organic sulfonic acid alkali metal salt is preferably 99% or more. If the purity is lower than this, the composition may be discolored or the thermal stability may be deteriorated.
Specific examples of such a fluorine-containing organic sulfonic acid alkali metal salt include DIC's product name MegaFuck F114P, LANXESS's product name Biowet C4, and Insight High Technology's product name IHT-FR21. Illustrated.

  The content of the organic sulfonic acid metal salt (B) in the polycarbonate resin composition of the present invention is 0.01 to 1 part by mass, preferably 0.02 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). Or more, more preferably 0.04 parts by mass or more, particularly preferably 0.05 parts by mass or more, preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass or less, particularly preferably 0.3 parts by mass. Or less. If the content of the organic sulfonic acid metal salt (B) is too small, the flame retardancy of the obtained polycarbonate resin composition becomes insufficient. Conversely, if the content is too large, the thermal stability of the polycarbonate resin is reduced, and the molded product Appearance defect and mechanical strength decrease occur.

[Stabilizer]
The polycarbonate resin composition of the present invention preferably contains a stabilizer, and various stabilizers can be used as the stabilizer, but a hindered phenol stabilizer and a phosphorus stabilizer are preferred.

[Hindered phenol stabilizer]
Examples of the hindered phenol stabilizer include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl). -4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3 , 5-di-tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphoate, 3,3 ', 3 ", 5,5', 5" -hexa-tert- Til-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [ 3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert- Butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) Ethyl] -4,6-di -tert- pentylphenyl acrylate.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such a phenol-based stabilizer include, for example, trade names (hereinafter the same) “Irganox 1010” and “Irganox 1076” manufactured by BASF, “ADEKA STAB AO-50” manufactured by ADEKA, “ Adekastab AO-60 "etc. are mentioned.
In addition, 1 type may contain hindered phenolic antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the hindered phenol stabilizer is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and preferably 0.5 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). It is not more than part by mass, more preferably not more than 0.3 part by mass. When the content is less than 0.01 parts by mass, heat stability, wet heat stability, and hue may be deteriorated. When the content exceeds 1 part by mass, gas is generated during molding and An appearance defect may occur, which is not preferable.

[Phosphorus stabilizer]
Any known phosphorous stabilizer can be used, but specific examples include phosphorous acid, phosphonic acid, phosphorous acid, phosphinic acid, polyphosphoric acid and other phosphorus oxo acids; acidic sodium pyrophosphate, acidic Acidic pyrophosphate metal salts such as potassium pyrophosphate and acid calcium pyrophosphate; Group 1 or Group 2B metal phosphates such as potassium phosphate, sodium phosphate, cesium phosphate, zinc phosphate; organic phosphate compounds, organic phosphates Phyto compounds, organic phosphonite compounds and the like can be mentioned, and organic phosphite compounds are particularly preferable.

Organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di- tert-butylphenyl) octyl phosphite and the like.
Specific examples of such an organic phosphite compound include, for example, trade names (hereinafter the same) “ADEKA STAB 1178”, “ADEKA STAB 2112”, “ADEKA STAB HP-10” manufactured by ADEKA Corporation, “ JP-351 ”,“ JP-360 ”,“ JP-3CP ”,“ Irgaphos 168 ”manufactured by BASF, and the like.

  One type of phosphorus stabilizer may be contained, and two or more types may be mixed and blended, but the content of the phosphorus stabilizer is 100 parts by mass of the polycarbonate resin (A). Preferably it is 0.01-0.5 mass part, More preferably, it is 0.02-0.1 mass part. If it is less than 0.01 parts by mass, the effect as a heat stabilizer is insufficient, the molecular weight during molding and the hue are deteriorated, particularly yellowing easily occurs at high temperature and high humidity, and 0.5 mass. When it exceeds the part, the molecular weight is lowered and the hue is further deteriorated.

[Ultraviolet absorber]
The polycarbonate resin composition of the present invention preferably contains an ultraviolet absorber.
Examples of ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; organics such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, and hindered amine compounds. Examples include ultraviolet absorbers. In these, an organic ultraviolet absorber is preferable and a benzotriazole compound is more preferable. By selecting the organic ultraviolet absorber, the polycarbonate resin composition of the present invention has good transparency and mechanical properties.

  Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like are particularly mentioned.

  Specific examples of the benzophenone compound include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxy Benzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4 4,4'-dimethoxybenzophenone and the like are preferred.

Specific examples of the salicylate compound preferably include phenyl salicylate and 4-tert-butylphenyl salicylate.
Specific examples of the cyanoacrylate compound include, for example, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like.
Examples of the triazine compound include compounds having a 1,3,5-triazine skeleton.

As a specific example of the oxanilide compound, for example, 2-ethoxy-2′-ethyloxalinic acid bisalinide and the like are preferably exemplified.
As the malonic acid ester compound, 2- (alkylidene) malonic acid esters are preferably exemplified, and 2- (1-arylalkylidene) malonic acid esters are more preferable.

  The content of the ultraviolet absorber is usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and usually 3 parts by mass or less, preferably 2 with respect to 100 parts by mass of the polycarbonate resin (A). It is 1 part by mass or less. If the content of the ultraviolet absorber is less than the lower limit of the range, the effect of improving the weather resistance may be insufficient, and if the content of the ultraviolet absorber exceeds the upper limit of the range, the mold Debogit etc. may occur and cause mold contamination. In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

[Release agent]
The polycarbonate resin composition of the present invention preferably contains a release agent.
Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane silicone oils, and the like.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic or alicyclic saturated monohydric alcohol or aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferable.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons.
Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.

  The content of the release agent is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 2 parts by mass or less, preferably 1 with respect to 100 parts by mass of the polycarbonate resin (A). It is below mass parts. When the content of the release agent is less than the lower limit of the range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the range, hydrolysis resistance And mold contamination during injection molding may occur.

[Other additives]
The polycarbonate resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Examples of such additives include dyes and pigments, fluorescent brighteners, anti-dripping agents, antistatic agents, antifogging agents, lubricants, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like. It is done.

In the present invention, in order to suppress dripping at the time of combustion of the resin composition, it is possible to add an anti-drip agent such as polytetrafluoroethylene, but the anti-drip agent may impair transparency. For this reason, the content of the anti-dripping agent is preferably 2% by mass or less, more preferably 1% by mass or less, and 0.5% by mass or less in the polycarbonate resin composition. Further preferred.
In the present invention, the specific polycarbonate resins (A1) and (A2) are used in combination, and a specific amount of the organic sulfonic acid metal salt (B) is contained therein. It is possible to achieve both high flame retardance and transparency that can be achieved by V-0 at 0 mm.

[Production Method of Polycarbonate Resin Composition]
There is no restriction | limiting in the method to manufacture the polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely, and polycarbonate resin (A) and organic sulfone containing polycarbonate resin (A1) and (A2) The acid metal salt (B) and other components to be blended as necessary are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then Banbury mixer, roll, Brabender, single screw kneading extrusion And a melt kneading method using a mixer such as a machine, a twin-screw kneading extruder, or a kneader.
Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, this master batch is again mixed with the remaining components and melt-kneaded. The polycarbonate resin composition of the present invention can also be produced.
The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

  In the present invention, the polycarbonate resin (A) and the organic sulfonic acid metal salt (B) containing the polycarbonate resin (A1) and (A2), and other components blended as necessary are kneaded by an extruder. At this time, it is also preferable to introduce an inert gas into the raw material inlet of the extruder. As for the inert gas, the ratio of the raw material amount F [kg / hr] and the inert gas amount G [L / min] of the polycarbonate resin composition supplied to the extruder per unit time is 0.005 ≦ G / F ≦. It is more preferable to knead while introducing to 0.2.

Hereinafter, specific examples will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of the configuration of an extruder suitable for producing the resin composition of the present invention.
The raw material polycarbonate resin (A) and the organic sulfonic acid metal salt (B) are stored in the raw material supply machine 1, and from there, an extruder having a screw 3 inside by a feeder 2 (quantitative supply machine or constant volume supply machine). 5 is supplied to a hopper 4 installed on 5. The feeder 2 and the hopper 4 are preferably connected by a hopper chute 7. The bottom of the hopper 4 is connected to the raw material inlet 6 of the extruder provided upstream of the extruder 5, and the raw material polycarbonate resin (A) and organic sulfonic acid metal salt (B) Sequentially supplied into the extruder 5 from the hopper 4 through the raw material inlet 6, heated by a band heater (not shown) disposed on the outer periphery of the extruder 5, and kneaded while being conveyed by the rotation of the screw 3. Then, it is extruded with an extrusion die, cooled, and cut by a cutting machine (not shown) to obtain pellets of a polycarbonate resin composition.
The extruder is preferably provided with a vent port 8 for degassing.

  Mixing of the organic sulfonic acid metal salt (B) added to the polycarbonate resin (A) and the optional additive can be performed at any stage before being charged into the extruder. For example, after all components are blended by a tumbler, a Henschel mixer, and a blender, they may be fed into the hopper 4 or the hopper chute 7 through the feeder 2 as necessary and supplied to the extruder 5. As the extruder, a single screw extruder, a twin screw extruder or the like can be used. Further, the organic sulfonic acid metal salt (B) and the optional additive may be supplied to the hopper 4 or the hopper chute 7 through a route different from that of the polycarbonate resin (A). At this time, these additives may be supplied alone or in a mixed state with other additives.

The method for introducing the inert gas into the raw material inlet 6 of the extruder is not particularly limited. For example, a gas inlet is provided in the vicinity of the raw material inlet 6 and the inert gas is directly introduced into the raw material inlet 6. A method, a method of providing an inert gas introduction port in the raw material hopper 4 and filling a portion from the hopper 4 to the raw material charging port with an inert gas, and introducing an inert gas from the upper part of the hopper chute 7 toward the hopper 4 And a method of introducing an inert gas by providing a gas inlet in the middle of the hopper chute 7.
In particular, a method of introducing an inert gas by providing a gas inlet (not shown) in the vicinity of the raw material inlet 6 located below the hopper 4 is such that the raw material comes into contact with the inert gas immediately before the raw material is supplied to the extruder. In addition, it is preferable because the concentration of the inert gas in the atmosphere below the hopper is maintained higher within the operable range of the extruder.
The inlet for the inert gas may be provided on the hopper 4 side, or may be attached from the extruder main body side. The direction in which the inert gas flows is preferably an upward flow with respect to the falling polycarbonate resin composition raw material. Moreover, it is preferable that the hopper 4 has airtightness to such an extent that the inert gas concentration in the internal atmosphere is maintained high. The inert gas inlets may be attached at two or more locations.

The length of the hopper chute 7 is not particularly limited, but is preferably 50 cm or more, more preferably 1 m or more, and further preferably 1.5 m or more. By providing the hopper chute 7 having such a length, the time during which the polycarbonate resin composition raw material is in contact with the inert gas in a dispersed state becomes longer, and the replacement of the air contained in the raw material with the inert gas further proceeds. And the foreign matter reduction effect of this invention becomes more remarkable and is preferable.
The material of the hopper chute 7 is not particularly limited, and may be a metal such as stainless steel or a resin such as polyethylene. In the present invention, a polyethylene resin is preferable.

  As described above, the ratio of the raw material amount F [kg / hr] and the inert gas amount G [L / min] of the polycarbonate resin composition supplied to the extruder per unit time is 0.005 ≦ G / It is preferable to be in the range of F ≦ 0.2. When G / F is less than 0.005, it is difficult to reduce the generation of foreign matter, and when G / F exceeds 0.2, it is difficult to stabilize the supply of the polycarbonate resin composition, and the resulting polycarbonate resin is obtained. There is a possibility that the quality of the composition may not be stable or the operation of the extruder may be difficult. G / F is more preferably 0.009 or more, further preferably 0.02 or more, more preferably 0.15 or less, further preferably 0.12 or less, and particularly preferably 0.1 or less. . By supplying the polycarbonate resin composition raw material and the inert gas to the extruder within such a range, the air substituted in the hopper 4 and the hopper chute 7 is discharged, and the oxygen concentration in the internal atmosphere is lowered. Since it can maintain, a foreign material does not generate | occur | produce easily in the obtained molded article, and it is more preferable. In addition, when carrying out side feed of inorganic fillers, such as glass fiber, from the middle of an extruder, these raw materials fed side are not included in the raw material amount F.

  The oxygen concentration in the hopper 4 (the center of the hopper) is preferably 20% by volume or less, more preferably 10% by volume or less, further preferably 5% by volume or less, and most preferably 1% by volume or less, preferably 0.01% by volume or more, more preferably 0.1% by volume or more, and most preferably 0.5% by volume or more. If the oxygen concentration in the hopper 4 is too high, there is a possibility that the occurrence of gel-like foreign matters and burns cannot be sufficiently suppressed, which is not preferable. Further, if the oxygen concentration in the hopper 4 is too low, it is likely that an excessive amount of inert gas needs to be supplied, the supply of the polycarbonate resin composition raw material is not stable, and the quality of the obtained polycarbonate resin composition is stable. Or the operation of the extruder may be difficult.

  Examples of the inert gas include nitrogen gas, carbon dioxide gas, and rare gas. Nitrogen gas is preferably used. The inert gas may be supplied continuously or intermittently.

  The extruder may be a single screw extruder or a twin screw extruder, but a twin screw extruder is preferred. Moreover, as an extruder, what is a vent type is also preferable. The number of vents may be one or two or more. The degree of vacuum of the vent during production is preferably −0.01 MPa or less, more preferably −0.05 MPa or less, and most preferably −0.1 MPa or less. If the vent pressure reduction degree is too high, devolatilization from the inside of the resin becomes insufficient, and bubbles may be generated in the strands to cause strand breakage. If the degree of reduced pressure in the vent is too low, the resin tends to be vented up, and stable production may be difficult.

  As L / D of the screw of an extruder, 10-80 are preferable, More preferably, it is 15-70, More preferably, it is 20-60. If the L / D of the screw of the extruder is too small, kneading is insufficient, and the quality of the obtained polycarbonate resin composition may become unstable, which is not preferable. If the L / D of the screw of the extruder is too large, the residence time in the extruder becomes long or the resin temperature rises, which may cause gel-like foreign matters and burning, which is not preferable.

  It is also preferable to use a filter in the extruder as necessary. As the filter, a candle filter, a leaf filter, a screen changer mesh filter, or the like is preferably used. In addition, it is possible to reduce gel-like foreign matters and burns by using the above-described preferable manufacturing method, but in order to remove even a few extraneous causes (fine dust, external contaminants) etc., a filter is used in combination. Sometimes it is better. However, when only a filter is used, it is particularly difficult to sufficiently remove gel-like foreign matters.

  Since the polycarbonate resin containing the structural unit derived from the aromatic dihydroxy compound represented by the general formula (1) is likely to be gelled or burnt at a high temperature, the resin temperature during melt-kneading is The resin temperature at the outlet is preferably 340 ° C. or lower, more preferably 320 ° C. or lower, further preferably 300 ° C. or lower, and usually 240 ° C. or higher, preferably 260 ° C. or higher. By kneading so that it becomes such resin temperature, generation | occurrence | production of a foreign material is suppressed more, and it becomes easy to maintain a kneadability and a mechanical physical property favorably.

  Further, when a polycarbonate resin composition is produced by a melt-kneading method using an extruder, the polycarbonate resin composition may be purged with a bisphenol A type polycarbonate resin before the raw material of the polycarbonate resin composition is charged into the extruder. preferable. The purge conditions are not particularly limited. For example, the resin temperature at the time of melt kneading is preferably 340 ° C. or lower, more preferably 320 ° C. or lower, more preferably 300 ° C. or lower, as the resin temperature at the exit of the extruder. Is more preferable, and is usually 240 ° C. or higher, preferably 260 ° C. or higher. The purge time is preferably 5 minutes or longer, more preferably 10 minutes or longer, and even more preferably 30 minutes or longer.

[Polycarbonate resin composition]
The polycarbonate resin composition thus obtained preferably contains a structural unit derived from the compound represented by the general formula (2). When the branched structure generated from the structural unit derived from the compound represented by the general formula (2) is included, the viscosity in the low shear region is increased, combustion drops are suppressed in the combustion test, and flame retardancy is improved. Conceivable.

  The content of the structural unit derived from the compound represented by the general formula (2) is preferably 10 to 5,000 mass ppm, more preferably 50 to 4,000 mass ppm in the polycarbonate resin composition. Preferably, 100 to 3,500 mass ppm is more preferable, and 500 to 3,000 mass ppm is most preferable. If the content of the compound represented by the general formula (2) is too small, the flame retardancy may be lowered, and if it is too much, the amount of foreign matter may be increased.

  When the polycarbonate resin composition contains a structural unit derived from the compound represented by the general formula (2), the branch structure amount may be adjusted according to the method for producing the polycarbonate resin. In particular, by appropriately adjusting the reaction temperature of the polymerization reaction, the reaction time, the resin temperature in the extruder, the residence time, and the like, a polycarbonate resin having a branched structure amount within a desired range can be easily obtained.

Further, the amount of terminal hydroxy groups of the obtained polycarbonate resin composition is usually 10 ppm by mass or more, preferably 40 ppm by mass or more, more preferably 80 ppm by mass or more, and further preferably 150 ppm by mass. As described above, it is particularly preferably 300 ppm by mass or more, and most preferably 400 ppm by mass or more. The amount of terminal hydroxy groups is usually 1,000 ppm by mass or less, preferably 800 ppm by mass or less, more preferably 700 ppm by mass or less, further preferably 650 ppm or less, and most preferably 600 ppm by mass or less. If the amount of terminal hydroxyl groups of the polycarbonate resin composition is too small, the initial hue at the time of molding tends to deteriorate.
When the amount of terminal hydroxy groups is excessively large, the residence heat stability and the heat and humidity resistance tend to decrease. In addition, the measuring method of the amount of terminal hydroxy groups is as the below-mentioned Example.

  Further, the glass transition temperature of the polycarbonate resin composition is preferably 140 ° C. or lower, more preferably 135 ° C. or lower, and particularly preferably 130 ° C. or lower. Moreover, it is preferable that it is 100 degreeC or more, and it is more preferable that it is 110 degreeC or more. By setting the glass transition temperature in such a range, it is preferable that the glass transition temperature be in such a range because the fluidity tends to be improved.

The polycarbonate resin composition of the present invention is excellent in all of flame retardancy, transparency, fluidity, and surface hardness.
The molded body obtained by injection molding the polycarbonate resin composition is preferably 2.0 mm in thickness, more preferably 1.5 mm, further preferably 1.2 mm, particularly preferably 1.0 mm, and most preferably 0.8 mm. The UL94 flame retardant property is V-0.
The total light transmittance of a molded product having a thickness of 2 mm obtained by injection molding a polycarbonate resin composition is preferably 85% or more, more preferably 88% or more, and further preferably 90% or more. Further, the molded body haze having a thickness of 3 mm obtained by injection molding the polycarbonate resin composition is preferably 3% or less, more preferably 2% or less, further preferably 1% or less, and particularly preferably 0.8 or less. .
The pencil hardness of a molded product having a thickness of 3 mm obtained by injection molding a polycarbonate resin composition is preferably F or higher, more preferably H or higher, and further preferably 2H or higher.
Of the polycarbonate resin composition, 300 ° C., melt volume rate measured under a load of 11.8 N (MVR) is preferably ^{5 cm} 3/10 minutes or more, more preferably ^{7 cm} 3/10 minutes or more, more preferably 8cm is ^3/10 minutes or more.
In addition, the evaluation method of a flame retardance, a total light transmittance, haze, pencil hardness, and MVR is as having described in the below-mentioned Example.

[Molded body]
The polycarbonate resin composition of the present invention can produce various molded articles by molding pellets obtained by pelletizing the above-described polycarbonate resin composition by various molding methods such as an injection molding method. Further, the resin melt-kneaded with an extruder can be directly molded into a molded body without going through the pellets.
There is no restriction | limiting in the shape of a molded object, a pattern, a color, a dimension, etc., What is necessary is just to set arbitrarily according to the use of the molded object.
The manufacturing method of the molded body includes, for example, an injection molding method, an ultra-high speed injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method such as gas assist, a molding method using a heat insulating mold, and a rapid heating mold. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press Examples include molding methods. A molding method using a hot runner method can also be used. Among these, it is preferable to employ an injection molding method or an extrusion molding method.

  In particular, when an extrusion molding method is employed to produce a sheet or film, an inert gas is introduced into the inlet of the polycarbonate resin composition (pellet) of the extruder as in the case of melt-kneading the polycarbonate resin composition. Is preferably introduced. As extrusion conditions for extruding a sheet or film while introducing an inert gas, the same conditions as in the above-described method of melt kneading while introducing nitrogen can be employed.

  Since the polycarbonate resin composition of the present invention provides a resin molded body with less foreign matter, high surface hardness and excellent flame retardancy and transparency as described above, for example, a casing of an electric or electronic device or its cover It is particularly suitable as a member for a display device or a cover for a display device, a protector, a vehicle-mounted component, a single layer or a multilayer sheet.

Examples of casings or covers for electric / electronic devices include televisions, radio cassettes, video cameras, audio players, DVD players, speakers, multi-function mobile phones, smart phones, mobile phone mobile chargers, PDAs, tablet terminals Cases or covers of electric / electronic devices such as personal computers, calculators, copiers, printers, facsimiles, and the like.
Examples of display device members include constituent members of various display (display) devices (liquid crystal panels and touch panels), personal control units, and the like, and examples of display device covers include these various display devices, multifunctional mobile phones, and smart phones. Protective covers and front panels for PDAs, tablet terminals, personal computers, etc., and for example, covers for display units of next-generation wattmeters. Examples of the transparent protector include a face cover (face guard) such as a helmet, a transparent shield, and the like.
In addition, as in-vehicle transparent parts, for example, glazing, resin window, headlamp lens, front (outside) member of car navigation (car audio, car AV, etc.), housing, etc., console box, center cluster, meter cluster Car interior parts such as front members are listed.
Furthermore, it is suitable for applications (liquid crystal display device members, transparent sheets, building materials, etc.) that require hardness, impact resistance, and transparency as single layer or multilayer sheets by single layer or multilayer extrusion.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.

In addition, the physical property of polycarbonate resin and the obtained polycarbonate resin composition was evaluated by the following method.
(1) Viscosity average molecular weight (Mv)
A polycarbonate resin was dissolved in methylene chloride (concentration 6.0 g / L) to obtain a solution. Using this solution, the specific viscosity (η _sp ) at 20 ° C. was measured with an Ubbelohde viscosity tube, and the viscosity average molecular weight (Mv) was calculated by the following formula.
η _sp /C=[η](1+0.28η _sp)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83

(2) Amount of terminal hydroxy groups For the polycarbonate resin or polycarbonate resin composition, the mass of the polycarbonate resin (A) was determined by colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method. It calculated with the mass ratio with respect to.

(3) Structural viscosity index (N value)
Using a capillary rheometer, the melt viscoelasticity at a temperature of 260 ° C. was measured, and from the above formula, from η _a at γ = 12.16 sec ⁻¹ and γ = 24.32 sec ⁻¹ , the polycarbonate resin (A1), N values of (A2) and (A3) were calculated.

(4) Glass transition temperature (Tg)
About polycarbonate resin or polycarbonate resin composition, according to JIS K7121: 1987, DSC7020 type high sensitivity type differential scanning calorimeter manufactured by SII NanoTechnology Co., Ltd. is heated from room temperature at a rate of 10 ° C./min in a nitrogen stream. The inflection point was measured as the glass transition temperature (Tg).

(5) Amount of branched structure (quantification of structural unit derived from the compound represented by the general formula (2))
After dissolving 0.5 g of the polycarbonate resin or the polycarbonate resin composition in 5 ml of methylene chloride, 45 ml of methanol and 5 ml of 25% by mass sodium hydroxide aqueous solution were added and stirred at 70 ° C. for 30 minutes. The obtained solution was analyzed by liquid chromatography, and the structural unit derived from the compound represented by the general formula (2) was quantified. The quantification was performed using a calibration curve for bisphenol A.

Liquid chromatography measurement was performed by the following method.
Device: Shimadzu Corporation System Controller: CBM-20A
Pump: LC-10AD
Column oven: CTO-10ASvp
Detector: SPD-M20A
Analytical column: YMC-Pack ODS-AM 75 mm × Φ4.6 mm
Oven temperature: 40 ° C
Detection wavelength: 280 nm
Eluent: A solution: 0.1% trifluoroacetic acid aqueous solution, B solution: acetonitrile A / B = 60/40 (vol%) to A / B = 95/5 (vol%) in 25 minutes Gradient flow rate: 1 mL / Min
Sample injection volume: 20 μl
A compound containing a structural unit derived from the compound represented by the general formula (2) was observed at a retention time of 21 minutes under the above liquid chromatography conditions.
For identification of each compound, a portion corresponding to the peak observed at the retention time was fractionated, and ¹ H-NMR, ¹³ C-NMR, two-dimensional NMR method, mass spectrometry (MS), It carried out by the infrared absorption spectrum method (IR spectrum).

(6) Pencil Hardness of Polycarbonate Resin and Resin Composition After drying polycarbonate resin or polycarbonate resin composition at 100 ° C. for 5 hours, injection molding machine (J55AD-60H (manufactured by Nippon Steel Co., Ltd. (clamping force 55t, maximum injection)) A plate (molded product) or a polycarbonate resin composition plate having a thickness of 3 mm, a length of 60 mm and a width of 60 mm under the conditions of a cylinder temperature of 270 ° C. and a mold temperature of 70 ° C. using a pressure of 2750 kgf / cm ² )) (Molded product) was injection molded. About this molded article, based on JISK5600-5-4 (1999), the pencil hardness measured by the load of 1,000g was calculated | required using the pencil hardness tester (made by Toyo Seiki Co., Ltd.).

(7) Total light transmittance According to JIS K-7105 (1981), a three-stage plate (3, 2, 1 mm thickness) obtained by the method described later was used as a test piece, and NDH4000 type turbidity manufactured by Nippon Denshoku Industries Co., Ltd. Using a photometer (D65 light source), the total light transmittance (unit:%) of a portion having a thickness of 2 mm was measured.

(8) Haze According to JIS K-7136 (2000), a three-stage plate (3, 2, 1 mm thickness) obtained by the method described later was used as a test piece, and a haze meter (NDH-2000 type manufactured by Nippon Denshoku Industries Co., Ltd.) ), The haze (unit:%) of the portion with a thickness of 3 mm was measured.

(9) UL94 flame retardancy A test specimen for UL test (thickness 2.0 mm, 1.5 mm, 1.2 mm, 1.0 mm, 0.8 mm) obtained by the method described later is used at a temperature of 23 ° C. and a relative humidity of 50. The humidity was controlled in a constant temperature room for 48 hours, and the test was conducted in accordance with the UL94 test (combustion test of plastic materials for equipment parts) established by the US Underwriters Laboratories (UL). UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 1 below.

  Here, the afterflame time is the length of time that the test piece continues to be flammed after the ignition source is moved away, and the residual flame time is the test piece after the ignition source is moved away. It is the length of time to continue the flameless combustion of. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece.

(10) Melt volume rate (MVR)
After the polycarbonate resin composition obtained by the method described below was dried at 100 ° C. for 5 hours, it was measured with a melt indexer manufactured by Toyo Seiki Co., Ltd. under a measurement temperature of 300 ° C. and a load of 11.8 N. in, ^MVR: was measured (in cm 3 / 10min). The higher this value, the better the fluidity and the better the moldability.

(11) Thin-wall moldability After the resin composition pellets obtained by the method described below were dried at 100 ° C. for 4 hours, SE50D molding machine manufactured by Sumitomo Heavy Industries, Ltd. (clamping force 50 t, maximum injection pressure 2170 kgf / cm ² ), a thin-wall moldability when a UL test specimen having a length of 125 mm, a width of 13 mm, and a thickness of 1.0 mm is molded at a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C. is as follows: Judged.
○: Full filling was possible.
X: The fluidity was insufficient, resulting in a short shot.

(12) Film foreign matter After the polycarbonate resin composition obtained by the method described below was dried at 100 ° C. for 5 hours, a film was produced as follows, and the number of foreign matters generated was evaluated.
Using a 30 mm diameter single screw extruder (made by Isuzu Chemical Co., Ltd.) with a 200 mm wide die and a film take-up device attached to the tip, while supplying a polycarbonate resin composition at 8 kg / hr, at a barrel temperature of 280 ° C. A film was formed to obtain a polycarbonate resin film having a thickness of 70 μm ± 5 μm. About this polycarbonate resin film, using an optical foreign material inspection apparatus (“GX40K” manufactured by Dia Instruments Co., Ltd.), the number of foreign materials (size: 50 μm) present in an area of 80 mm width × 1.7 m length selected from the center of the film. The total number of foreign substances) was measured. The measurement was performed twice, and the average value was defined as the number of film foreign matter.

The raw materials used in the following Examples and Comparative Examples are as shown in Table 2 below.
In addition, as polycarbonate resin containing the structural unit derived from the aromatic dihydroxy compound represented by General formula (1), polycarbonate resin (A1-1)-(A1-4) manufactured with the following method was used.

<Manufacture of polycarbonate resin (A1-1)>
2,2-bis (3-methyl-4-hydroxyphenyl) propane (hereinafter referred to as “BPC”) 26.14 mol (6.75 kg) and diphenyl carbonate 26.79 mol (5.74 kg) The reactor was placed in a SUS reactor (with an internal volume of 10 liters) equipped with a stirrer and a distillation condenser, and the reactor was replaced with nitrogen gas.
Next, the reaction solution in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) is used as a transesterification reaction catalyst in the molten reaction solution so that the amount becomes 1.5 × 10 ⁻⁶ mol per 1 mol of BPC. In addition, the reaction solution was stirred and brewed at 220 ° C. for 30 minutes in a nitrogen gas atmosphere. Next, under the same temperature, the pressure in the reactor was reduced to 100 Torr over 40 minutes, and the reaction was further performed for 100 minutes to distill phenol.

Next, the temperature in the reactor was raised to 284 ° C. over 60 minutes and the pressure was reduced to 3 Torr, and phenol corresponding to almost the entire distillation amount was distilled. Next, the pressure in the reactor was kept below 1 Torr at the same temperature, and the reaction was further continued for 60 minutes to complete the polycondensation reaction.
At this time, the stirring rotation speed of the stirrer was 38 rotations / minute, the reaction liquid temperature just before the completion of the reaction was 289 ° C., and the stirring power was 1.00 kW.
Next, the reaction solution in a molten state is fed into a twin screw extruder, and 4-fold molar amount of butyl p-toluenesulfonate is supplied from the first supply port of the twin screw extruder with respect to cesium carbonate, After kneading with the reaction solution, the reaction solution was extruded into a strand shape through a die of a twin screw extruder and cut with a cutter to obtain polycarbonate resin pellets.

The physical properties of the obtained polycarbonate resin (A1-1) were as follows.
Viscosity average molecular weight (Mv): 26,000
Terminal hydroxy group content: 850 mass ppm
Pencil hardness: 2H
Structural viscosity index N: 1.2
Branched structure amount derived from general formula (2): 2,900 mass ppm
Glass transition temperature: 120 ° C

<Manufacture of polycarbonate resin (A1-2)>
A polycarbonate resin pellet was obtained in the same manner as the polycarbonate resin (A1-1) except that BPC was changed to 26.02 mol.
The physical properties of the obtained polycarbonate resin (A1-2) were as follows.
Viscosity average molecular weight (Mv): 26,000
Terminal hydroxy group content: 650 mass ppm
Pencil hardness: 2H
Structural viscosity index N: 1.2
Branched structure amount derived from general formula (2): 3,100 ppm by mass
Glass transition temperature: 120 ° C

<Manufacture of polycarbonate resin (A1-3)>
6.59 mol (1.69 kg) of BPC and 6.73 mol (1.44 kg) of diphenyl carbonate were placed in a SUS reactor (with an internal volume of 10 liters) equipped with a stirrer and a distillation condenser. Was replaced with nitrogen gas, and the temperature was raised to 220 ° C. over 30 minutes in a nitrogen gas atmosphere.
Next, the reaction solution in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) is used as a transesterification reaction catalyst in the molten reaction solution so that the amount becomes 1.5 × 10 ⁻⁶ mol per 1 mol of BPC. In addition (3.20 mg as Cs ₂ CO ₃ ), the reaction solution was stirred and brewed at 220 ° C. for 30 minutes under a nitrogen gas atmosphere. Next, under the same temperature, the pressure in the reactor was reduced to 100 Torr over 40 minutes, and the reaction was further performed for 100 minutes to distill phenol.
Next, the temperature in the reactor was raised to 284 ° C. over 60 minutes and the pressure was reduced to 3 Torr, and phenol corresponding to almost the entire distillation amount was distilled. Next, the pressure in the reactor was kept below 1 Torr at the same temperature, and the reaction was further continued for 60 minutes to complete the polycondensation reaction. At this time, the stirring rotation speed of the stirrer was 16 rotations / minute, the reaction liquid temperature immediately before the completion of the reaction was 300 ° C., and the stirring power was 1.15 kW.
Next, the reaction solution in a molten state is fed into a twin screw extruder, and 4-fold molar amount of butyl p-toluenesulfonate is supplied from the first supply port of the twin screw extruder with respect to cesium carbonate, After kneading with the reaction solution, the reaction solution was extruded in a strand shape through a die of a twin screw extruder and cut with a cutter to obtain carbonate resin pellets.

The physical properties of the obtained polycarbonate resin (A1-3) were as follows.
Viscosity average molecular weight (Mv): 32,000
Terminal hydroxy group content: 900 ppm by mass
Pencil hardness: 2H
Structural viscosity index N: 1.15
Branched structure amount derived from general formula (2): 4,500 mass ppm
Glass transition temperature: 121 ° C

<Manufacture of polycarbonate resin (A1-4)>
BPC 13.80 kg / h, sodium hydroxide (NaOH) 5.8 kg / h and water 93.5 kg / h were dissolved at 35 ° C. in the presence of hydrosulfite 0.017 kg / h and then cooled to 25 ° C. The aqueous phase and the organic phase of 61.9 kg / h of methylene chloride cooled to 5 ° C. are supplied to a fluororesin pipe having an inner diameter of 6 mm and an outer diameter of 8 mm, respectively, and fluorine having an inner diameter of 6 mm and a length of 34 m is connected thereto. In a resin pipe reactor, it was brought into contact with 7.2 kg / hour of liquefied phosgene cooled to 0 ° C. separately introduced here.

The raw material is subjected to phosgenation and oligomerization reaction while flowing through phosgene and a pipe reactor at a linear velocity of 1.7 m / second for 20 seconds. At this time, the reaction temperature reached a tower top temperature of 60 ° C. in an adiabatic system. The temperature of the reaction product was adjusted by external cooling to 35 ° C. before entering the next oligomerization tank. In the oligomerization, triethylamine 5 g / hour (0.9 × 10 ⁻³ mole relative to 1 mole of BPC) was used as a catalyst, and pt-butylphenol 0.153 kg / hour was used as a molecular weight regulator. Introduced.

In this way, the oligomerized emulsion obtained from the pipe reactor is further guided to a reaction vessel equipped with a stirrer having an internal volume of 50 liters and stirred at 30 ° C. in a nitrogen gas (N ₂ ) atmosphere to be oligomerized. Thus, the unreacted sodium salt of BPC (BPC-Na) present in the aqueous phase was consumed, and then the aqueous phase and the oil phase were allowed to stand and separate to obtain an oligomeric methylene chloride solution. Of the oligomer methylene chloride solution, 23 kg was charged into a 70 liter Faudler-bladed reaction tank, and 10 kg of methylene chloride for dilution was added thereto. Further, 2.2 kg of 25% by weight aqueous sodium hydroxide solution and 6 kg of water were added. And 2.2 g of triethylamine (1.1 × 10 ⁻³ mol relative to 1 mol of BPC) were added, and the mixture was stirred at 30 ° C. in a nitrogen gas atmosphere and subjected to a polycondensation reaction for 60 minutes to obtain a polycarbonate resin.

Next, 30 kg of methylene chloride and 7 kg of water were added, and after stirring for 20 minutes, stirring was stopped and the aqueous phase and the organic phase were separated. To the separated organic phase, 20 kg of 0.1N hydrochloric acid was added and stirred for 15 minutes to extract triethylamine and a small amount of remaining alkali component, and then stirring was stopped to separate the aqueous phase and the organic phase. Further, 20 kg of pure water was added to the separated organic phase, and the mixture was stirred for 15 minutes, and then the stirring was stopped to separate the aqueous phase and the organic phase. This operation was repeated (three times) until no chlorine ions were detected in the extracted waste water. The obtained purified organic phase was pulverized by feeding into 40 ° C. warm water and dried to obtain a flaky powder of polycarbonate resin.

The physical properties of the obtained polycarbonate resin (A1-4) were as follows.
Viscosity average molecular weight (Mv): 30,000
Terminal hydroxy group content: 30 mass ppm
Pencil hardness: 2H
Structural viscosity index N: 1.3
Branched structure amount derived from general formula (2): 20 ppm by mass
Glass transition temperature: 121 ° C

(Examples 1-4, Comparative Examples 1-6)
[Production of resin composition pellets]
Each component described above was blended in the proportions (parts by mass) shown in Table 3 below, and mixed for 20 minutes with a tumbler.
Using a twin screw vent type extruder (TEM48SS manufactured by Toshiba Machine Co., Ltd., cylinder length 38D (D is the cylinder inner diameter)) having a configuration as shown in FIG. 1, the melting zone 25D, the kneading zone 4D, and the decompression zone 9D Melt kneading was performed using a screw.
A cylindrical hopper chute 7 (length 2 m, diameter 150 mm) made of polyethylene was prepared, and the feeder 2 and the hopper 4 were connected. While supplying nitrogen gas (purity 99.9%) at a rate of 10 L / min so as to counterflow with the raw material of the polycarbonate resin composition to be fed upward from the vicinity of the raw material inlet of the twin screw extruder, Melt kneading was performed under the conditions of a preset temperature of 260 ° C. and a screw rotation speed of 200 rpm. The feed rate F is 150 kg / hr, the ratio of the inert gas flow rate G to the feed rate F (G / F) is 0.07, the oxygen concentration in the hopper 4 (the hopper center) is 0.6% by volume, vent The degree of reduced pressure was -0.1 MPa. Moreover, it was 270 degreeC when the resin temperature in an extruder exit was measured. The driving condition was stable.

The obtained pellets were dried at 100 ° C. for 4 hours, and then the cylinder temperature was 280 ° C. with an injection molding machine (“J55AD-60H” manufactured by Nippon Steel Works, Ltd. (clamping force 55 t, maximum injection pressure 2750 kgf / cm ² )). Then, injection molding was performed under the conditions of a mold temperature of 80 ° C. and a molding cycle of 50 seconds to form a three-stage plate (three-stage shape with a thickness of 3 mm, 2 mm, and 1 mm).
Further, for the flame retardancy test, the obtained pellets were dried at 100 ° C. for 4 hours, and then an injection molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd. (clamping force 100 t, maximum injection pressure 3500 kgf / cm ^2). )), Injection molding was performed under the conditions of a cylinder temperature of 300 ° C., a mold temperature of 80 ° C., and a molding cycle of 30 seconds. Test pieces for 0 mm and 0.8 mm UL tests were molded.

Using the obtained pellets, the various measurements described above were performed.
The results are shown in Tables 3-4 below.

From the said Table 3, the composition of Examples 1-4 contains specific polycarbonate resin (A1) and (A2) prescribed | regulated by this invention, and organic sulfonic-acid alkali metal salt (B) by predetermined amount. Compared with Comparative Examples 1-6, it is understood that the total light transmittance, MVR, thin-wall formability, flame retardancy, and pencil hardness are all excellent, and there are few foreign substances.
In particular, it can be seen that the composition of Example 3 in which the amount of terminal hydroxy groups of the polycarbonate resin (A) is as low as 640 ppm is a resin composition that has an extremely small number of film foreign matters of 25 and is excellent in residence heat stability.
On the other hand, Comparative Example 1 not containing the polycarbonate resin (A2) has a low flame retardancy, and Comparative Example 2 having a high content of the polycarbonate resin (A2) has a low MVR and poor fluidity, and has a thin moldability. there were. Moreover, the flame retardance and pencil hardness fell in the comparative example 3 which does not contain polycarbonate resin (A1).
In Comparative Examples 4 and 5, which did not contain the polycarbonate resin (A2) and used the polycarbonate resin (A1) having a high Mv, the flame retardancy was V-0, but the MVR and the thin-wall moldability were poor. Since the amount of the branched structure derived from the formula (2) is relatively large, the number of film foreign matter was also large. In Comparative Example 6, the polycarbonate resin (A1) has a high Mv, the thin wall fluidity is lowered, and the flame retardancy is also lowered.

  The polycarbonate resin composition of the present invention is a high-hardness polycarbonate resin material that is transparent with few foreign substances, excellent in flame retardancy, good fluidity, and excellent in thin-wall moldability. In particular, it is suitable for a housing of an electric / electronic device or its cover, a member for a display device or a cover for a display device, a protector, a vehicle-mounted component, a single layer or a multilayer sheet, and has very high industrial applicability. .

Claims (17)

Polycarbonate resin (A1) having a structural unit derived from an aromatic dihydroxy compound represented by the following general formula (1) having a viscosity average molecular weight of less than 30,000: 50 to 98% by mass, and a viscosity average molecular weight of 50,000 to 95 Polycarbonate resin (A3) 2-30% by mass and polycarbonate resin (A1) having a polymer structure different from that of the viscosity average molecular weight of 10,000-30,000 (A3) 0-30% by mass (however, It is characterized by containing 0.01 to 1 part by mass of organic sulfonic acid metal salt (B) with respect to 100 parts by mass of polycarbonate resin (A) containing at least 100% by mass of polycarbonate resin (A) as a whole. Polycarbonate resin composition.
(In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and X is
R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and Z is a C 6-12 fat which may be bonded to a carbon atom (C) to have a substituent. The group which forms a cyclic hydrocarbon is shown. )   The polycarbonate resin composition according to claim 1, wherein the organic sulfonic acid metal salt (B) is a fluorine-containing organic sulfonic acid alkali metal salt.   The polycarbonate resin composition according to claim 1 or 2, wherein the polycarbonate resin (A1) has a viscosity average molecular weight of 24,000 to 29,000.   The polycarbonate resin composition according to any one of claims 1 to 3, wherein the polycarbonate resin (A2) has a viscosity average molecular weight of 60,000 to 85,000.   The polycarbonate resin composition according to any one of claims 1 to 4, wherein the content of the polycarbonate resin (A3) in the polycarbonate resin (A) is 2 to 25 mass%. The polycarbonate resin composition according to any one of claims 1 to 5, wherein the aromatic dihydroxy compound represented by the general formula (1) is a bisphenol compound represented by the following formula (1a).
  The polycarbonate resin composition according to any one of claims 1 to 6, wherein the polycarbonate resin (A2) is a polycarbonate resin having a structural unit derived from bisphenol A.   The polycarbonate resin composition according to any one of claims 1 to 7, wherein the polycarbonate resin (A3) is a polycarbonate resin having a structural unit derived from bisphenol A.   The polycarbonate resin composition according to any one of claims 1 to 8, wherein the amount of terminal hydroxy groups of the polycarbonate resin (A) is 10 to 700 ppm by mass.   The polycarbonate resin composition according to any one of claims 1 to 9, wherein the amount of terminal hydroxy groups of the polycarbonate resin (A1) is 10 to 800 ppm by mass.   The polycarbonate resin composition according to any one of claims 1 to 10, wherein the structural viscosity index N1 of the polycarbonate resin (A1) and the structural viscosity index N2 of the polycarbonate resin (A2) satisfy N1 <N2.   The polycarbonate resin composition according to any one of claims 1 to 11, wherein the structural viscosity index N1 of the polycarbonate resin (A1) is 1.0 to 1.4.   The polycarbonate resin composition according to any one of claims 1 to 12, wherein the structural viscosity index N2 of the polycarbonate resin (A2) is 1.2 to 1.9. The polycarbonate according to any one of claims 1 to 13, wherein the content of the structural unit derived from the compound represented by the following general formula (2) in the polycarbonate resin composition is 10 to 4,000 mass ppm. Resin composition.
(In the general formula (2), R ¹ , R ² and X have the same meaning as in the general formula (1).)   The polycarbonate according to any one of claims 1 to 14, wherein the content of the structural unit derived from the compound represented by the general formula (2) in the polycarbonate resin (A1) is 60 to 6,000 mass ppm. Resin composition.   The polycarbonate resin composition according to any one of claims 1 to 15, wherein UL 1.0 flame retardancy of a molded article having a thickness of 1.0 mm obtained by injection molding the polycarbonate resin composition is V-0.   A method for producing the polycarbonate resin composition according to any one of claims 1 to 16 by melt-kneading using an extruder, wherein an inert gas is extruded into a raw material inlet of the extruder per unit time. While introducing the ratio of the raw material amount F [kg / hr] and the inert gas amount G [L / min] of the polycarbonate resin composition supplied to the machine to 0.005 ≦ G / F ≦ 0.2 A method for producing a polycarbonate resin composition, comprising kneading.