JP2012236991A - Polycarbonate resin and method for production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin having high surface hardness, high flame retardancy and with less foreign matters.SOLUTION: The polycarbonate resin has a repeating unit derived from bisphenol or biphenolic compound, and the content of the structural unit derived from a compound represented by formula (2) is ≥20 ppm but ≤1,000 ppm. In the formula (2), Rand Rare each independently (un)substituted 1-20C alkyl or (un)substituted aryl, and X is single bond, (un)substituted alkylene, (un)substituted alkylidene, or (un)substituted sulfur or oxygen.

Description

  The present invention relates to a polycarbonate resin and a method for producing a polycarbonate resin.

  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 electric / electronic equipment fields and automobile fields. In recent years, in these fields of application, molding products have become thinner, smaller, and lighter, and further improvements in the performance of molding materials are required. Among them, the development of polycarbonate resins that are thin but have high hardness is desired. Some proposals have been made.

  For example, a method of forming a polycarbonate or copolycarbonate having excellent surface hardness using bisphenols different from conventional bisphenol A (Patent Document 1, Patent Document 2), dimethyl bisphenol cyclohexane type polycarbonate and bisphenol A type polycarbonate A method of balancing fluidity and hardness by blending (Patent Document 3) is known.

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

Even a polycarbonate resin obtained by a conventionally known technique may still not have sufficient performance in terms of surface hardness and flame retardancy, and is further required to be thin and have good flame retardancy.
An object of the present invention is to provide a polycarbonate resin having a high surface hardness, high flame retardancy, and less foreign matter.

The inventors of the present invention have intensively studied to achieve the above object, and in a polycarbonate resin having a specific repeating unit, by adjusting the content of a specific structural unit to a specific range, the surface hardness is high and difficult. The inventors have found that a polycarbonate resin having high flammability and less foreign matters can be obtained, and the present invention has been completed. That is, the gist of the present invention resides in the polycarbonate resin and the method for producing the polycarbonate resin according to [1] to [8] below.
[1]
A polycarbonate resin having a repeating unit derived from the compound represented by the following formula (1), wherein the content of the structural unit derived from the compound represented by the following formula (2) is 20 ppm or more and 1000 ppm or less, and A polycarbonate resin having a viscosity average molecular weight of 15,000 or more and 24,000 or less.

(In Formula (1), R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and X represents a single bond, A substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom;

(In Formula (2), R ¹ and R ² represent the same group as in Formula (1), and R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or Represents an unsubstituted aryl group.)
[2]
A polycarbonate resin having a repeating unit derived from the compound represented by the following formula (1), wherein the content of the structural unit derived from the compound represented by the following formula (3) is 200 ppm to 3000 ppm, and A polycarbonate resin having a viscosity average molecular weight of 15,000 or more and 24,000 or less.

(In Formula (1), R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and X represents a single bond, A carbonyl group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom.)

(In Formula (3), R ¹ , R ² and X represent the same group as in Formula (1), and R ⁴ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted group. Represents a substituted aryl group.)
[3]
A polycarbonate resin having a repeating unit derived from the compound represented by the following formula (1), wherein the content of the structural unit derived from the compound represented by the following formula (4) is 50 ppm or more and 600 ppm or less, and A polycarbonate resin having a viscosity average molecular weight of 15,000 or more and 24,000 or less.

(In Formula (1), R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and X represents a single bond, A substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom;

(In formula (4), R ¹ and X have the same meanings as in formula (1). R ⁵ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted group. An aryl group of
[4]
A polycarbonate resin having a repeating unit derived from the compound represented by the formula (1), wherein the content of the structural unit derived from the compound represented by the formula (2) is 20 ppm or more and 1000 ppm or less [2 ] Polycarbonate resin as described in.
[5]
A polycarbonate resin having a repeating unit derived from the compound represented by the formula (1), wherein the content of the structural unit derived from the compound represented by the formula (4) is 50 ppm or more and 600 ppm or less [2 ] Polycarbonate resin as described in.
[6]
The total content of metals of Group 1 and Group 2 of the long-term periodic table in the polycarbonate resin is 5.0 × 10 ⁻⁶ mol or less with respect to 1 mol of repeating units derived from all dihydroxy compounds constituting the polycarbonate resin. The polycarbonate resin according to any one of [1] to [5].
[7]
Manufacture of the polycarbonate resin of any one of [1] to [6] obtained by superposing | polymerizing the dihydroxy compound component containing the compound represented by said Formula (1), and a carbonate formation compound component. A method for producing a polycarbonate resin, wherein the carbonate-forming compound component is a carbonic acid diester.
[8]
The method for producing a polycarbonate resin according to [7], wherein the polymerization is performed in the presence of a compound containing at least one metal selected from the group consisting of metals of Group 1 and Group 2 of the long-period periodic table.

  According to the present invention, it is possible to obtain a polycarbonate resin having a high surface hardness, a high flame retardancy, and a small amount of foreign matter, as compared with a conventionally known polycarbonate resin.

Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
The polycarbonate resin of the present invention has a repeating unit derived from a compound represented by the following formula (1), and further a structural unit derived from a compound represented by the following formula (2), represented by the following formula (3): A specific amount of at least one structural unit selected from a structural unit derived from a compound represented by the following formula (4) and a structural unit derived from a compound represented by the following formula (4) is included.

<Polycarbonate resin>
The polycarbonate resin of the present invention has a repeating unit derived from the compound represented by the formula (1). In the formula (1), R ¹ and R ² are each independently substituted or unsubstituted carbon number 1 Represents an alkyl group of 20 or less, or a substituted or unsubstituted aryl group, and X represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or oxygen Indicates an atom.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R ¹ and R ² include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Examples thereof include a butyl group, a tert-butyl group, an n-pentyl group, a sec-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. Examples of the substituted or unsubstituted 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 methyl group, an ethyl group, an n-propyl group, or a 4-methylphenyl group, and particularly preferably a methyl group.
Here, the bonding positions of R ¹ and R ² in the formula (1) are arbitrary positions selected from 2-position, 3-position, 5-position and 6-position with respect to X on each phenyl ring. Among these, the third and fifth positions with respect to X are preferred.

In the formula (1), X represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom. The substituted or unsubstituted sulfur atom, for example, -S -, - SO ₂ -, and the like.
A substituted or unsubstituted alkylene group and a substituted or unsubstituted alkylidene group are shown below.

Here, R ⁶ and R ⁷ 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 Z is substituted or unsubstituted. An alkylene group or a polymethylene group having 4 to 20 carbon atoms. n represents an integer of 1 to 10.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R ⁶ and R ⁷ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Examples thereof include a butyl group, a tert-butyl group, an n-pentyl group, a sec-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. Examples of the substituted or unsubstituted aryl group include a phenyl group, a benzyl group, a tolyl group, a 4-methylphenyl group, and a naphthyl group.
Among these, R ⁶ and R ⁷ are preferably a methyl group, an ethyl group, an n-propyl group, or a 4-methylphenyl group, more preferably a methyl group, and in particular, both R ⁶ and R ⁷ are methyl groups. And n is 1, that is, X in formula (1) is preferably an isopropylidene group.

Z is bonded to carbon bonding two phenyl groups in formula (1) to form a substituted or unsubstituted divalent carbocycle. Examples of the divalent carbocycle include a cycloalkylidene group such as a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group (preferably a carbon number of 5 To 8). Examples of the substituted ones include those having these methyl substituents and ethyl substituents. Among these, a methyl-substituted product of a cyclohexylidene group, a cyclohexylidene group, or a cyclododecylidene group is preferable.
As for the polycarbonate resin of this invention, what has a repeating unit derived from the compound represented by following formula (6) among the compounds represented by Formula (1) is more preferable.

In Formula (6), R ¹ and R ² each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and in Formula (1) described above, The same as R ¹ and R ² .
Among these, the repeating unit possessed by the polycarbonate resin of the present invention is particularly preferably a repeating unit derived from 2,2-bis (3-methyl-4-hydroxyphenyl) propane.

  The polycarbonate resin of the present invention has at least repeating units derived from the compound represented by the formula (1), but the content thereof is represented by the formula (1) with respect to all repeating units derived from the dihydroxy compound. It is preferable that the repeating unit derived from a compound is 50 weight% or more, More preferably, it is 70 weight% or more, More preferably, it is 90 weight% or more. When the amount of the structural unit represented by the formula (1) is excessively small, the surface hardness and fluidity tend to be inferior.

  The polycarbonate resin of the present invention is further represented by the structural unit derived from the compound represented by the formula (2), the structural unit derived from the compound represented by the formula (3), and the formula (4). A specific amount of at least one structural unit selected from structural units derived from the compound. In the present invention, the structural unit derived from the compound represented by the formula (2), the structural unit derived from the compound represented by the formula (3), and the formula (4) contained in the polycarbonate resin of the present invention. The amount of at least one structural unit selected from the structural units derived from the compound represented by) is a value measured by liquid chromatography when the polycarbonate resin of the present invention is alkali-hydrolyzed by the method described later. Defined by

  In the polycarbonate resin of the present invention, the content of the structural unit derived from the compound represented by the formula (2) is usually 20 ppm to 2000 ppm, preferably 20 ppm to 1300 ppm, preferably 20 ppm to 1000 ppm. Is more preferable, and 50 ppm or more and 1000 ppm or less is still more preferable. If the content of the structural unit derived from the compound represented by the 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. The content of the structural unit derived from the compound represented by the formula (3) is usually 200 ppm to 5000 ppm, preferably 200 ppm to 3000 ppm, and more preferably 200 ppm to 2000 ppm. preferable. If the content of the structural unit derived from the compound represented by the formula (3) is too small, the flame retardancy may be lowered, and if it is too much, the amount of foreign matter may be increased. The content of the structural unit derived from the compound represented by the formula (4) is usually 50 ppm to 600 ppm, preferably 50 ppm to 500 ppm, more preferably 50 ppm to 400 ppm. preferable. If the content of the structural unit derived from the compound represented by the formula (4) is too small, the flame retardancy may be lowered, and if it is too much, the amount of foreign matter may be increased.

-Compound represented by the formula (2) In the compound represented by the following formula (2) of the present invention, R ¹ and R ² represent the same group as the formula (1), R ³ represents a hydrogen atom, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
Or a substituted or unsubstituted aryl group;

  The compound represented by the formula (2) is represented by the following formula (7) when the case where the formula (1) is 2,2-bis (3-methyl-4-hydroxyphenyl) propane is taken as an example. (Hereinafter, this compound may be abbreviated as “Compound 2”).

-Compound represented by Formula (3) In the compound represented by the following Formula (3) of the present invention, R ¹ and R ² represent the same groups as those in Formula (1), R ³ represents a hydrogen atom, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group is shown.

  The compound represented by the formula (3) is represented by the following formula (8) when the formula (1) is 2,2-bis (3-methyl-4-hydroxyphenyl) propane. (Hereinafter, this compound may be abbreviated as “Compound 3”).

-Compound represented by formula (4) In the compound represented by the following formula (4) of the present invention, R ¹ and R ² represent the same group as the formula (1), R ³ represents a hydrogen atom, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group is shown.

  The compound represented by the formula (4) is represented by the following formula (9) when the formula (1) is 2,2-bis (3-methyl-4-hydroxyphenyl) propane. (Hereinafter, this compound may be abbreviated as “compound 4”).

  These compounds represented by the formula (2), the compound represented by the formula (3), and the compound represented by the formula (4) are particularly exposed to the polycarbonate and its raw material under a high temperature such as a melt polymerization method. From this, it is assumed that they are generated. The structure of the compound represented by the formula (2), the compound represented by the formula (3), and the compound represented by the formula (4) is estimated to be a branch point in the polycarbonate resin from the structure. The The structure represented by the compound represented by the formula (2), the compound represented by the formula (3), and the compound represented by the formula (4) has not been observed in a polycarbonate using bisphenol A as a raw material. It is considered that the structure is unique to the polycarbonate resin of the present invention.

-Determination method by alkali hydrolysis The polycarbonate resin of the present invention has a structural unit derived from the compound represented by the formula (2), a structural unit derived from the compound represented by the formula (3), and the formula The amount of at least one structural unit selected from structural units derived from the compound represented by (4) is defined as a value measured by liquid chromatography when the polycarbonate resin of the present invention is subjected to alkali hydrolysis. Is done. As a measuring method, 0.5 g of polycarbonate resin was dissolved in 5 ml of methylene chloride, 45 ml of methanol and 5 ml of 25% by weight sodium hydroxide aqueous solution were added, and the resulting solution was stirred at 70 ° C. for 30 minutes. Derived from the compound represented by Formula (2), the structural unit derived from the compound represented by Formula (3), and the compound represented by Formula (4) The amount of at least one structural unit selected from the structural units is quantified.

Derived from the structural unit derived from the compound represented by the formula (2), the structural unit derived from the compound represented by the formula (3), and the compound represented by the formula (4) by liquid chromatography The amount of at least one structural unit selected from the structural units to be measured can be measured, for example, under the following conditions.
(Analysis conditions)
Liquid chromatography device: manufactured by 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
From A / B = 60/40 (vol%) to A / B = 95/5 (vol%)
Gradient in 25 minutes Flow rate: 1 mL / min
Sample injection volume: 20 μl

  More specifically, taking the case where the compound represented by the formula (1) is 2,2-bis (3-methyl-4-hydroxyphenyl) propane as an example, the compound represented by (2) Compound 2, which is a structural unit derived from the above, Compound 3, which is a structural unit derived from the compound represented by the above formula (3), and Compound 4, which is a structural unit derived from the compound represented by the above formula (4) Is observed at the following retention time under the above liquid chromatography conditions.

Compound 4: 13.9 minutes represented by formula (4) Compound 2: 15.9 minutes represented by formula (2) Compound 21: 21 minutes represented by formula (3) The portion corresponding to the peak observed at the retention time is fractionated, and can be carried out by ¹ H NMR, ¹³ C NMR, mass spectrometry (MS), infrared absorption spectrum (IR spectrum), etc. of the collected sample. .

Polycarbonate resins of the present invention is long-form periodic table Group 1 and Group 2 5.0 relative to repeating units 1 mole of content total amount of the metal is derived from all dihydroxy compounds constituting the polycarbonate resin of × 10 ^-6 It is preferably at most mol, more preferably at most 4.0 × 10 ⁻⁶ mol, even more preferably at most 3.0 × 10 ⁻⁶ mol. On the other hand, the lower limit is preferably 1.0 × 10 ⁻⁸ mol, more preferably 3.0 × 10 ⁻⁸ mol, and still more preferably 5.0 × 10 ⁻⁸ mol with respect to 1 mol of the dihydroxy compound. When the amount of the catalyst is large, the polymer hue deteriorates, and a gel-like substance or a foreign substance insoluble in the solvent is generated, which may cause poor appearance and mechanical properties of the polycarbonate resin. When the amount of the catalyst is small, the flame retardancy may be deteriorated.

<Physical properties of polycarbonate resin>
In the polycarbonate resin of the present invention, the ratio (Mw / Mn) of polystyrene-equivalent weight average molecular weight Mw and number average molecular weight Mn measured by gel permeation chromatography (GPC) is 3.0 or more and 5.0 or less. A range is preferable. Furthermore, (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 tends to be difficult.

  The polycarbonate resin of the present invention preferably has a pencil hardness according to JIS K5400 of HB or higher. Further, the pencil hardness of the polycarbonate resin is preferably F or more, more preferably H or more. 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.

  The terminal hydroxyl group concentration of the polycarbonate resin of the present invention is not particularly limited. When the transesterification method to be described later is adopted as the production method, the terminal hydroxyl group concentration of the obtained polycarbonate resin is usually 100 ppm or more, preferably 200 ppm or more, and more preferably 300 ppm or more. However, it is usually 2000 ppm or less, preferably 1800 ppm or less, and more preferably 1200 ppm or less. If the terminal hydroxyl group concentration of the polycarbonate resin is too small, the initial hue at the time of molding tends to deteriorate. When the terminal hydroxyl group concentration is excessively large, the residence heat stability tends to decrease.

  The viscosity average molecular weight of the polycarbonate resin of the present invention is 15,000 or more, preferably 17,000 or more, more preferably 18,000 or more, and particularly preferably 20,000 or more. Moreover, it is 24,000 or less, Preferably it is 23,000 or less, Most preferably, it is 22,000 or less. If the viscosity average molecular weight is too low, flame retardancy and mechanical properties may be reduced. On the other hand, if the viscosity average molecular weight is too high, the fluidity is lowered and the amount of foreign matter may be increased.

<Production method of polycarbonate resin>
Next, the manufacturing method of the polycarbonate resin of this invention is demonstrated. There is no restriction | limiting in particular in the manufacturing method of polycarbonate resin of this invention, It has a repeating unit derived from the compound represented by the said Formula (1), Furthermore, the structural unit derived from the compound represented by the said Formula (2) A specific amount of at least one structural unit selected from the structural unit derived from the compound represented by the formula (3) and the structural unit derived from the compound represented by the formula (4) is included. As long as it can be manufactured, it may be manufactured by any method. Usually, the polycarbonate resin is obtained by polymerizing a dihydroxy compound component and a carbonate-forming compound component.

  The polycarbonate resin production method of the present invention includes a melt polycondensation method based on a transesterification reaction using a dihydroxy compound component containing the compound represented by the formula (1) and a carbonic acid diester as a carbonate-forming compound component ( Hereinafter, an interfacial polycondensation method (hereinafter referred to as an interfacial method) using a dihydroxy compound component containing the compound represented by the formula (1) and carbonyl chloride as a carbonate-forming compound component may be abbreviated as a melting method. May be abbreviated as). Among these, the structural unit derived from the compound represented by the following formula (2), the structural unit derived from the compound represented by the following formula (3), and the compound represented by the following formula (4) The melting method is preferable in that it is easy to control the amount of at least one structural unit selected from the structural units to a specific amount.

(Dihydroxy compound component)
The dihydroxy compound component preferably contains a compound represented by the following formula (1) for both the melting method (transesterification method) and the interface method.

(In Formula (1), R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and X represents a single bond, A substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom;

  Specific examples of the compound represented by the formula (1) include 2,2-bis (3-methyl-4-hydroxyphenyl) propane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl). ) Propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -3,5,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) adamantane, 1,4-bis (4-hydroxy-3-methylphenyl) adamantane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane, 2,2- Bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-cyclohexylphenyl) propane, 2,2- (4-hydroxy-3-phenylphenyl) propane, 5,5-bis (4-hydroxy-3-methylphenyl) hexahydro-4,7-methanoindane, 2,2-bis (4-hydroxy-3-methylphenyl) ) Sulfone, 2,2-bis (4-hydroxy-3-methylphenyl) sulfide, 3,3′-dimethylbiphenol, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1 -Bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylcyclohexane, 1,1-bis (4 -Hydroxy-3,5-dimethylphenyl) adamantane, 1,4-bis (4-hydroxy-3,5-dimethylphenyl) adamanta 2,2-bis (3-ethyl-4-hydroxy-5-methylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxy-5-methylphenyl) propane, 2,2-bis (4-hydroxy-3-methyl-5-phenylphenyl) propane, 2,2-bis (3,5-diethyl-4) -Hydroxyphenyl) propane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-di-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-diphenylphenyl) propane, 5,5-bis (4-hydroxy-3,5-dimethylphenyl) hexahydro -4,7-methanoindane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) sulfone, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) sulfide, 3,3 ', Examples include 5,5′-tetramethylbiphenol and 2,2-bis (4-hydroxy-3-methylphenyl) cyclododecane.

Among these, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-) Methylphenyl) -3,5,5-trimethylcyclohexane, 5,5-bis (4-hydroxy-3-methylphenyl) hexahydro-4,7-methanoindane, 3,3′-dimethylbiphenol, 2,2-bis ( 4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl)- 3,5,5-trimethylcyclohexane, 5,5-bis (4-hydroxy-3,5-dimethylphenyl) hexahydro-4,7-meta Noindan, 3,3 ′, 5,5′-tetramethylbiphenol, 2,2-bis (4-hydroxy-3-methylphenyl) cyclododecane and the like can be mentioned.

Furthermore, among these, 2,2-bis (3-methyl-4-hydroxyphenyl) propane (hereinafter sometimes abbreviated as bisphenol C or BPC), 2,2-bis (3,5-dimethyl-4) -Hydroxyphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -3,5,5-trimethylcyclohexane are preferred 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxy-3-methyl) Phenyl) cyclohexane and 2,2-bis (4-hydroxy-3-methylphenyl) cyclododecane are preferred.
The compound represented by Formula (1) can be used 1 type or in mixture of 2 or more types.

(Melting method: transesterification method)
In the melting method, a dihydroxy compound component containing the compound represented by the above formula (1) as a raw material and a carbonic acid diester as a carbonate-forming compound component are used, and melt weight is continuously performed in the presence of a transesterification catalyst. A polycarbonate resin is produced by a condensation reaction.

(Carbonated diester)
Examples of the carbonic acid diester used in the present invention include a carbonic acid diester compound represented by the following formula.

  Here, in the above formula, A ′ is a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. Two A's may be the same or different from each other. Examples of the substituent on A ′ include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, and an amide. Examples thereof include a group and a nitro group.

Specific examples of the carbonic acid diester compound include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate.
Among these, diphenyl carbonate (hereinafter sometimes abbreviated as DPC) and substituted diphenyl carbonate are preferable. These carbonic acid diesters can be used alone or in admixture of two or more.

Moreover, the amount of the carbonic acid diester compound is preferably 50 mol% or less, more preferably 30 mol% or less, and may be substituted with dicarboxylic acid or dicarboxylic acid ester.
Typical dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate, and the like. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

In the present invention, these carbonic acid diester compounds (including the above-mentioned substituted dicarboxylic acid or dicarboxylic acid ester; the same shall apply hereinafter) are used in excess with respect to the aromatic dihydroxy compound.
That is, with respect to 1 mol of the aromatic dihydroxy compound, the carbonic acid diester compound is usually used in the range of 1.01 mol to 1.30 mol, preferably 1.02 mol to 1.20 mol. When the usage-amount of the said carbonic acid diester compound is too small, the terminal hydroxyl group density | concentration of the obtained polycarbonate resin will become high, and it will become the tendency for thermal stability to deteriorate. In addition, if the amount of carbonic acid diester compound used is excessively large, the transesterification reaction rate decreases, and it becomes difficult to produce a polycarbonate resin having a desired molecular weight, and the carbonic acid diester compound remains in the resin. The amount increases, which may cause odors during molding or when formed into a molded product, which is not preferable.

(Transesterification catalyst)
In the present invention, the polycarbonate resin is preferably polymerized in the presence of a transesterification catalyst. Examples of the transesterification catalyst include, but are not particularly limited to, catalysts used when producing a polycarbonate resin by a transesterification method. In general, for example, a compound containing at least one metal selected from the group consisting of metals of Group 1 and Group 2 of the long-period periodic table, beryllium compound, magnesium compound, basic boron compound, basic phosphorus Examples include basic compounds such as compounds, basic ammonium compounds, and amine compounds. Among these, a compound containing at least one metal selected from the group consisting of metals of Group 1 and Group 2 of the long-period periodic table is practically desirable. These transesterification catalysts may be used alone or in combination of two or more.

The amount of the transesterification catalyst used is usually in the range of 1 × 10 ⁻⁹ to 1 × 10 ⁻¹ mol per 1 mol of the wholly aromatic dihydroxy compound, but an aromatic polycarbonate excellent in molding characteristics and hue is used. In order to obtain the transesterification catalyst, the amount of the transesterification catalyst is preferably 1.0 × 10 ⁻ to 1 mol of the wholly aromatic dihydroxy compound when using the metal compounds of Group 1 and Group 2 of the long-period periodic table. Within the range of ^{7 to} 5 × 10 ⁻⁶ mol, more preferably 0.5 × 10 ⁻⁶ to 4
It exists in the range of * 10 <^-6> mol, ^Most preferably, it exists in the range of 1.0 * 10 < ^-6 > -3 * 10 <^-6> mol. If less than the lower limit, the structural unit derived from the compound represented by the formula (2), the structural unit derived from the compound represented by the formula (3), and the compound represented by the formula (4) The content of at least one type of structural unit selected from structural units derived from is likely to be reduced, and the flame retardancy may be deteriorated. When the content is large, the polymer hue is deteriorated, and represented by the formula (2). A structural unit derived from the compound represented by formula (3), a structural unit derived from the compound represented by formula (3), and a structural unit derived from the compound represented by formula (4). If the amount is too large, gel-like substances or foreign substances insoluble in the solvent may be generated, resulting in poor appearance and reduced mechanical properties of the polycarbonate resin.

  Long-period periodic table Group 1 metal compounds include inorganic metal compounds such as hydroxides, carbonates and hydrogencarbonates of the metals; organics such as salts of the metals with alcohols, phenols and organic carboxylic acids. A metal compound etc. are mentioned. Here, examples of the long-period periodic table group 1 metal include lithium, sodium, potassium, rubidium, and cesium. Among these metal compounds, cesium compounds are preferable, and cesium carbonate, cesium hydrogen carbonate, and cesium hydroxide are particularly preferable.

Examples of the group 2 metal compound of the long-period type periodic table include inorganic metal compounds such as hydroxides and carbonates of the metals; salts of the metals with alcohols, phenols, and organic carboxylic acids. Here, examples of the long-period periodic table group 2 metal include calcium, strontium, and barium.
Examples of the beryllium compound and magnesium compound include inorganic metal compounds such as metal hydroxides and carbonates; salts of the metals with alcohols, phenols, and organic carboxylic acids.

  Examples of basic boron compounds include sodium salts, potassium salts, lithium salts, calcium salts, magnesium salts, barium salts, strontium salts, and the like of boron compounds. Here, as the boron compound, for example, tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributyl Examples include benzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, and butyltriphenylboron.

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

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

(Catalyst deactivator)
In the present invention, a catalyst deactivator for neutralizing and deactivating the transesterification catalyst may be added after completion of the transesterification reaction. The heat resistance and hydrolysis resistance of the polycarbonate resin obtained by such treatment are improved.
As such a catalyst deactivator, an acidic compound having a pKa of 3 or less, such as sulfonic acid and sulfonic acid ester, is preferable. Specifically, benzenesulfonic acid, p-toluenesulfonic acid, methyl benzenesulfonate, benzenesulfone Examples include ethyl acetate, propyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, and butyl p-toluenesulfonate.

Among these, p-toluenesulfonic acid and butyl p-toluenesulfonate are preferably used.
The method for producing a polycarbonate resin by a melting method is to prepare a raw material mixed melt of a raw material dihydroxy compound and a carbonic acid diester (original preparation step), and the raw material mixed melt is melted in the presence of a transesterification reaction catalyst. The polycondensation reaction is performed in multiple stages using a plurality of reaction tanks (polycondensation step). The reaction system may be any of a batch system, a continuous system, or a combination of a batch system and a continuous system. As the reaction tank, a plurality of vertical stirring reaction tanks and, if necessary, at least one horizontal stirring reaction tank subsequent thereto are used. Usually, these reaction tanks are installed in series and processed continuously.

After the polycondensation process, the reaction is stopped, the unreacted raw materials and reaction byproducts in the polycondensation reaction liquid are devolatilized and removed, the process of adding a thermal stabilizer, mold release agent, colorant, etc., polycarbonate resin You may add suitably the process etc. which form in a predetermined particle size.
Next, each process of the manufacturing method will be described.

(Primary process)
The dihydroxy compound and the carbonic acid diester compound used as the raw material of the polycarbonate resin are usually raw materials using a batch type, semi-batch type or continuous type stirring tank type apparatus in an atmosphere of an inert gas such as nitrogen or argon. Prepared as a mixed melt. For example, when bisphenol C is used as the dihydroxy compound and diphenyl carbonate is used as the carbonic acid diester compound, the melt mixing temperature is usually selected from the range of 120 ° C. to 180 ° C., preferably 125 ° C. to 160 ° C.

Hereinafter, a case where bisphenol C is used as a dihydroxy compound and diphenyl carbonate is used as a raw material as a carbonic acid diester compound will be described as an example.
At this time, the ratio of the dihydroxy compound and the carbonic acid diester compound is adjusted so that the carbonic acid diester compound becomes excessive. The carbonic acid diester compound is usually 1.01 mol to 1.30 mol with respect to 1 mol of the dihydroxy compound. Preferably, it is adjusted to a ratio of 1.02 mol to 1.20 mol.

(Polycondensation process)
The polycondensation by the transesterification reaction between the dihydroxy compound and the carbonic acid diester compound is usually carried out continuously in a multistage system of two or more stages, preferably 3 to 7 stages. Specific reaction conditions for each stage include temperature: 150 ° C. to 330 ° C., pressure: normal pressure to 0.01 Torr (1.3 Pa), and average residence time: 5 minutes to 150 minutes.

In each multi-stage reactor, in order to more effectively remove monohydroxy compounds such as phenol as a by-product from the system as the transesterification progresses, the reaction temperature is increased stepwise in the above reaction conditions. Set to high vacuum.
In particular, the reaction temperature in the final polymerization tank is usually 250 ° C to 330 ° C, preferably 270 ° C to 320 ° C, more preferably 280 ° C to 300 ° C. When the reaction temperature of the final polymerization tank is too low, the polycarbonate resin of the present invention has a structural unit derived from the compound represented by the formula (2), a structural unit derived from the compound represented by the formula (3) And the quantity of the at least 1 sort (s) of structural unit chosen from the structural unit derived from the compound represented by said Formula (4) decreases, and there exists a possibility that a flame retardance may fall. Moreover, there is a possibility that the polymerization reaction does not proceed sufficiently and only a polycarbonate having a low molecular weight can be obtained. On the other hand, when the reaction temperature of the final polymerization tank is too high, the polymer hue deteriorates, and the structural unit derived from the compound represented by the formula (2), which the polycarbonate resin of the present invention has, the formula (3) The amount of at least one structural unit selected from the structural unit derived from the compound represented by formula (4) and the structural unit derived from the compound represented by the formula (4) is too large, and is a gel-insoluble matter in a solvent. Or foreign matter may occur, resulting in poor appearance and reduced mechanical properties of the polycarbonate resin.

  The average residence time in the final polymerization tank is usually 5 minutes to 150 minutes, preferably 30 minutes to 120 minutes, and more preferably 60 minutes to 90 minutes. If the average residence time in the final polymerization tank is too short, the amount of compound 2, compound 3, and compound 4 produced is reduced, and flame retardancy may be reduced. Moreover, there is a possibility that the polymerization reaction does not proceed sufficiently and only a polycarbonate having a low molecular weight can be obtained. On the other hand, if the average residence time in the final polymerization tank is too long, the polymer hue deteriorates, and the structural unit derived from the compound represented by the formula (2) possessed by the polycarbonate resin of the present invention, the formula (3) The amount of at least one structural unit selected from the structural unit derived from the compound represented by formula (4) and the structural unit derived from the compound represented by the formula (4) is too large, and the gel is insoluble in the solvent. There is a possibility that an object or a foreign matter may be generated to deteriorate the appearance and the mechanical properties of the polycarbonate resin.

When the polycondensation step is performed in a multistage manner, usually, a plurality of reaction vessels including a vertical stirring reaction vessel are provided to increase the average molecular weight of the polycarbonate resin. The reaction tank is usually installed in 2 to 6 groups, preferably 4 to 5 groups.
Here, as a reaction tank, for example, a stirring tank type reaction tank, a thin film reaction tank, a centrifugal thin film evaporation reaction tank, a surface renewal type biaxial kneading reaction tank, a biaxial horizontal type stirring reaction tank, a wet wall reaction tank, a free tank A perforated plate type reaction vessel that polycondenses while dropping, a perforated plate type reaction vessel with wire that polycondenses while dropping along a wire, and the like are used.

The types of stirring blades in the vertical stirring reaction tank include, for example, turbine blades, paddle blades, fiddler blades, anchor blades, full zone blades (manufactured by Shinko Environmental Solution Co., Ltd.), Sun Meller blades (manufactured by Mitsubishi Heavy Industries, Ltd.), Max blend blades (manufactured by Sumitomo Heavy Industries, Ltd.), helical ribbon blades, twisted lattice blades (manufactured by Hitachi Plant Technology Co., Ltd.), and the like.
Moreover, a horizontal stirring reaction tank means that the rotating shaft of a stirring blade is a horizontal type (horizontal direction). As a stirring blade of a horizontal stirring reaction tank, for example, a uniaxial stirring blade such as a disk type or a paddle type, HVR, SCR, N-SCR (manufactured by Mitsubishi Heavy Industries, Ltd.), Vivolak (Sumitomo Heavy Industries, Ltd.) )), Or biaxial stirring blades such as spectacle blades and lattice blades (manufactured by Hitachi Plant Technology Co., Ltd.).

In addition, the transesterification catalyst used for the polycondensation of a dihydroxy compound and a carbonic acid diester compound may usually be prepared as a solution in advance. The concentration of the catalyst solution is not particularly limited, and is adjusted to an arbitrary concentration according to the solubility of the catalyst in the solvent. As the solvent, acetone, alcohol, toluene, phenol, water and the like can be appropriately selected.
When water is selected as the solvent for the catalyst, the nature of the water is not particularly limited as long as the type and concentration of impurities contained are constant, but usually distilled water or deionized water is preferably used.

(Interface method)
In the production method of the polycarbonate resin by the interfacial method, usually, an aqueous solution of a salt of a long-period type periodic table group 1 and / or group 2 of a dihydroxy compound component is prepared, and in the presence of an amine compound used as a polymerization catalyst, An interfacial polycondensation reaction between a dihydroxy compound component and a carbonyl chloride (hereinafter also referred to as CDC) which is a carbonate-forming compound component is performed, and then a polycarbonate resin is obtained through neutralization, water washing and drying steps.

CDC is usually used in liquid or gaseous form. The preferred amount of CDC used is appropriately selected depending on the reaction conditions, particularly the reaction temperature and the concentration of the metal salt of the aromatic dihydroxy compound in the aqueous phase, and is not particularly limited. Usually, CDC is 1 mol to 2 mol, preferably 1.05 mol to 1.5 mol, per 1 mol of the aromatic dihydroxy compound. When the amount of CDC used is excessively large, unreacted CDC increases and the basic unit tends to be extremely deteriorated. On the other hand, if the amount of CDC used is excessively small, the amount of chloroformate group is insufficient and proper molecular weight elongation tends not to be performed.

In the interface method, an organic solvent is usually used. Examples of the organic solvent include inert organic solvents that dissolve reaction products such as carbonyl chloride, carbonate oligomer, and polycarbonate resin and are incompatible with water (or do not form a solution with water).
Examples of such inert organic solvents include aliphatic hydrocarbons such as hexane and n-heptane; chlorinations such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, and 1,2-dichloroethylene. Aliphatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; chlorinated aromatic hydrocarbons such as chlorobenzene, o-dichlorobenzene and chlorotoluene; and other substituted aromatic hydrocarbons such as nitrobenzene and acetophenone It is done.

Among these, for example, chlorinated hydrocarbons such as dichloromethane or chlorobenzene are preferably used. These inert organic solvents can be used alone or as a mixture with other solvents.
The condensation catalyst can be arbitrarily selected from many condensation catalysts used in the two-phase interfacial condensation method. For example, trialkylamine, N-ethylpyrrolidone, N-ethylpiperidine, N-ethylmorpholine, N-isopropylpiperidine, N-isopropylmorpholine and the like can be mentioned. Of these, triethylamine and N-ethylpiperidine are preferable.

  Monophenol is used as the chain terminator. Examples of the monophenol include phenols; alkylphenols having 1 to 20 carbon atoms such as pt-butylphenol and p-cresol; halogenated phenols such as p-chlorophenol and 2,4,6-tribromophenol. It is done. The usage-amount of monophenol is suitably selected according to the molecular weight of the carbonate oligomer obtained, and is 0.5 mol%-10 mol% normally with respect to an aromatic dihydroxy compound.

In the interface method, the molecular weight of the polycarbonate resin is determined by the addition amount of a chain terminator such as monophenol. For this reason, from the viewpoint of controlling the molecular weight of the polycarbonate resin, the chain stopper is preferably added immediately after the consumption of the carbonate-forming compound is completed and before the molecular weight elongation starts.
When monophenol is added in the presence of a carbonate-forming compound, a large amount of condensates (diphenyl carbonates) of monophenols are produced, and it is difficult to obtain a polycarbonate resin having a target molecular weight. If the addition time of monophenol is extremely delayed, it becomes difficult to control the molecular weight, and furthermore, the resin has a specific shoulder on the low molecular weight side of the molecular weight distribution, and there is a tendency that problems such as dripping occur during molding.

  In the interface method, any branching agent can be used. Examples of such a branching agent include 2,4-bis (4-hydroxyphenylisopropyl) phenol, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4- Hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, 1,4-bis (4,4′-dihydroxytriphenylmethyl) benzene and the like. In addition, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and the like can also be used. Among these, a branching agent having at least three phenolic hydroxyl groups is preferable. The amount of the branching agent used is appropriately selected according to the degree of branching of the obtained carbonate oligomer, and is usually 0.05 mol% to 2 mol% with respect to the aromatic dihydroxy compound.

(Manufacture of polycarbonate resin by interface method)
The polycarbonate resin of the present invention by the interfacial method is usually prepared by preparing a long-period group 1 metal aqueous solution of a dihydroxy compound and, as a condensation catalyst, for example, interfacial polycondensation of the dihydroxy compound and phosgene in the presence of an amine compound. Reaction is performed, and then a polycarbonate resin is obtained through neutralization, washing with water, and drying. Specifically, the polycarbonate resin production process by the interfacial method includes a raw material process for preparing raw materials such as monomer components, an oligomerization process in which an oligomerization reaction is performed, a polycondensation process in which a polycondensation reaction using an oligomer is performed, A washing step for washing the reaction solution after the polycondensation reaction by alkali washing, acid washing and water washing, a polycarbonate resin isolation step for pre-concentrating the washed reaction solution and isolating the polycarbonate resin after granulation, It has at least a drying step for drying the polycarbonate resin particles. Hereinafter, each step will be described.

(Primary process)
In the primary process, the primary tank is filled with a dihydroxy compound and an aqueous solution of a long-period periodic table Group 1 metal compound such as sodium hydroxide (NaOH) or a long-period periodic table Group 2 metal compound such as magnesium hydroxide. An aqueous solution of a long-period periodic table group 1 and / or group 2 metal salt of a dihydroxy compound containing a reducing agent such as demineralized water (DMW) and a reducing agent such as hydrosulfite (HS) as necessary The raw material is prepared.

(Long Periodic Periodic Table Group 1 and Group 2 metal compounds)
As the metal compound of Group 1 and Group 2 of the long-period periodic table, a hydroxide is usually preferable, and examples thereof include sodium hydroxide, lithium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and the like. It is done. Among these, sodium hydroxide is particularly preferable.
The ratio of the metal compounds of Group 1 and Group 2 of the long-period periodic table to the dihydroxy compound is usually 1.0 to 1.5 (equivalent ratio), preferably 1.02 to 1.04 (equivalent ratio). It is. When the ratio of the compounds of Group 1 and Group 2 of the long-period periodic table is excessively large or excessively small, it affects the terminal group of the carbonate oligomer obtained in the oligomerization step described later, and as a result, polycondensation reaction Tend to be abnormal.

(Oligomerization process)
Next, in the oligomerization step, an aqueous solution of a metal salt of Group 1 and / or Group 2 of the long-period periodic table of the dihydroxy compound prepared in the original preparation step and phosgene (CDC) are prepared in a predetermined reactor. In the presence of an organic solvent such as methylene chloride (CH ₂ Cl ₂ ), a phosgenation reaction of a dihydroxy compound is performed.

Subsequently, a condensation catalyst such as triethylamine (TEA) and a chain terminator such as pt-butylphenol (pTBP) are added to the mixed solution in which the phosgenation reaction of the dihydroxy compound is performed, and the oligomerization reaction of the dihydroxy compound Is done.
Next, the oligomerization reaction liquid of the dihydroxy compound was introduced into a predetermined stationary separation tank after further oligomerization reaction, and the organic phase containing the carbonate oligomer and the aqueous phase were separated and separated. The organic phase is fed to the polycondensation process.
Here, from when the aqueous solution of the metal salt of Group 1 and / or Group 2 of the long-period type periodic table of the dihydroxy compound is supplied to the reactor in which the phosgenation reaction of the dihydroxy compound is performed, the reactor enters the stationary separation tank. The residence time in the oligomerization step is usually 120 minutes or less, preferably 30 to 60 minutes.

(CDC)
The CDC used in the oligomerization step is usually used in liquid or gaseous form. The preferred amount of CDC used in the oligomerization step is appropriately selected depending on the reaction conditions, particularly the reaction temperature and the concentration of the dihydroxy compound in the aqueous phase, and is not particularly limited. Usually, the amount of CDC is 1 mol to 2 mol, preferably 1.05 mol to 1.5 mol, per 1 mol of the dihydroxy compound. When the amount of CDC used is excessively large, unreacted CDC increases and the basic unit tends to be extremely deteriorated. On the other hand, if the amount of CDC used is excessively small, the amount of chloroformate group is insufficient and proper molecular weight elongation tends not to be performed.

(Organic solvent)
In the oligomerization step, an organic solvent is usually used. As the organic solvent, any reaction product that dissolves reaction products such as CDC, carbonate oligomer, and polycarbonate resin at the reaction temperature and reaction pressure in the oligomerization step and is incompatible with water (or does not form a solution with water). An active organic solvent is mentioned.

Examples of such inert organic solvents include aliphatic hydrocarbons such as hexane and n-heptane; chlorinations such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, and 1,2-dichloroethylene. Aliphatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; chlorinated aromatic hydrocarbons such as chlorobenzene, o-dichlorobenzene and chlorotoluene; and other substituted aromatic hydrocarbons such as nitrobenzene and acetophenone It is done.
Among these, chlorinated hydrocarbons such as dichloromethane or chlorobenzene are preferably used. These inert organic solvents can be used alone or as a mixture with other solvents.

(Condensation catalyst)
The oligomerization reaction can be performed in the presence of a condensation catalyst. The addition timing of the condensation catalyst is preferably after CDC is consumed. The condensation catalyst can be arbitrarily selected from many condensation catalysts used in the two-phase interfacial condensation method. For example, trialkylamine, N-ethylpyrrolidone, N-ethylpiperidine, N-ethylmorpholine, N-isopropylpiperidine, N-isopropylmorpholine and the like can be mentioned. Of these, triethylamine and N-ethylpiperidine are preferable.

(Chain terminator)
In the present embodiment, monophenol is usually used as a chain terminator in the oligomerization step. Examples of the monophenol include phenols; alkylphenols having 1 to 20 carbon atoms such as pt-butylphenol and p-cresol; halogenated phenols such as p-chlorophenol and 2,4,6-tribromophenol. It is done. The usage-amount of monophenol is suitably selected according to the molecular weight of the carbonate oligomer obtained, and is 0.5 mol%-10 mol% normally with respect to a dihydroxy compound.

In the interface method, the molecular weight of the polycarbonate resin is determined by the addition amount of a chain terminator such as monophenol. For this reason, from the viewpoint of controlling the molecular weight of the polycarbonate resin, the chain stopper is preferably added immediately after the consumption of the carbonate-forming compound is completed and before the molecular weight elongation starts.
When monophenol is added in the presence of a carbonate-forming compound, a large amount of condensates (diphenyl carbonates) of monophenols are produced, and it is difficult to obtain a polycarbonate resin having a target molecular weight. When the addition time of monophenol is extremely delayed, it becomes difficult to control the molecular weight, and furthermore, the resin has a specific shoulder on the low molecular weight side of the molecular weight distribution, and there is a tendency that problems such as dripping occur during molding.

(Branching agent)
In the oligomerization step, any branching agent can be used. Examples of such a branching agent include 2,4-bis (4-hydroxyphenylisopropyl) phenol, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2
-(4-Hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, 1,4-bis (4,4′-dihydroxytriphenylmethyl) benzene and the like. In addition, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and the like can also be used. Among these, a branching agent having at least three phenolic hydroxyl groups is preferable. The amount of branching agent used is appropriately selected according to the degree of branching of the carbonate oligomer obtained, and is usually 0.05 mol% to 2 mol% with respect to the dihydroxy compound.

  In the oligomerization step, when the two-phase interfacial condensation method is adopted, prior to the contact of the long-period periodic table group 1 metal compound aqueous solution or long-period periodic table group 2 metal compound aqueous solution of the dihydroxy compound with phosgene, the dihydroxy compound An organic phase containing a compound, an aqueous phase containing a long-period periodic table group 1 metal compound or a long-period periodic table group 2 metal compound, and an organic phase which is not arbitrarily mixed with water are brought into contact with each other. It is particularly preferable to form it.

Examples of means for forming such an emulsion include a stirrer having a predetermined stirring blade, a homogenizer, a homomixer, a colloid mill, a flow jet mixer, a dynamic mixer such as an ultrasonic emulsifier, a static mixer, and the like. It is preferable to use a mixer. The emulsion usually has a droplet diameter of 0.01 μm to 10 μm and has emulsion stability.
The emulsion state of the emulsion is usually represented by the Weber number or P / q (load power value per unit volume). The Weber number is preferably 10,000 or more, more preferably 20,000 or more, and most preferably 35,000 or more. Also, the upper limit is about 1,000,000 or less. P / q is preferably 200 kg · m / L or more, more preferably 500 kg · m / L or more, and most preferably 1,000 kg · m / L or more.

  The contact between the emulsion and the CDC is preferably carried out under a mixing condition that is weaker than the emulsification conditions described above in order to suppress the dissolution of CDC in the organic phase. The Weber number is less than 10,000, preferably less than 5,000, and more preferably less than 2,000. Further, P / q is less than 200 kg · m / L, preferably less than 100 kg · m / L, and more preferably less than 50 kg · m / L. CDC contact can be achieved by introducing CDC into a tubular reactor or tank reactor.

The reaction temperature in the oligomerization step is usually 80 ° C. or lower, preferably 60 ° C. or lower, more preferably 10 ° C. to 50 ° C. The reaction time is appropriately selected depending on the reaction temperature, and is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. If the reaction temperature is excessively high, side reactions cannot be controlled and the CDC basic unit tends to deteriorate. If the reaction temperature is excessively low, this is a favorable situation in terms of reaction control, but the refrigeration load increases and the cost tends to increase.
The concentration of the carbonate oligomer in the organic phase may be in a range in which the obtained carbonate oligomer is soluble, and is specifically about 10 wt% to 40 wt%. The ratio of the organic phase is a volume ratio of 0.2 to 1.0 with respect to the aqueous phase containing the long-period periodic table group 1 metal salt aqueous solution or the long-period periodic table group 2 metal salt aqueous solution of the dihydroxy compound. It is preferable.

(Polycondensation process)
Next, in the polycondensation step, the organic phase containing the carbonate oligomer separated from the aqueous phase in the stationary separation tank is transferred to an oligomer storage tank having a stirrer. A condensation catalyst such as triethylamine (TEA) is further added to the oligomer storage tank.
Subsequently, the organic phase stirred in the oligomer storage tank is introduced into a predetermined polycondensation reaction tank. Subsequently, an organic solvent such as demineralized water (DMW) or methylene chloride (CH ₂ Cl ₂ ) is added to the polycondensation reaction tank. Then, an aqueous sodium hydroxide solution is supplied and mixed with stirring to carry out a polycondensation reaction of the carbonate oligomer.
Thereafter, the polycondensation reaction liquid in the polycondensation reaction tank is successively introduced successively into a plurality of polycondensation reaction tanks, and the polycondensation reaction of the carbonate oligomer is completed.
Here, in the polycondensation step, the residence time in the polycondensation reaction tank in which the polycondensation reaction of the carbonate oligomer is continuously performed is usually 12 hours or less, preferably 0.5 to 5 hours.

  As a preferred embodiment of the polycondensation step, first, an organic phase containing a carbonate oligomer and an aqueous phase are separated, and an inert organic solvent is added to the separated organic phase as necessary to adjust the concentration of the carbonate oligomer. In this case, the amount of the inert organic solvent is adjusted so that the concentration of the polycarbonate resin in the organic phase obtained by the polycondensation reaction is 5% by weight to 30% by weight. Next, an aqueous solution containing water and a long-period type periodic table Group 1 metal compound or a long-period type periodic table Group 2 metal compound is added, and a condensation catalyst is preferably added to adjust polycondensation conditions. Then, a polycondensation reaction is performed according to the interfacial polycondensation method. The ratio of the organic phase to the aqueous phase in the polycondensation reaction is preferably about volume ratio of organic phase: aqueous phase = 1: 0.2 to 1: 1.

  Examples of the long-period periodic table group 1 metal compound or the long-period periodic table group 2 metal compound include compounds similar to those used in the oligomerization step described above. Of these, sodium hydroxide is preferred industrially. The amount of the long-period periodic table group 1 metal compound or long-period periodic table group 2 metal compound used may be more than the amount that the reaction system is always kept basic during the polycondensation reaction. At the start of the reaction, the whole amount may be added all at once, or may be added in appropriate portions during the polycondensation reaction.

When the amount of the long-period periodic table group 1 metal compound or long-period periodic table group 2 metal compound used is excessively large, the hydrolysis reaction as a side reaction tends to proceed. Therefore, the concentration of the long-period periodic table group 1 metal compound or the long-period periodic table group 2 metal compound contained in the aqueous phase after the completion of the polycondensation reaction is 0.05 N or more, preferably 0.05 N to 0.00. It is good to make it about 3N.
The temperature of the polycondensation reaction in the polycondensation step is usually around room temperature. The reaction time is about 0.5 to 5 hours, preferably about 1 to 3 hours.

(Washing process)
Next, after the polycondensation reaction in the polycondensation reaction tank is completed, the polycondensation reaction solution is subjected to alkali washing with an alkali washing solution, acid washing with an acid washing solution, and water washing with washing water by a known method. In addition, the total residence time of the washing step is usually 12 hours or less, preferably 0.5 to 6 hours.

(Polycarbonate resin isolation process)
In the polycarbonate resin isolation step, first, the polycondensation reaction solution containing the polycarbonate resin washed in the washing step is prepared as a concentrated solution concentrated to a predetermined solid content concentration. The solid content concentration of the polycarbonate resin in the concentrate is usually 5% to 35% by weight, preferably 10% to 30% by weight.

Next, the concentrate is continuously supplied to a predetermined granulation tank, and stirred and mixed with demineralized water (DMW) at a predetermined temperature. And the granulation process which evaporates an organic solvent is performed, maintaining a suspended state in water, and the water slurry containing a polycarbonate resin granular material is formed.
Here, the temperature of the demineralized water (DMW) is usually 37 ° C to 67 ° C, preferably 40 ° C to 50 ° C. Moreover, the solidification temperature of polycarbonate resin by the granulation process performed in a granulation tank is 37 to 67 degreeC normally, Preferably, it is 40 to 50 degreeC.
The water slurry containing the polycarbonate resin powder continuously discharged from the granulation tank is then continuously introduced into a predetermined separator, and water is separated from the water slurry.

(Drying process)
In the drying process, in the separator, the polycarbonate resin powder from which water has been separated from the water slurry is continuously supplied to a predetermined dryer, retained for a predetermined residence time, and then continuously extracted. . Examples of the dryer include a fluidized bed dryer. A plurality of fluidized bed dryers may be connected in series to continuously perform the drying process.

Here, the dryer usually has a heating means such as a heat medium jacket, for example, with water vapor, usually 0.1 MPa-G to 1.0 MPa-G, preferably 0.2 MPa-G to 0. .6 MPa-G. Thereby, the temperature of nitrogen (N2) circulating in the dryer is
Usually, it is maintained at 100 ° C to 200 ° C, preferably 120 ° C to 180 ° C.
The polycarbonate resin obtained by the interface method described above is usually the content of structural units derived from the compound represented by the formula (2), the content of structural units derived from the compound represented by the formula (3), In some cases, the content of the structural unit derived from the compound represented by the formula (4) is very small. Therefore, the following method is used to obtain the polycarbonate resin of the present invention.

  The content of the structural unit derived from the compound represented by the formula (2) by the heat treatment of the polycarbonate resin obtained by the interfacial method, the content of the structural unit derived from the compound represented by the formula (3) And at least one structural unit selected from the content of the structural unit derived from the compound represented by the formula (4) can be controlled to a specific amount. Any method may be used as the heat treatment method. Specifically, a method of heating a polycarbonate resin in a tank by a batch method, a method of heating a polycarbonate resin in a tank by a continuous method, a method of heating a polycarbonate resin by an extruder, etc. Is mentioned. Of these, heating by a single screw extruder or a twin screw extruder is more preferable, and heating by a twin screw extruder with a vent port is more preferable. The heat treatment temperature is preferably 200 ° C to 400 ° C, more preferably 260 ° C to 390 ° C, further preferably 270 ° C to 380 ° C, and most preferably 280 ° C to 370 ° C as the polycarbonate resin temperature. When the polycarbonate resin temperature is too low, the content of the structural unit derived from the compound represented by the formula (2) in the polycarbonate resin of the present invention, the content of the structural unit derived from the compound represented by the formula (3) The content of the structural unit derived from the amount and the compound represented by the formula (4) is small, and the flame retardancy may be lowered. On the other hand, when the polycarbonate resin temperature is too high, the polymer hue deteriorates, and the content of the structural unit derived from the compound represented by the formula (2), which the polycarbonate resin of the present invention has, the formula (3) Both of the content of the structural unit derived from the compound represented by formula (1) and the content of the structural unit derived from the compound represented by the formula (4) are too large, and a gel-like substance or foreign matter insoluble in the solvent is present. It may occur, and there is a risk of poor appearance and mechanical properties of the polycarbonate resin.

The polycarbonate resin temperature is the temperature of the polycarbonate resin at the exit of the extruder if it is an extruder, and the temperature of the polycarbonate resin in the tank if it is a reaction tank.
The heat treatment time is preferably 0.5 minutes to 2 hours, more preferably 1 minute to 1 hour, further preferably 1.5 minutes to 30 minutes, and most preferably 2 minutes to 10 minutes. When the heat treatment time is too short, the content of the structural unit derived from the compound represented by the formula (2) in the polycarbonate resin of the present invention, the content of the structural unit derived from the compound represented by the formula (3) Both the amount and the content of the structural unit derived from the compound represented by the formula (4) are decreased, and the flame retardancy may be lowered. On the other hand, if the heat treatment time is too long, the polymer hue deteriorates, and the content of the structural unit derived from the compound represented by the formula (2) in the polycarbonate resin of the present invention is represented by the formula (3). When both the content of the structural unit derived from the compound and the content of the structural unit derived from the compound represented by the formula (4) are too large, a gel-like substance or a foreign substance insoluble in the solvent is generated. There is a risk of poor appearance and reduced mechanical properties of the polycarbonate resin. In the case of heat treatment by an extruder, the heat treatment time is calculated from the extrusion speed and the volume in the barrel.

  In addition to the polycarbonate resin obtained by polymerizing a dihydroxy compound containing a compound represented by the formula (1) as a main component and a carbonate-forming compound, the polycarbonate resin of the present invention may have the following formula (10 And a polycarbonate resin obtained by polymerizing a dihydroxy compound containing a compound represented by (2) as a main component and a carbonate-forming compound.

Here, in formula (10), X has the same meaning as in formula (1).
Specific examples of the polycarbonate resin having the structural unit represented by the formula (10) include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

  In the present invention, in addition to a polycarbonate resin obtained by polymerizing a dihydroxy compound containing a compound represented by the formula (1) as a main component and a carbonate-forming compound, the compound represented by the formula (10) is a main component. In the case of using together a dihydroxy compound containing as a polycarbonate resin obtained by polymerizing a carbonate-forming compound, the dihydroxy compound containing as a main component a compound represented by formula (1) and a carbonate-forming compound are polymerized. The content of the polycarbonate resin thus obtained is more preferably 10% by weight or more in the total polycarbonate resin, more preferably 20% by weight or more, and most preferably 30% by weight or more. Moreover, 99 weight% or less is preferable and 90 weight% or less is more preferable. If the content of the polycarbonate resin obtained by polymerizing a dihydroxy compound containing a compound represented by the formula (1) as a main component and a carbonate-forming compound is too large, the impact resistance may be lowered, and the amount is too small. The color tone may deteriorate, the pencil hardness may decrease, and the flame retardancy may decrease.

(Flame retardants)
When the polycarbonate resin of the present invention is added with a flame retardant to form a polycarbonate resin composition, the polycarbonate resin exhibits a more remarkable effect and improves the flame retardancy. Examples of the flame retardant to be used include at least one selected from the group consisting of sulfonic acid metal salt flame retardants, halogen-containing compound flame retardants, phosphorus-containing compound flame retardants, and silicon-containing compound flame retardants. Among these, a sulfonic acid metal salt flame retardant is preferable.

The amount of the flame retardant used in the present invention is usually 0.01 parts by weight or more, preferably 0.05 parts by weight or more with respect to 100 parts by weight of the polycarbonate resin. If the blending amount of the flame retardant is too small, the flame retardant effect is lowered. When the blending amount of the flame retardant is excessively large, the mechanical strength of the resin molded product tends to decrease too much.
Examples of the sulfonic acid metal salt flame retardant include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts. The metals of these metal salts include sodium, lithium, potassium, rubidium, and cesium long-period periodic table group 1 metals; beryllium and magnesium magnesiums; long-period periodic table group 2 such as calcium, strontium, and barium. Metal etc. are mentioned. A sulfonic acid metal salt can also be used 1 type or in mixture of 2 or more types. Examples of the sulfonic acid metal salt include aromatic sulfonesulfonic acid metal salts and perfluoroalkane-sulfonic acid metal salts.

The sulfonic acid metal salt flame retardant is preferably added in an amount of 0.04 to 0.3 parts by weight, more preferably 0.05 to 0.2 parts by weight, based on 100 parts by weight of the polycarbonate resin.
Specific examples of the aromatic sulfonesulfonic acid metal salt include, for example, sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, sodium 4,4′-dibromodiphenyl-sulfone-3-sulfonate, 4 , 4′-Dibromodiphenyl-sulfone-3-sulfone potassium, 4-chloro-4′-nitrodiphenylsulfone-3-calcium sulfonate, disodium diphenylsulfone-3,3′-disulfonate, diphenylsulfone-3,3 Examples include dipotassium di-sulfonate.

  Specific examples of perfluoroalkane-sulfonic acid metal salt include perfluorobutane-sodium sulfonate, perfluorobutane-potassium sulfonate, perfluoromethylbutane-sodium sulfonate, perfluoromethylbutane-potassium sulfonate, perfluoro Examples include octane-sodium sulfonate, potassium perfluorooctane-sulfonate, and tetraethylammonium salt of perfluorobutane-sulfonic acid.

  Specific examples of the halogen-containing compound flame retardant include, for example, tetrabromobisphenol A, tribromophenol, brominated aromatic triazine, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A epoxy polymer, decabromodiphenyl oxide, tribromo Examples include allyl ether, tetrabromobisphenol A carbonate oligomer, ethylene bistetrabromophthalimide, decabromodiphenylethane, brominated polystyrene, hexabromocyclododecane and the like.

The halogen-containing compound flame retardant is preferably added in an amount of 5 to 30 parts by weight, more preferably 10 to 25 parts by weight, based on 100 parts by weight of the polycarbonate resin.
Examples of the phosphorus-containing compound flame retardant include red phosphorus, coated red phosphorus, polyphosphate compound, phosphate ester compound, and phosphazene compound. Among these, specific examples of the phosphate ester compound include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl. Phosphate, diisopropylphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3- Dibromopropyl) phosphate, bis (chloropropyl) monooctyl phosphate, bisphenol A bisphosphate, hydro Non bisphosphate, resorcinol bisphosphate, trioxybenzene phosphate.

The phosphorus-containing compound flame retardant is preferably added in an amount of 3 to 15 parts by weight, more preferably 5 to 25 parts by weight, and most preferably 10 to 12 parts by weight based on 100 parts by weight of the polycarbonate resin.
Examples of the silicon-containing compound flame retardant include silicone varnish, a silicone resin in which a substituent bonded to a silicon atom is an aromatic hydrocarbon group and an aliphatic hydrocarbon group having 2 or more carbon atoms, and a main chain having a branched structure. And a silicone compound having an aromatic group in the organic functional group contained therein, a silicone powder carrying a polydiorganosiloxane polymer which may have a functional group on the surface of the silica powder, and an organopolysiloxane-polycarbonate copolymer Etc.

The molded body formed from the polycarbonate resin of the present invention is obtained by combining, for example, a polycarbonate resin having a structural unit represented by the above-described formula (1) and a flame retardant, for example, a polycarbonate resin obtained using bisphenol A as a raw material monomer ( Compared with the molded object formed from the resin composition using "A-PC".), A flame retardance improves.
The reason why the flame retardancy of the molded product formed from the polycarbonate resin of the present invention is not clear is not clear, but for example, the polycarbonate resin component contains an aromatic dihydroxy compound 2,2-bis (3-methyl-4-hydroxy). Taking the case of using a polycarbonate resin (referred to as “C-PC”) obtained by using phenyl) propane as a raw material monomer, it is considered as follows.

  That is, the polycarbonate resin of the present invention has a structural unit derived from the compound represented by the formula (2), a structural unit derived from the compound represented by the formula (3), and the formula (4). Due to the branched structure generated from at least one structural unit selected from the structural units derived from the compound to be produced, the viscosity in the low shear region increases, which suppresses combustion drops (drip) in the combustion test. It is considered that the flame retardancy is improved. Furthermore, C-PC and the like have a methyl group in the benzene ring forming the skeleton, and thus the molecular chain is easily broken and decomposition is quicker than A-PC. For this reason, C-PC or the like is rapidly decomposed and graphitized, and easily exhibits flame retardancy by forming a heat insulating layer (char). The thermal decomposition onset temperature of C-PC and the like is lower than that of A-PC because of the structural difference that “the 3-position of two benzene rings is substituted with a methyl group” of the bisphenol skeleton. It is thought that.

Since the molded body formed from the polycarbonate resin of the present invention has such characteristics, for example, a casing for precision equipment such as a mobile phone and a PC; a housing for home appliances such as a TV; a film for a screen; Useful as a raw material for resin parts that require high dimensional accuracy, such as multi-layer molded products of two or more layers, such as carports, agricultural houses, and soundproof boards. It is.
In addition, from the polycarbonate resin of the present invention, it is possible to prepare a resin molded body having high hardness and improved flame retardancy, and the molded body can be used for illumination of LEDs such as a lamp lens, a protective cover, and a diffusion plate. Related resin molded products; suitably used for spectacle lenses, vending machine buttons, keys for portable devices, and the like.

<Additives>
Various additives are blended in the polycarbonate resin composition of the present invention as necessary. Examples of additives include stabilizers, ultraviolet absorbers, mold release agents, colorants, antistatic agents, thermoplastic resins, thermoplastic elastomers, glass fibers, glass flakes, glass beads, carbon fibers, wollastonite, silicic acid. Examples thereof include calcium and aluminum borate whiskers.
There are no particular limitations on the method of mixing the polycarbonate resin, the flame retardant, and the additives blended as necessary. In the present invention, for example, after mixing a polycarbonate resin in a solid state such as pellets or powder and a flame retardant, etc., a method of kneading with an extruder or the like, a method of mixing a polycarbonate resin in a molten state and a flame retardant, a melting method or Examples thereof include a method of adding a flame retardant during the polymerization reaction of the raw material monomer in the interface method or at the end of the polymerization reaction.

<Polycarbonate resin molding>
A polycarbonate resin molded article is prepared using the polycarbonate resin and the polycarbonate resin composition of the present invention. The molding method of the polycarbonate resin molding is not particularly limited, and examples thereof include a molding method using a conventionally known molding machine such as an injection molding machine.
Polycarbonate resin molded article of the present invention, for example, as compared with the case of using the polycarbonate resin obtained a bisphenol A as a monomer, decrease in surface hardness and transparency of the molded body is suppressed, and excellent flame retardancy It is.
Specifically, the molded body formed from the polycarbonate resin composition of the present invention preferably satisfies the V-0 standard in the flame retardancy test of UL94 using a test piece having a thickness of 2 mm or less. . About transparency, it is preferable that the haze value by the test piece of thickness 3mm based on prescription | regulation of JIS-K7136 is 1.0 or less.

<Pencil hardness>
The polycarbonate resin and the polycarbonate resin composition of the present invention preferably have a pencil hardness according to JIS K5600 of HB or higher. The pencil hardness is more preferably F or more, and still more preferably H or more. However, it is usually 3H or less. When the pencil hardness is less than HB, the surface of the resin molded body tends to be damaged.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to a following example. The physical properties of the polycarbonate resin and the composition used in the examples were evaluated by the following methods.
(1) Viscosity average molecular weight (Mv)
The polycarbonate resin was dissolved in methylene chloride (concentration 6.0 g / L), the specific viscosity (ηsp) at 20 ° C. was measured using an Ubbelohde viscosity tube, and the viscosity average molecular weight (Mv) was calculated by the following formula.
ηsp / C = [η] (1 + 0.28ηsp)
[η] = 1.23 × 10 ⁻⁴ Mv ^0.83
(2) Terminal hydroxyl group concentration of polycarbonate (OH)
The terminal hydroxyl group concentration of the polycarbonate was measured by colorimetric determination according to the titanium tetrachloride / acetic acid method (see Makromol. Chem. 88, 215 (1965)).

(3) Formula (2) Quantitative determination of structural units derived from the compounds represented by Formula (3) and Formula (4) After dissolving 0.5 g of polycarbonate resin in 5 ml of methylene chloride, 45 ml of methanol and 25% by weight of hydroxide Add 5 ml of aqueous sodium solution and stir at 70 ° C. for 30 minutes. The obtained solution is analyzed by liquid chromatography, and the structural units derived from the compounds represented by formula (2), formula (3) and formula (4) are quantified. The quantification was performed using a calibration curve created by quantification of the repeating unit represented by the formula (1).

Liquid chromatography measurement was performed by the following method.
Device: manufactured by 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
From A / B = 60/40 (vol%) to A / B = 95/5 (vol%)
Gradient in 25 minutes Flow rate: 1 mL / min
Sample injection volume: 20 μl

  Moreover, the compound 2 which is a structural unit derived from the compound represented by the formula (2), the compound 3 which is a structural unit derived from the compound represented by the formula (3), and the formula (4) Compound 4, which is a structural unit derived from the above compound, was observed at the following retention time under the above liquid chromatography conditions.

Compound 4: 13.9 minutes represented by formula (4) Compound 2: 15.9 minutes represented by formula (2) Compound 21: 21 minutes represented by formula (3) The portion corresponding to the peak observed at the retention time was collected, and the collected sample was analyzed by ¹ H NMR, ¹³ C NMR, two-dimensional NMR method, mass spectrometry (MS), infrared absorption spectrum method (IR spectrum). Carried out.

  The compound 4 represented by the formula (4) was identified from the molecular weight of the sample collected by mass spectrometry, the NMR spectrum signal, and the signal derived from the aldehyde in the IR spectrum. The compound 2 represented by the formula (2) was identified from the molecular weight of the sample collected by mass spectrometry, the NMR spectrum signal, and the signal derived from the carboxylic acid in the IR spectrum. The compound 3 represented by the formula (3) was identified from the molecular weight of each sample obtained by mass spectrometry and each NMR spectrum signal.

(4) Determination of presence or absence of methylene chloride insoluble matter 0.5 g of polycarbonate resin was immersed in 5 ml of methylene chloride, stirred for 30 minutes, and then filtered through a glass filter. The glass filter was vacuum-dried at room temperature for 2 hours, and when the weight increase was 0.01 g or more compared to before filtration, it was determined that methylene chloride was insoluble. Moreover, when the weight increase was 0.01 g or less, it was determined that there was no methylene chloride insoluble matter.

(5) Pencil hardness of injection-molded body Polycarbonate having a thickness of 3 mm, a length of 60 mm, and a width of 60 mm under the conditions of a barrel temperature of 280 ° C. and a mold temperature of 90 ° C. using an injection molding machine (J50E2 manufactured by Nippon Steel) A resin plate (molded product) or a polycarbonate resin composition plate (molded product) was injection molded. This molded body conforms to ISO 15184 and is a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd.)
Was used to determine the pencil hardness measured at a load of 750 g.

(6) V-0 Achieved Thickness of Injection Molded Body with Addition of Flame Retardant Polycarbonate resin is kneaded at a barrel temperature of 280 ° C. with a twin-screw extruder (TEX30XCT manufactured by Nippon Steel Works) to obtain a polycarbonate resin composition pellet. It was. At that time, 0.1% by weight of perfluorobutanesulfonic acid potassium salt (Biowet C4 manufactured by Bayer) as a flame retardant and 0.1% of pentaerythritol tetrastearate (Unistar H-476 manufactured by NOF Corporation) as a release agent. Weight percent was added. The obtained pellets were dried at 80 ° C. for 5 hours, and the thickness was determined by an injection molding machine (SE100DU manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of 260 ° C. to 280 ° C. and a molding cycle of 30 seconds according to UL standards. The changed test piece was injection-molded and subjected to a UL standard 94 vertical combustion test.

  In the present invention, V-0 is achieved most when each polycarbonate resin composition is evaluated with test pieces having thicknesses of 3 mm, 2 mm, 1.8 mm, 1.5 mm, 1.2 mm, 1.0 mm, and 0.8 mm. The thick thickness was defined as V-0 achieved thickness. In addition, it means that the flame retardance with thin wall is so high that V-0 achievement thickness is thin.

(7) Number of foreign matter of 300 μm or more in 70 μm polycarbonate film Filmed at a barrel temperature of 280 ° C. by a single-screw extruder equipped with a polycarbonate resin at the tip and a 180 mm wide die and a film take-up device to obtain a 70 μm polycarbonate film It was. This polycarbonate film, using visual and microscopic counts the number of foreign matters than 300 [mu] m, and evaluated as number per 1 m ^2.

(8) Metal amounts of Group 1 and Group 2 metal compounds per mole of the compound represented by Formula (1) Total amount of about 0.3 g of polycarbonate resin was accurately weighed, nitric acid was added, and heat was applied in a sealed state. Decomposition was performed. The decomposition solution was quantified with pure water, and the amounts of Group 1 and Group 2 metals were quantified with ICP-MS (ELEMENT 2 manufactured by Thermo Fisher Scientific).

[Example 1]
As the dihydroxy compound, 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter sometimes abbreviated as “BPC”) (manufactured by Honshu Chemical) 37.6 kg (about 147 mol) and diphenyl carbonate The mixture was prepared by adding an aqueous solution of cesium carbonate to 32.2 kg (about 150 mol) of (DPC) so that the cesium carbonate was 1.5 μmol per mol of the dihydroxy compound. Next, the mixture was charged into a first reactor having an internal volume of 200 L equipped with a stirrer, a heating medium jacket, a vacuum pump, and a reflux condenser.

  Next, the operation of depressurizing the inside of the first reactor to 1.33 kPa (10 Torr) and then restoring the pressure to the atmospheric pressure with nitrogen was repeated five times to replace the inside of the first reactor with nitrogen. After nitrogen substitution, the internal temperature of the first reactor was gradually raised through a heat medium having a temperature of 230 ° C. through the heat medium jacket to dissolve the mixture. Then, the stirrer was rotated at 300 rpm, the temperature in the heating medium jacket was controlled, and the internal temperature of the first reactor was kept at 220 ° C. The pressure in the first reactor was 101.3 kPa (760 Torr) in absolute pressure over 40 minutes while distilling off phenol produced as a by-product by the oligomerization reaction of BPC and DPC performed in the first reactor. To 13.3 kPa (100 Torr).

  Subsequently, a transesterification reaction was performed for 80 minutes while maintaining the pressure in the first reactor at 13.3 kPa and further distilling off the phenol. The inside of the system was restored to absolute pressure of 101.3 kPa with nitrogen, the gauge pressure was increased to 0.2 MPa, and the oligomer in the first reactor was passed through a transfer pipe heated to 200 ° C. or higher in advance. Two reactors were pumped. The second reactor had an internal volume of 200 L, was equipped with a stirrer, a heat medium jacket, a vacuum pump and a reflux condenser, and the internal pressure was controlled to atmospheric pressure and the internal temperature was controlled to 240 ° C.

Next, the oligomer fed into the second reactor was stirred at 38 rpm, the internal temperature was raised with a heating medium jacket, and the inside of the second reactor was absolute pressure from 101.3 kPa to 13.3 kPa over 40 minutes. The pressure was reduced to. Thereafter, the temperature increase was continued, and the internal pressure was reduced from 13.3 kPa to 399 Pa (3 Torr) as an absolute pressure over an additional 40 minutes, and phenol distilled out was removed out of the system. Further, the temperature was continuously raised, and after the absolute pressure in the second reactor reached 70 Pa (about 0.5 Torr), the pressure was maintained at 70 Pa, and a polycondensation reaction was performed. The final internal temperature in the second reactor was 279 ° C. The polycondensation reaction was completed when the stirrer of the second reactor reached a predetermined stirring power. The polymerization reaction time in the second reactor was 120 minutes.
Each evaluation was carried out on this polycarbonate resin according to the above-mentioned procedure. The results are shown in Table 1.

[Example 2]
As a dihydroxy compound, 181.8 kg of 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter sometimes abbreviated as “BPC”) (Honshu Chemical Co., Ltd.) and diphenyl carbonate (DPC) 157 The mixture was prepared by adding an aqueous solution of cesium carbonate to 0.7 kg so that cesium carbonate was 2.0 μmol per 1 mol of the dihydroxy compound. Next, the mixture was charged into a first reactor having an internal volume of 400 L equipped with a stirrer, a heat medium jacket, a vacuum pump, and a reflux condenser.

Next, the operation of depressurizing the inside of the first reactor to 1.33 kPa (10 Torr) and then restoring the pressure to the atmospheric pressure with nitrogen was repeated 10 times to replace the inside of the first reactor with nitrogen. After nitrogen substitution, the internal temperature of the first reactor was gradually raised through a heat medium having a temperature of 230 ° C. through the heat medium jacket to dissolve the mixture. This molten mixture was then transferred to the second reactor. The second reactor had an internal capacity of 400 L and was equipped with a stirrer, a heat medium jacket, a vacuum pump, and a reflux condenser.

  The stirrer was rotated at 60 rpm, the temperature in the heating medium jacket was controlled, and the internal temperature of the second reactor was kept at 220 ° C. The pressure in the first reactor is 101.3 kPa (760 Torr) to 13.3 kPa in terms of absolute pressure while distilling off phenol by-produced by the oligomerization reaction of BPC and DPC performed in the second reactor. The pressure was reduced to (100 Torr).

Next, the second reactor was stirred at 30 rpm, the internal temperature was raised with a heat medium jacket, and the pressure inside the second reactor was reduced from 101.3 kPa to 13.3 kPa in absolute pressure. Thereafter, the temperature was continuously raised, and the internal pressure was reduced from 13.3 kPa to 399 Pa (3 Torr) in absolute pressure, and the distilled phenol was removed from the system. Further, the temperature was continuously raised, and after the absolute pressure in the second reactor reached 70 Pa (about 0.5 Torr), the pressure was maintained at 70 Pa, and a polycondensation reaction was performed. At that time, the rotation speed of stirring was 10 rpm according to the stirring power, and the final internal temperature in the second reactor was 275 ° C. The polycondensation reaction was completed when the stirrer of the second reactor reached a predetermined stirring power. The polymerization reaction time in the second reactor was 310 minutes.
Each evaluation was carried out on this polycarbonate resin according to the above-mentioned procedure. The results are shown in Table 1.

[Comparative Example 6]
It implemented like Example 2 except having changed the predetermined stirring power value at the time of completion | finish of the stirrer of a 2nd reactor. The polymerization reaction time in the second reactor was 342.

[Comparative Example 7]
Cesium carbonate was added to 0.5 μmol per 1 mol of the dihydroxy compound, the temperature at the end of the stirrer of the second reactor was set to 285 ° C., and the predetermined stirring power value at the end of the stirrer of the second reactor was changed. Except for this, the same procedure as in Example 1 was performed. The polymerization reaction time in the second reactor was 235 minutes.
Each evaluation was carried out on this polycarbonate resin according to the above-mentioned procedure. The results are shown in Table 1.

[Comparative Example 8]
Cesium carbonate was added to 4.0 μmol per 1 mol of the dihydroxy compound, the temperature at the end of the stirrer of the second reactor was changed to 285 ° C., and the predetermined stirring power value at the end of the stirrer of the second reactor was changed. Except for this, the same procedure as in Example 2 was performed. The polymerization reaction time in the second reactor was 354 minutes.
Each evaluation was carried out on this polycarbonate resin according to the above-mentioned procedure. The results are shown in Table 1.

[Comparative Example 1]
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 water phase and the organic phase of 61.9 kg / h of methylene chloride cooled to 5 ° C. are supplied to a Teflon (registered trademark) pipe having an inner diameter of 6 mm and an outer diameter of 8 mm, respectively. In a 34 m Teflon (registered trademark) 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 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. Then, 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 above methylene chloride solution of oligomer, 23 kg was charged into a reaction vessel equipped with a 70 liter Faudler vane, and 10 kg of methylene chloride for dilution was added thereto. Further, 2.2 kg of 25 wt% 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 it into 40 ° C. warm water, and after drying, a granular powder of polycarbonate resin was obtained.

[Comparative Example 2]
It carried out like the comparative example 1 except having used 0.204 kg / hour of pt-butylphenol as a molecular weight regulator.
Each evaluation was carried out on this polycarbonate resin according to the above-mentioned procedure. The results are shown in Table 1.

[Example 3]
In the Nippon Steel Works twin screw extruder (LABOTEX30HSS-32) having one vent port, the powdered polycarbonate resin obtained in Comparative Example 2 was set at an inlet barrel set temperature of 100 ° C, an outlet barrel set temperature of 330 ° C, The mixture was melt-kneaded at a resin outlet temperature of 367 ° C. and a residence time of 4 minutes, extruded into a strand form from the outlet of a twin-screw extruder, cooled and solidified with water, and then pelletized with a rotary cutter to obtain polycarbonate resin pellets. During melt-kneading, the vent port of the twin screw extruder was connected to a vacuum pump, and the pressure at the vent port was controlled to 500 Pa.
Each evaluation was carried out on this polycarbonate resin according to the above-mentioned procedure. The results are shown in Table 1.

[Comparative Example 3]
The same procedure as in Example 1 was carried out except that cesium carbonate was added at 10.0 μmol per 1 mol of dihydroxy compound, the temperature at the end of the stirrer of the second reactor was 270 ° C., and the predetermined stirring power value was changed. did. The polymerization reaction time in the second reactor was 205 minutes.
Each evaluation was carried out on this polycarbonate resin according to the above-mentioned procedure. The results are shown in Table 1.

[Comparative Example 4]
The same procedure as in Example 1 was carried out except that cesium carbonate was added to 2.0 μmol per 1 mol of the dihydroxy compound, the temperature at the end of the stirrer of the second reactor was 306 ° C., and the predetermined stirring power value was changed. did. The polymerization reaction time in the second reactor was 202 minutes. Each evaluation was carried out on this polycarbonate resin according to the above-mentioned procedure. The results are shown in Table 1. This polycarbonate resin contained methylene chloride insolubles.

[Comparative Example 5]
In the Nippon Steel Works twin screw extruder (LABOTEX30HSS-32) having one vent port, the powdered polycarbonate resin obtained in Comparative Example 1 was set at an inlet barrel set temperature of 100 ° C, an outlet barrel set temperature of 340 ° C, The mixture was melt-kneaded at a resin outlet temperature of 375 ° C. and a residence time of 10 minutes, extruded into a strand form from the outlet of a twin-screw extruder, cooled and solidified with water, and then pelletized with a rotary cutter to obtain polycarbonate resin pellets. During melt-kneading, the vent port of the twin screw extruder was connected to a vacuum pump, and the pressure at the vent port was controlled to 500 Pa.
Each evaluation was carried out on this polycarbonate resin according to the above-mentioned procedure. The results are shown in Table 1.

  According to the present invention, it is possible to obtain a polycarbonate resin composition and a molded product having excellent surface hardness, high flame retardancy, and few foreign substances by a simple method, and in the field of electric / electronic devices such as mobile phones and personal computers, It is possible to expand the field of use to applications that require surface hardness, such as the field of automobiles such as headlamp lenses and vehicle windows, and the field of building materials such as lighting and exterior.

Claims (8)

A polycarbonate resin having a repeating unit derived from the compound represented by the following formula (1), wherein the content of the structural unit derived from the compound represented by the following formula (2) is 20 ppm or more and 1000 ppm or less, and A polycarbonate resin having a viscosity average molecular weight of 15,000 or more and 24,000 or less.

(In Formula (1), R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and X represents a single bond, A substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom;

(In Formula (2), R ¹ and R ² represent the same group as in Formula (1), and R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or Represents an unsubstituted aryl group.) A polycarbonate resin having a repeating unit derived from the compound represented by the following formula (1), wherein the content of the structural unit derived from the compound represented by the following formula (3) is 200 ppm to 3000 ppm, and A polycarbonate resin having a viscosity average molecular weight of 15,000 or more and 24,000 or less.

(In Formula (1), R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and X represents a single bond, A carbonyl group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom.)

(In Formula (3), R ¹ , R ² and X represent the same group as in Formula (1), and R ⁴ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted group. Represents a substituted aryl group.) A polycarbonate resin having a repeating unit derived from the compound represented by the following formula (1), wherein the content of the structural unit derived from the compound represented by the following formula (4) is 50 ppm or more and 600 ppm or less, and A polycarbonate resin having a viscosity average molecular weight of 15,000 or more and 24,000 or less.

(In Formula (1), R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and X represents a single bond, A substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a substituted or unsubstituted sulfur atom, or an oxygen atom;

(In formula (4), R ¹ and X have the same meanings as in formula (1). R ⁵ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted group. An aryl group of   A polycarbonate resin having a repeating unit derived from the compound represented by the formula (1), wherein the content of the structural unit derived from the compound represented by the formula (2) is 20 ppm or more and 1000 ppm or less. 2. The polycarbonate resin according to 2.   A polycarbonate resin having a repeating unit derived from the compound represented by the formula (1), wherein the content of the structural unit derived from the compound represented by the formula (4) is 50 ppm or more and 600 ppm or less. 2. The polycarbonate resin according to 2. Repeating unit 1 in which the total content of metals of Group 1 and Group 2 of the long-term periodic table in the polycarbonate resin is derived from all dihydroxy compounds constituting the polycarbonate resin
The polycarbonate resin according to any one of claims 1 to 5, wherein the amount is 5.0 x ^10-6 mol or less based on mol.   The production of a polycarbonate resin according to any one of claims 1 to 6, obtained by polymerizing a dihydroxy compound component containing a compound represented by the formula (1) and a carbonate-forming compound component. A method for producing a polycarbonate resin, wherein the carbonate-forming compound component is a carbonic acid diester.   The method for producing a polycarbonate resin according to claim 7, wherein the polymerization is performed in the presence of a compound containing at least one metal selected from the group consisting of metals of Group 1 and Group 2 of the long-period periodic table.