JP3498766B2 - Continuous production method of optical polycarbonate resin - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a continuous process for producing an optical polycarbonate resin containing a small amount of low molecular weight substances. Polycarbonate resin is used as a raw material for optical discs and compact discs for reading signals by reflecting or transmitting laser light. By using the optical polycarbonate resin having a small amount of low molecular weight product obtained in the present invention, it is possible to reduce the stain of the stamper generated at the time of disk molding and suppress the occurrence of white spots in the molded product under a high humidity and high temperature environment. Therefore, it is particularly useful as a raw material for optical discs and compact discs.

[0002]

2. Description of the Related Art Generally, a polycarbonate resin is used as a substrate material for optical information disks, a molding material for optical parts such as lenses and fibers by taking advantage of its characteristics such as transparency, heat resistance and dimensional stability. Particularly, as the optical information recording material, high-purity polycarbonate is required from the viewpoints of durability of the recording film, durability of the polycarbonate substrate itself, and prevention of stamper contamination during substrate production. The inventors of the present invention have little dirt on the stamper when molding the disc,
As a result of diligent study to obtain a polycarbonate resin that has few white spots in the substrate when exposed to high temperature and high humidity of the molded product, as a result of stains on the stamper and white spots under high temperature and high humidity, interface weight The low molecular weight material remains in the legal polycarbonate resin, and the volatiles of this low molecular weight material cause stains on the stamper during the molding of the optical disc substrate, resulting in remarkable productivity for maintenance. However, there is a problem that the pits are dropped or the transferability of pits is lowered. Furthermore, this low molecular weight compound is a raw material monomer:
There are oligomers produced by the reaction of the end-capping agent at a ratio of 1: 1; monomer oligomers produced by the reaction at a ratio of 1: 2; and dimers of the end-capping agent.
It has been found that the most problematic one among them is the monomer oligomer having a high content in the polymer.

Here, the interfacial polymerization method for obtaining a polycarbonate resin is a mixture of a methylene chloride solution of a polycarbonate oligomer obtained by phosgenation of an aqueous caustic alkali solution of a dihydric phenol, a caustic alkali and a terminal terminator (molecular weight modifier). The polymerization reaction is promoted by adding a catalyst to the solution. In such an interfacial polymerization method, unreacted dihydric phenol or a chloroformate of dihydric phenol remains in the aqueous phase after the phosgene reaction, and as described above, during the polymerization reaction, It is considered that the unreacted dihydric phenol and the like react with the terminal terminator to form a monomer oligomer. Therefore, it is difficult to avoid formation of a monomer oligomer in the conventional interfacial polymerization method, and it has been known that the content of the monomer oligomer is usually 1% by weight or more in the polymer.

Japanese Patent Publication No. 6-23243 discloses a method for reducing low molecular weight substances produced during the polymerization reaction.
It describes a method of regulating the timing of charging raw materials and the caustic concentration during the polymerization reaction. However, with this method, the reduction rate of low molecular weight substances is not yet sufficient. Further, in JP-A-6-336522, when a molecular weight of a polycarbonate oligomer or a content of a bishaloformate compound of an aromatic dihydroxy compound reaches a desired value, by adding a molecular weight regulator, There is a description of how to reduce the content of low molecular weight oligomers. However, it is difficult to constantly monitor the molecular weight of the polycarbonate oligomer and the content of the bishaloformate compound of the aromatic dihydroxy compound. Further, in JP-A-3-109420, a tubular reactor is used at the time of phosgenation reaction, and a molecular weight regulator is added in the tubular reactor or at the outlet of the tubular reactor. Methods for reducing the production of oligomeric oligomers are described. However, even with this method, the reduction rate of the above-mentioned monomer oligomer is not sufficient.

Further, as a method similar to the method of the present invention, JP-A-50-22089 and JP-A-6-100.
Japanese Patent No. 685, etc. describes a method of using a tubular reactor at the time of polymerization reaction, but no description of low molecular weight substances is found.

On the other hand, as a method for removing low molecular weight substances from the produced polymer, JP-A-63-278929, JP-A-64-6020 and JP-A-4-3062 are known.
No. 27, etc. describe a method of extracting a low molecular weight substance from a polycarbonate powder with acetone. However, in this method, the apparatus becomes large in size to extract the low molecular weight substance from the polycarbonate powder once produced by granulation, and the process of removing the low molecular weight substance from the used acetone is complicated, which leads to an increase in cost. In addition, due to the difference in the specific surface area of the powder, the extraction ratio of the low molecular weight substance when performing acetone extraction is different, there is a drawback that the average molecular weight of the obtained powder will vary, and a sufficient method I can not say.

[0007]

Therefore, in the above-mentioned interfacial polymerization method, a new method of suppressing the formation of low molecular weight substances during the polymerization reaction is not a method of removing the low molecular weight substances in the produced polymer. Development was needed.

[0008]

As a result of intensive studies, the present inventors have found a method for suppressing the formation of low molecular weight compounds during the polymerization reaction in the above-mentioned interfacial polymerization method. That is, the present invention provides a reaction solution of a polycarbonate oligomer by reacting with phosgene in a mixed solution of a caustic aqueous solution of a dihydric phenol and an organic solvent while maintaining the mixed solution in an oil-in-water suspension type suspension state. And pressurizing the reaction solution to pass through the orifice holes at a speed of 100 to 2500 cm / s to invert the phase into a water-in-oil dispersion type emulsion, and then add a polymerization catalyst to the emulsion. And agitation is performed to complete the polymerization reaction. Furthermore, in a preferred embodiment, after the phase is changed to the above emulsion, the emulsion is further added at least once 10 times before the addition of the polymerization catalyst.
It is the above method of passing through the orifice hole at a speed of 0 to 2500 cm / s. In addition, the emulsion after passing through the orifice holes is
It is the above method of aging for ~ 600 seconds. Furthermore, it is the above-mentioned method in which the terminal stopper is added to the emulsion prior to the addition of the polymerization catalyst.

The present inventors presume that the method of the present invention can improve the polymerization reaction rate, so that the catalyst can be reduced and, in turn, the production of low molecular weight compounds due to side reactions can be suppressed. According to the present invention, the obtained polycarbonate resin has a content of the monomer oligomer reduced to 0.2% by weight or less, and thus is useful as an optical material requiring high quality. It was also found that the residual amount of terminal chloroformate groups in the polymer, which affects the heat resistance, is also reduced.

The present invention will be described in detail below.
The polycarbonate resin referred to in the present invention is obtained by reacting phosgene with an interfacial polymerization method, containing a dihydric phenol compound as a main component. Aromatic homo- or copolycarbonate resins using bisphenols, further branched ones, ones having a long-chain alkyl group introduced at the end, etc. have a viscosity average molecular weight of 13
Those in the range of 000 to 100,000 are applicable.
Further, as a terminal terminating agent or comonomer, a polycarbonate resin having a double bond produced by reacting a compound having a carbon-carbon double bond is produced, and a polycarbonate resin obtained by graft reaction of styrene or the like, or a phenol to polystyrene or the like. Any of a hydroxyl group and a polycarbonate resin obtained by graft-polymerizing other reactive monomers can be applied. Among these, examples of the aromatic polycarbonate resin include a polycarbonate containing bisphenol A as a main raw material, and examples thereof include bisphenol Z and tetrabromobisphenol A (TB
A polycarbonate copolymer obtained by using A) or the like in combination, a branched product thereof, or a product modified with a long-chain alkyl at the end is preferable.

Preferred bisphenol compounds used in the method for producing the polycarbonate resin of the present invention are specifically bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether and bis (4-hydroxyphenyl). ) Sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl)
Ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane 2 (TBA), 2-bis (4- Hydroxyphenyl)
Butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ), 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-) 3,5-Dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-
Hydroxy-3-chlorophenyl) propane, 2,2-
Bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, α, ω-bis [3- (O
Examples include -hydroxyphenyl) propyl] polydimethylsiloxane (PDS) and biphenol. You may use these in combination of 2 or more types. Among them, those selected from bisphenol A, bisphenol Z, TBA and PDS are preferable.

Examples of the terminal terminator (or molecular weight regulator) used in the present invention include compounds having a monovalent phenolic hydroxyl group, which are ordinary phenol and pt-
In addition to butylphenol, tribromophenol, etc., long-chain alkylphenol, aliphatic carboxylic acid chloride, aliphatic carboxylic acid, aromatic carboxylic acid, aromatic acid chloride, hydroxybenzoic acid alkyl ester, alkyl ether phenol and the like can be mentioned. Further, it may be used as a terminal terminating agent having a reactive double bond, and examples thereof include acrylic acid, vinyl acetic acid, 2-pentenoic acid, 3-pentenoic acid, 5-hexenoic acid, 9-undecenoic acid and the like. Unsaturated carboxylic acids; acrylic acid chlorides, sorbic acid chlorides, allyl alcohol chloroformates, acid chlorides or chloroformates such as isopropenylphenol chloroformate or hydroxystyrene chloroformate; isopropenylphenol,
Hydroxystyrene, hydroxyphenylmaleimide,
Examples thereof include phenols having an unsaturated group such as hydroxybenzoic acid allyl ester and hydroxybenzoic acid methylallyl ester. Of these, phenol and pt-butylphenol are preferable.

The amount of the terminator used is 2 as described above.
Usually, 1 to 25 relative to 1 mol of the phenolic compound.
It is used in the range of mol%, preferably 1.5 to 10 mol%. In addition, the end-capping agent can be added in the state of an organic solvent solution or an aqueous solution of caustic alkali, but if left in the state of an alkaline aqueous solution, it will turn red and affect the hue of the molded article of polycarbonate. It is preferable to add it as a solution, and usually it is added as a 10 to 30% by weight solution.

In the present invention, the organic solvent used is dichloromethane, 1,2-dichloroethane, 1,
1,2,2-tetrachloroethane, chloroform, 1,
Chlorinated hydrocarbons such as 1,1-trichloroethane, carbon tetrachloride, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; and ether compounds such as diethyl ether. These organic solvents may be used as a mixture of two or more kinds. In addition, if desired, solvents other than the above, such as ethers, ketones, esters, and nitriles, which have an affinity for water may be used within the limit that the mixed solvent system is not completely compatible with water.

Further, the branching agent is used in an amount of 0.01 to 3.0 mol%, particularly 0.1%, based on the above dihydric phenol compound.
It can be used as a branched polycarbonate in combination within a range of from 1.0 to 1.0 mol%. As a branching agent, phloroglucin, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,4,6-dimethyl-
2,4,6-tri (4-hydroxyphenyl) heptene-2,1,3,5-tri (2-hydroxyphenyl) benzole, 1,1,1-tri (4-hydroxyphenyl) ethane, 2,6 -Bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, α, α ^' , α ^"
-Polyhydroxy compounds exemplified by tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene and 3,3-bis (4-hydroxyphenyl)
Oxindole (= Isatin bisphenol), 5-
Examples include chloroisatin bisphenol, 5,7-dichloroisatin bisphenol, and 5-bromoisatin bisphenol.

In the present invention, a mixed solution of a caustic aqueous solution of a dihydric phenol and an organic solvent is made into an oil-in-water dispersion type suspension state by stirring means such as a stirring tank equipped with a stirrer, a tubular reactor and a static mixer. The polycarbonate oligomer is formed by reacting with phosgene while maintaining the temperature. The molar ratio of dihydric phenol and phosgene is usually in the range of 1: 1.02 to 1.35. Forming a water-in-oil dispersion type emulsion during the phosgenation reaction is not preferable because the decomposition rate of phosgene increases and the side reaction is promoted. As a means for forming an oil-in-water dispersion type suspension, a method in which stirring is continued from the beginning of phosgene introduction to the end of the phosgenation reaction is generally used. The viscosity-average molecular weight of the polycarbonate oligomer thus obtained is in the range of 2000-4500. In the caustic aqueous solution of the reaction solution at the end of the phosgenation reaction, unreacted dihydric phenol is 0.2 to 2.
0 w / v% remains.

When the phosgenation reaction is completed, additional caustic alkali and an organic solvent are added to the reaction solution containing the polycarbonate oligomer, if necessary. At this time, if the reaction liquid is phase-inverted to the water-in-oil dispersion type emulsion, poor dispersion of the additional raw material occurs, which is not preferable.When adding these additional raw materials, continue stirring or the like. It is particularly preferable that the reaction solution is kept as an oil-in-water dispersion type suspension.

In the present invention, the terminal stopper may be added immediately after the completion of the phosgenation reaction, but it is preferable to add the required amount of the terminal stopper to the water-in-oil dispersion type emulsion prior to the addition of the polymerization catalyst described below. It is particularly preferable because the reduction rate of the oligomer oligomer is high.

The reaction solution thus obtained is introduced into the orifice hole by using a pressurizing device such as a pump, and the orifice hole is passed at a flow rate of 100 to 2500 cm / s. At this time, the reaction solution of the oil-in-water dispersion is subjected to a strong stirring force to be phase-inverted into a water-in-oil dispersion emulsion.
The hole diameter of the orifice is adjusted according to the production amount (total reaction liquid amount) so that the flow rate of the reaction liquid is 100 to 2500 cm / s. If the flow rate is less than 100 cm / s, a sufficient emulsion cannot be obtained, and phase inversion to the water-in-oil dispersion type may not occur, which is not preferable. On the other hand, when it exceeds 2500 cm / s, the aqueous phase particles in the emulsion become too fine and the side reaction is promoted, the amount of the low molecular weight product is increased, and the separation work after polymerization becomes difficult. In addition, the power for passing through the orifice becomes too large, which is not preferable. A more preferable range is 200 to 1500 cm / s.

The emulsified liquid generated is retained at the outlet side of the orifice hole, and this emulsified liquid acts as a seed emulsified liquid and is mixed with the oil-in-water type dispersion liquid which successively flows in, thereby continuously Therefore, phase inversion into a water-in-oil dispersion type emulsion is possible. Since there is no emulsified liquid on the outlet side of the orifice hole at the start of operation, it is preferable to fill the area after the outlet of the orifice hole with an organic solvent to facilitate phase inversion.

The emulsion produced by the phase inversion into the water-in-oil dispersion type emulsion has a significantly large contact area between the water phase and the organic phase and has an increased polymerization rate. Can be reduced. In the present invention, prior to addition of the polymerization catalyst, the emulsion liquid is further added at 100 to 2500 cm / s.
It is preferable to pass through the orifice hole at least once at a speed of. As a result, the contact area between the water phase and the organic phase is further increased, and efficient polymerization reaction is performed. The passage through the orifice hole is usually selected in the range of 2 to 20 times, but particularly preferably in the range of 2 to 10 times.

In the present invention, further, prior to the addition of the polymerization catalyst, it is preferable that the emulsion is aged for 1 to 600 seconds for the purpose of increasing the molecular weight of the emulsion after passing through the orifice. As the aging method, the emulsion liquid is allowed to stand still, or it is allowed to pass through a pipe to increase the residence time. Since the effect does not improve even if the aging time is too long, it is particularly preferable to carry out the aging in the range of 1 to 300 seconds.

As a method for confirming the formation of the oil-in-water dispersion type suspension and the water-in-oil dispersion type emulsion, a capacitance type or conductivity type monitor is used.

In the present invention, the polymerization catalyst is added to the emulsion obtained by the above method and stirred to complete the polymerization reaction. It is a preferred method to improve the polymerization reaction rate by adding a polymerization catalyst. As the polymerization catalyst, a commonly used catalyst such as tertiary amine or quaternary ammonium salt can be used. The catalyst is preferably added after being dissolved in an organic solvent or water, and the concentration of the solution is 0.2 to 15 v / v for the purpose of improving the dispersibility of the catalyst and sharpening the molecular weight distribution of the polymer.
It is prepared and used in the range of v%. If the concentration is lower than this range, the composition of the emulsion changes significantly, and the amount of low-molecular weight products increases, which is not preferable. On the other hand, if the concentration is higher than this range, poor dispersion in the reaction solution may occur, which is not preferable. After the addition of the catalyst, stirring is continued for 10 to 120 minutes to complete the polymerization reaction and obtain a polymerized resin liquid.

As a stirring method, it is possible to use a simple stirring blade (paddle, propeller, turbine, chi-type blade, etc.) to increase the rotation speed to complete the polymerization reaction. As the apparatus for obtaining, there are a homogenizer, a high-speed stirrer such as a homomixer, a colloid mill, an orifice mixer, a flow jet mixer, and an ultrasonic emulsifier.When these are used, the polymerization rate can be improved. it can.

As a method of confirming that the molecular weight of the polymer at the completion of the polymerization reaction is within the target range, the fact that the viscosity average molecular weight and the viscosity of the emulsion have a positive correlation is used to prepare each composition. A method is preferred in which the viscosity average molecular weight of the polycarbonate is known by grasping this relationship in advance and continuously measuring the viscosity of the emulsion.

The solvent solution is separated from the polycarbonate resin solution, the catalyst is removed, neutralized, washed with water, concentrated, and the like, and further subjected to centrifugation or microfiltration to obtain a purified polycarbonate resin solution. As a method for obtaining a solid substance from the polycarbonate resin solution, a known method can be used. For example, a method in which an organic solvent solution of polycarbonate is added and mixed with a poor solvent if necessary, and then dropped into warm water under stirring, an organic solvent solution of polycarbonate is put into a kneader with a heating jacket, and granulation and drying are performed. The method etc. are used.

[0028]

The present invention will be described in more detail with reference to the following examples, but the invention is not limited thereto as long as the scope of the present invention is not exceeded.

(1) Content of monomer / oligomer in polymer: 100 mg of pellets were dissolved in 20 ml of chloroform, and GPC (Column: Shodex) manufactured by Waters.
K803L x 2 pieces, Detector: 490UV detector, 254
nm, AUFS1.0), sample amount 100μ
1, the solvent flow rate was 1.0 ml / min, and the content (wt%) of the monomer / oligomer in the polymer was determined from the peak area around the retention time of 19.25 minutes.

(2) Hue evaluation method: Polymer is held using an injection molding machine, resin temperature is 320 ° C., mold temperature is 80 ° C., and is maintained by an injection molding machine (Neomat 350/120 manufactured by Sumitomo Heavy Industries, Ltd.) 50 mm x 60 m at a pressure of 1000 kg / cm ^2.
Five molded pieces with a thickness of 3 mm and a thickness of 3 mm are continuously molded, and the molded pieces are color-measured with a color difference meter manufactured by Nippon Denshoku Co., Ltd., and the YI value (a yellowish index; the smaller the number, the better) I asked.

(3) Chlorine concentration derived from terminal chloroformate group: The polymer was dissolved in a dichloromethane solvent at a concentration of 0.05 to 5 g / L according to the remaining amount of the chloroformate group, and 4- (nitrobenzyl ) Pyridine 0.8 g / L
Is added so that the concentration becomes, and color is developed. The absorbance of the obtained colored solution at 440 nm was measured to be 0.2 to 20.
Using a factor obtained from the absorbance of a mol / L phenyl chloroformate standard solution, the concentration was converted into the chloroformate concentration, and further converted into the chlorine concentration.

Example 1 In a stirring tank having an internal volume of 50 L, in which an agitator type agitator (manufactured by Shimazaki Seisakusho Co., Ltd., triangular type two blades, reversal number 135 cpm) was installed, 63 kg / h of bisphenol A and 8.0 w / w% water. An aqueous solution of sodium oxide (340 L / h) and hydrosulfite (HD) (270 g / h) were continuously fed, and the overflowing mixed liquid and methylene chloride 140 L / h.
Is continuously supplied to a phosgenation tank having an internal volume of 50 L in which an agitator-type stirrer is installed, and phosgene of 31 kg /
Phosgenation was carried out by feeding at h. During the phosgenation, the reaction solution maintained an oil-in-water dispersion type suspension.
In the reaction solution overflowing from the phosgenation tank, as a terminal stopper, a methylene chloride solution of pt-butylphenol (13.3 w / w%) 17.3 kg / h, methylene chloride 75 L / h, 8.8 w / A w% aqueous solution of sodium hydroxide (50 L / h) was added, and the mixture was stirred in a stirring tank (internal volume: 50 L) equipped with a propeller blade stirrer while maintaining the oil-in-water dispersion suspension.

Using a plunger pump, the reaction solution thus obtained was passed at a rate of 640 L / h through an orifice having a hole diameter of 5 mm at a rate of 905 cm / s to give an internal volume of 10 L. It was blown into an emulsion container and aged for a residence time of 56 seconds. In the container, the reaction solution was in a water-in-oil dispersion type emulsified state, and the emulsion overflowing from the container was equipped with an agitator-type stirrer.
L to a stirring tank, and a solution of triethylamine in methylene chloride (10 v / v) was used as a polymerization catalyst.
%) Was added to complete the polymerization reaction.
The polymerized resin liquid was separated into two phases, an alkaline aqueous phase and an organic phase in which the polycarbonate resin was dissolved. Remove the upper liquid,
The methylene chloride phase was neutralized with phosphoric acid and then washed with pure water to obtain a purified resin solution of polycarbonate. The obtained purified resin solution was placed in an evaporation dish and dried at 140 ° C. for 4 hours to obtain a dry solid. As a result of GPC measurement of the solid matter, the viscosity average molecular weight was 15,800, the content of the monomer oligomer in the polymer was 0.15 wt%, the chlorine concentration derived from the terminal chloroformate group was 0.055 ppm, the hue of the continuous plate The YI value was 0.95.

Example 2 In Example 1, the reaction solution of oil-in-water dispersion type was pumped using a plunger pump at a feed rate of 620 L / h to 3 mm.
Through an orifice with a hole diameter of 2440 cm / s
Polymerization reaction / purification / solidification / drying work was carried out in the same manner as in Example 1 except that the mixture was passed through at a rate of 10 L and was blown into an emulsion container having an internal volume of 10 L and aged for a residence time of 58 seconds.
A dry polycarbonate was obtained. The viscosity average molecular weight of the polymer is 15900, the content of the monomer oligomer in the polymer is 0.14 wt%, the chlorine concentration derived from the terminal chloroformate group is 0.050 ppm, and the hue YI value of the continuous plate is 0.93. Met.

Example 3 In Example 1, the reaction solution of oil-in-water dispersion type was pumped using a plunger pump at a liquid feed rate of 185 L / h to 8 mm.
Polymerization reaction was performed in the same manner as in Example 1 except that the mixture was passed through an orifice having a hole diameter of 102 cm / s at a speed of 102 cm / s, blown into an emulsion container having an internal volume of 10 L and aged for a residence time of 194 seconds.・ Refining, solidifying, and drying work
A dry polycarbonate was obtained. The viscosity average molecular weight of the polymer is 15500, the content of the monomer oligomer in the polymer is 0.17 wt%, the chlorine concentration derived from the terminal chloroformate group is 0.062 ppm, and the hue YI value of the continuous plate is 0.97. Met.

Comparative Example 1 In Example 1, the reaction solution of oil-in-water dispersion type was pumped using a plunger pump at a feed rate of 300 L / h for 12 m.
Polymerization reaction in the same manner as in Example 1 except that the mixture was passed through an orifice having a hole diameter of m at a speed of 74 cm / s, blown into an emulsification container having an internal volume of 10 L and aged for a residence time of 120 seconds. As a result, a water-in-oil dispersion type emulsion was not obtained, and the oil-in-water dispersion type suspension was maintained. Subsequently, the same purification, solidification, and drying operations as in Example 1 were carried out to obtain a dry polycarbonate. The viscosity average molecular weight of the polymer was 8500, the content of the monomer oligomer in the polymer was 5.22 wt%, the chlorine concentration derived from the terminal chloroformate group was 20.5 ppm, and the hue YI value of the continuous plate was 4.3. Met.

COMPARATIVE EXAMPLE 2 In Example 1, the reaction solution of oil-in-water dispersion type was pumped using a plunger pump at a liquid feed rate of 400 L / h to 2 mm.
Through an orifice with a hole diameter of 3536 cm / s
Polymerization, purification, solidification, and drying were carried out in the same manner as in Example 1 except that the mixture was passed through the emulsion container at an internal volume of 10 L and blown into an emulsion container having an internal volume of 10 L and aged for a residence time of 90 seconds. Obtained. The viscosity average molecular weight of the polymer is 15300, the content of the monomer oligomer in the polymer is 2.15 wt%, the chlorine concentration derived from the terminal chloroformate group is 0.30 ppm, and the hue YI value of the continuous plate is 1.42. Met.

Example 4 In Example 1, the emulsified liquid overflowing from the emulsified liquid container was used as a pipe (diameter 5 cm × length 130 cm) having an orifice plate with a hole diameter of 4 mm installed at the inlet (retention time 14.3).
Example 1 except that the emulsion was aged by press-fitting it through a plunger pump into an emulsion aging apparatus in which 4 seconds) were connected in series to each other (the linear velocity at each orifice was 1412 cm / s). Repeat as above. As a result of GPC measurement of the obtained solid, the viscosity average molecular weight was 15,300, and the content of the monomer oligomer in the polymer was 0.1.
1 wt%, chlorine concentration derived from terminal chloroformate group is 0.041 ppm, hue YI value of continuous plate is 0.8
It was 8.

Example 5 In Example 1, the emulsified liquid overflowing from the emulsified liquid container was filled with an orifice plate having a hole diameter of 4 mm at the inlet of the introduction pipe and a tank having an internal volume of 100 L (residence time: 563).
Sec) was press-fitted via a plunger pump, overflowed, and then, in the same manner as in Example 1, except for aging with an emulsion aging device in which the same introducing pipe and tank were connected in series in 10 stages. And repeated. As a result of GPC measurement of the obtained solid, the viscosity average molecular weight was 15100, and the content of the monomer oligomer in the polymer was 0.1.
2 wt%, chlorine concentration derived from terminal chloroformate group is 0.038 ppm, hue YI value of continuous plate is 0.9
It was 5.

Example 6 An agitator-type stirrer (manufactured by Shimazaki Seisakusho Co., Ltd., triangular two-blade, reversal number 135 cpm) was installed in a stirring tank having an internal volume of 50 L, and 63 kg / h of bisphenol A and 8.0 w / w% of water. An aqueous solution of sodium oxide (340 L / h) and hydrosulfite (HD) (270 g / h) were continuously fed, and the overflowing mixed liquid and methylene chloride 140 L / h.
Is continuously supplied to a phosgenation tank having an internal volume of 50 L in which an agitator-type stirrer is installed, and phosgene of 31 kg /
Phosgenation was carried out by feeding at h. During the phosgenation reaction, the reaction solution was kept in an oil-in-water dispersion type suspension state. To the reaction solution overflowing from the phosgenation tank, 75 L / h of methylene chloride and 50 L / h of 8.8 w / w% sodium hydroxide aqueous solution were added, and the stirring tank was installed with a propeller blade stirrer (internal volume 50 L). Then, stirring was performed while maintaining the oil-in-water dispersion type suspension.

The obtained reaction solution was passed with a plunger pump at a liquid feed rate of 640 L / h through an orifice having a hole diameter of 5 mm at a speed of 905 cm / s to give an internal volume of 10 L. It was blown into an emulsion container and aged for a residence time of 56 seconds. In the container, the reaction solution exhibits a water-in-oil dispersion type emulsified state, and the emulsion liquid overflowing from the emulsion liquid container is provided with an orifice plate having a hole diameter of 4 mm at the inlet of each pipe, A pipe having a diameter of 5 mm and a length of 130 cm (residence time: 14.3 seconds) was press-fitted into a device in which 25 stages were connected in series via a plunger pump. To the outlet of the 5th stage of this device, a methylene chloride solution of pt-butylphenol (13.3 w) was used as a terminal stopper.
/ W%) at a feed rate of 17.3 kg / h, and a methylene chloride solution of triethylamine (10 v / v%) as a polymerization catalyst at the outlet of the 10th stage.
0.5 L / h was added to complete the polymerization reaction. The polymerized resin liquid overflowing from the apparatus was separated into two phases, an alkaline aqueous phase and an organic phase in which the polycarbonate resin was dissolved. The upper liquid was removed, the methylene chloride phase was neutralized with phosphoric acid, and then washed with pure water to obtain a purified resin liquid of polycarbonate. The obtained purified resin solution was placed in an evaporation dish and dried at 140 ° C. for 4 hours to obtain a dry solid. Solid GPC
As a result of the measurement, the viscosity average molecular weight was 15600, the content of the monomer oligomer in the polymer was 0.10 wt%,
Chlorine concentration derived from terminal chloroformate group is 0.034p
The hue YI value of the pm, continuous plate was 0.80.

[0042]

According to the production method of the present invention, it is possible to suppress the formation of a monomer oligomer during a polymerization reaction, which was difficult in the conventional production method of a polycarbonate resin by an interfacial polymerization method. In addition, heat resistance is adversely affected,
Since the residual amount of the terminal chloroformate group in the polymer can also be reduced, it is especially useful as a raw material for optical discs and compact discs that require high quality under high temperature and high humidity environment.
It is possible to provide a continuous production method of a useful optical polycarbonate resin.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-100686 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 64/00-64/42

Claims (4)

(57) [Claims] 1. A reaction solution of a polycarbonate oligomer by reacting with a phosgene in a mixed solution of a caustic aqueous solution of a dihydric phenol and an organic solvent while maintaining the mixed solution in an oil-in-water suspension state. Then, the reaction solution was pressurized, passed through an orifice hole at a speed of 100 to 2500 cm / s, phase-inverted into a water-in-oil dispersion type emulsion, and then a polymerization catalyst was added to the emulsion and stirred. A continuous process for producing an optical polycarbonate resin, which comprises completing a polymerization reaction. 2. After phase inversion to an emulsion, prior to addition of the polymerization catalyst, the emulsion is further added at least once 100 to 2 times.
The method according to claim 1, wherein the orifice hole is passed at a speed of 500 cm / s. 3. The method according to claim 1, wherein, prior to the addition of the polymerization catalyst, the emulsion after passing through the orifice hole is aged for 1 to 600 seconds each time. The 4. A terminal capping agent, prior to the addition of a polymerization catalyst, the method according to any one of claims 1 to 3 added to the emulsion.