KR20140009421A - Polycarbonate-resin manufacturing method - Google Patents

Abstract

12000 ≤ W/S ≤ 60000 … (2)A polycarbonate resin is obtained by a polycondensation reaction using at least a dihydroxy compound represented by the following general formula (1) as a raw material monomer, the resulting polycarbonate resin is fed to an extruder, kneaded, and then discharged from a die to be polycarbonate As a method of producing a resin, a polycarbonate that satisfies the following formula (2) when the weight of the resin extruded per hour by the extruder is W (kg / h) and the cross-sectional area of the barrel of the extruder is S (m 2). Method for producing a resin.

12000? W / S? (2)

Description

Production Method of Polycarbonate Resin {POLYCARBONATE-RESIN MANUFACTURING METHOD}

The present invention relates to a method for efficiently and stably producing a polycarbonate resin that is excellent in thermal stability, color and mechanical strength and is low in foreign matter.

Polycarbonate resins generally have bisphenols as monomer components, and take advantage of transparency, heat resistance, and mechanical strength, and are widely used as so-called engineering plastics in optical fields such as electrical and electronic parts, automotive parts, optical recording media, and lenses. It is used. However, in retardation film applications and lens applications such as flat panel displays, which are rapidly spreading in recent years, more advanced optical properties such as low birefringence and low photoelastic coefficient are required, and aromatic bisphenols having monomers as conventional monomers. Polycarbonate resin was unable to meet the demand.

Recently, polycarbonate resins having a dihydroxy compound having a fluorene structure as a monomer have been proposed, and a retardation film expressing a specific retardation (for example, Patent Documents 1 to 4), and a lens having a small birefringence (for example, a patent) It is proposed to apply to Documents 5 and 6). In applications where such high optical properties are required, high optical reliability is required compared to general injection molded parts and extrusion molded parts, and the optical properties, as well as the remaining volatiles, the coloring is suppressed, and the foreign materials are reduced. Is required. As a method of solving this, the method of filtering out the polycarbonate resin which has a fluorene structure by the extruder, and then filtering by a filter is disclosed (for example, patent document 7).

Japanese Patent Publication No. 3325560 Japanese Unexamined Patent Publication No. 2003-90914 Japanese Unexamined Patent Publication No. 2007-171756 Japanese Unexamined Patent Publication No. 2010-230832 Japanese Unexamined Patent Publication No. 2004-67990 Japanese Unexamined Patent Publication No. 2010-189508 Japanese Unexamined Patent Publication No. 2007-70392

However, when the polycarbonate resin having a fluorene structure is to be extruded by a conventional method, the melt viscosity is too high, the devolatilization efficiency is lowered, and there is a problem that the resin is deteriorated due to shear heat generation during extrusion. In Patent Literature 7, it is intended to increase the devolatilization efficiency by reducing the amount of polycarbonate resin to be treated per unit time with an extruder, but in such a method, not only the production efficiency is lowered, but also the residence time in the extruder is increased, There has been a dilemma that it is not possible to stably produce pellets or to form a film by encouraging the generation of coloring or foreign matters, or by causing cracking of the strands by gas or decomposition of the film due to decomposition gas.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to provide a method for efficiently and stably producing a polycarbonate resin that is excellent in optical properties, thermal stability, color and mechanical strength, and has few foreign substances.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, in the method of manufacturing the polycarbonate resin which has a fluorene structure, it is excellent in optical characteristic, mechanical strength, and color by extruding a polycarbonate resin on specific conditions. Then, the inventors discovered a method of efficiently and stably producing a polycarbonate resin containing few foreign matters.

That is, the summary of this invention exists in the following [1]-[32].

[One]

A polycarbonate resin is obtained by a polycondensation reaction using at least a dihydroxy compound represented by the following general formula (1) as a raw material monomer, the resulting polycarbonate resin is fed to an extruder, kneaded, and then discharged from a die to be polycarbonate As a method of producing a resin, a polycarbonate that satisfies the following formula (2) when the weight of the resin extruded per hour by the extruder is W (kg / h) and the cross-sectional area of the barrel of the extruder is S (m 2). Method for producing a resin.

[Formula 1]

(In General Formula (1), R ₁ to R ₄ each independently represent a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 cycloalkyl group, or a substituted or unsubstituted group. A C6-C20 aryl group is represented, X is a substituted or unsubstituted C2-C10 alkylene group, a substituted or unsubstituted C6-C20 cycloalkylene group, or a substituted or unsubstituted C6-C20 aryl group A rene group, m and n each independently represent an integer of 0 to 5)

12000? W / S? (2)

[2]

The glass transition temperature of the polycarbonate resin discharged | emitted from the said dice is 120 degreeC or more and 150 degrees C or less,

The manufacturing method of the polycarbonate resin as described in said [1] whose temperature at the time of supplying to the said extruder is 180 degreeC or more and 250 degrees C or less.

[3]

The barrel which comprises the said extruder is equipped with some heater, The manufacturing method of the polycarbonate resin as described in said [1] or [2] which makes at least one heater preset temperature of these heaters 100 degreeC or more and less than 250 degreeC.

[4]

The manufacturing method of the polycarbonate resin as described in said [3] which makes all the preset temperatures of the said some heater 100-100 degreeC or less.

[5]

The manufacturing method of the polycarbonate resin as described in said [3] or [4] which does not make each set temperature of the said some heater higher than the heater set temperature adjacent to the polycarbonate resin supply side of the said extruder.

[6]

The method for producing a polycarbonate resin according to any one of the above [1] to [5], wherein the reduced viscosity (η _sp / c) of the polycarbonate resin discharged from the die is 0.2 dl / g or more and 0.6 dl / g or less.

[7]

Of the polycarbonate resin obtained is discharged from the die, a shear rate of 91.2 sec measured at 240 ℃ ^- a melt viscosity of from ¹ 1000 ㎩ · s at least 5000 ㎩ · s or less according to any one of the above [1] to [6] Method for producing a polycarbonate resin.

[8]

The manufacturing method of the polycarbonate resin in any one of said [1]-[7] which uses 18 mol% or more of dihydroxy compounds represented by the said General formula (1) as said raw material monomers with respect to all the dihydroxy compounds.

[9]

The manufacturing method of polycarbonate resin in any one of said [1]-[8] whose temperature of polycarbonate resin discharged from the said dice | dies is 230 degreeC or more and less than 280 degreeC.

[10]

The screw of the extruder is composed of a plurality of elements, at least one of the elements is a kneading disk, and the total length of the kneading disk is 20% or less of the entire length of the screw, according to any one of the above [1] to [9]. The manufacturing method of polycarbonate resin described.

[11]

The manufacturing method of the polycarbonate resin in any one of said [1]-[10] which performs the operation of kneading a heat stabilizer using the said extruder.

[12]

After kneading with the said extruder, the manufacturing method of the polycarbonate resin in any one of said [1]-[11] which performs the operation of filtering using the filter whose mesh is 50 micrometers or less in a molten state.

[13]

The manufacturing method of the polycarbonate resin as described in said [12] whose linear velocity of molten resin in the said filter surface is 0.01-0.5 m / h.

[14]

The manufacturing method of the polycarbonate resin as described in said [12] or [13] which arrange | positions a gear pump between the said extruder and the said filter.

[15]

The said filter is stored in the container, The value divided by the flow volume (m <3> / min) of the said polycarbonate resin which filters the internal volume (m <3>) of the said storage container is 2 to 10 minutes, Any one of said [12]-[14]. The manufacturing method of polycarbonate resin of one.

[16]

The method for producing a polycarbonate resin according to any one of the above [12] to [15], wherein the filter contains a metal which has been subjected to a roasting treatment at a temperature of 350 ° C or higher and 500 ° C or lower in advance.

[17]

[12] to [16], wherein the filter is stored in a container, the polycarbonate resin before the filtration is supplied from the lower part of the storage container of the filter, and the polycarbonate resin after the filtration is discharged from the upper part of the storage container. The manufacturing method of the polycarbonate resin in any one of them.

[18]

The method for producing a polycarbonate resin according to any one of the above [12] to [17], wherein the polycarbonate resin is supplied to the filter after performing an operation for devolatilizing with a twin screw extruder having a vent port.

[19]

The reduced viscosity (η _sp / c) of the polycarbonate resin supplied to the extruder is a,

When the filter is filtered using the filter, discharged from the die, and the reduced viscosity (η _sp / c) of the polycarbonate resin obtained after cooling is set to B,

The manufacturing method of the polycarbonate resin in any one of said [12]-[18] which satisfy | fills following formula (3).

0.8 <B / a <1.1 ‥ (3)

[20]

Any of the above-mentioned [1] to [19] obtained by polycondensing the dihydroxy compound and diester carbonate represented by the said General formula (1) by the transesterification reaction in the presence of a catalyst for the polycarbonate resin supplied to the said extruder The manufacturing method of polycarbonate resin of one.

[21]

The polycarbonate resin production method according to the above [20], wherein the polycarbonate resin produced by polycondensation by the transesterification reaction is fed to the extruder and kneaded without being solidified.

[22]

The method for producing a polycarbonate resin according to the above [20] or [21], wherein the catalyst is at least one metal compound selected from the group consisting of a metal of a long-period type periodic table group 2 and lithium.

[23]

Any one of the above-mentioned [1] to [22] which uses a dihydroxy compound which has a site | part represented by following General formula (4) in a part of structure other than the dihydroxy compound represented by the said General formula (1) as a raw material monomer. The manufacturing method of the polycarbonate resin of Claim.

(2)

(Except the case where the site represented by the general formula (4) is part of -CH ₂ -OH)

[24]

The method for producing a polycarbonate resin according to the above [23], wherein the dihydroxy compound having a moiety represented by General Formula (4) is a compound having a cyclic ether structure.

[25]

The manufacturing method of the polycarbonate resin as described in said [24] whose dihydroxy compound which has a site | part represented by the said General formula (4) is isosorbide.

[26]

In addition to the dihydroxy compound represented by the said General formula (1) as a raw material monomer, the dihydroxy compound represented by the following General formula (5), the dihydroxy compound represented by the following General formula (6), and following General formula (7) The manufacturing method of the polycarbonate resin in any one of said [1]-[25] using the 1 or more types of dihydroxy compound chosen from the group which consists of a dihydroxy compound shown.

(3)

(In said general formula (5), R <_5> represents a C4-C20 substituted or unsubstituted cycloalkylene group.)

[Chemical Formula 4]

(In said general formula (6), R <_6> represents a C4-C20 substituted or unsubstituted cycloalkylene group.)

[Chemical Formula 5]

(In formula (7), R ₁₁ represents a chain alkylene group having 2 to 20 carbon atoms.)

[27]

The manufacturing method of the polycarbonate resin in any one of said [1]-[26] whose content of the aromatic monohydroxy compound contained in the said polycarbonate resin is 0.0001 weight% or more and less than 0.2 weight%.

[28]

The method for producing a polycarbonate resin according to any one of the above [1] to [27], wherein the raw material monomer is filtered with a raw material filtration filter before the polycondensation reaction is performed.

[29]

The polycarbonate resin whose yellow index value obtained by the manufacturing method in any one of said [1]-[28] is 70 or less.

[30]

When the resin is molded into a film having a thickness of 35 μm ± 5 μm as the polycarbonate resin obtained by the production method according to any one of the above [1] to [28], or the polycarbonate resin according to the above [29], Polycarbonate resin having a maximum length of 25 ㎛ or more foreign matter contained in the film is 1000 pieces / ㎡ or less.

[31]

The polycarbonate resin film whose thickness obtained by shape | molding the polycarbonate resin as described in said [30] is 20 micrometers-200 micrometers.

[32]

A polycarbonate resin is obtained by a polycondensation reaction using at least a dihydroxy compound represented by the following general formula (1) as a raw material monomer, the resulting polycarbonate resin is fed to an extruder, kneaded, and then discharged from a die to be polycarbonate As a method for producing a resin,

The glass transition temperature of the polycarbonate resin discharged | emitted from the said dice is 120 degreeC or more and 150 degrees C or less,

The temperature at the time of feeding to the said extruder is 180 degreeC or more and less than 250 degreeC,

The manufacturing method of polycarbonate resin which satisfy | fills following formula (2), when the weight of resin extruded per hour by the said extruder is W (kg / h), and the cross-sectional area of the barrel of the extruder is S (m <2>).

[Chemical Formula 6]

(In General Formula (1), R ₁ to R ₄ each independently represent a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 cycloalkyl group, or a substituted or unsubstituted group. A C6-C20 aryl group is represented, X is a substituted or unsubstituted C2-C10 alkylene group, a substituted or unsubstituted C6-C20 cycloalkylene group, or a substituted or unsubstituted C6-C20 aryl group A rene group, m and n each independently represent an integer of 0 to 5)

12000? W / S? (2)

According to the present invention, a performance that can be applied to an optical field such as a retardation film having excellent optical properties, mechanical strength and color, and less foreign matter, and also a lens such as a camera lens, a finder lens, a lens for a CCD or a CMOS, etc. It is possible to efficiently and stably produce the polycarbonate resin having

1 shows a flowchart showing an example of a manufacturing process according to the present invention.

EMBODIMENT OF THE INVENTION Although embodiment of this invention is described in detail below, description of the element | module described below is an example (representative example) of embodiment of this invention, and this invention is not limited to the following content unless the summary is exceeded. Do not. In addition, when the expression "-" is used in this specification, it is used by the meaning containing the numerical value or physical value before and after that.

In addition, in this specification, "mass%", "weight%", "mass ppm", "weight ppm", "mass part", and "weight part" are the same meaning, respectively. In addition, when it describes simply as "ppm", it represents "weight ppm."

<Raw monomer and polymerization catalyst>

(Dihydroxy compound)

In the manufacturing method of the polycarbonate resin of this invention, although a dihydroxy compound is used at least as a raw material monomer, at least 1 type of dihydroxy compound is a dihydroxy compound represented by following General formula (1), It is characterized by the following (following) And "dihydroxy compound of the present invention" may be referred to).

[Formula 7]

(In General Formula (1), R ₁ to R ₄ each independently represent a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 cycloalkyl group, or a substituted or unsubstituted group. A C6-C20 aryl group is represented, X is a substituted or unsubstituted C2-C10 alkylene group, a substituted or unsubstituted C6-C20 cycloalkylene group, or a substituted or unsubstituted C6-C20 aryl group A rene group, m and n each independently represent an integer of 0 to 5)

As a substituent of the alkyl group, cycloalkyl group, or aryl group represented by R <_1> -R <_4> , an ester group, an ether group, a carboxylic acid, an amide group, and a halogen are mentioned. As R <_1> -R <_4> , a hydrogen atom, an unsubstituted C1-C4 alkyl group, an unsubstituted C5-C7 cycloalkyl group, or a phenyl group is preferable.

As a substituent of the alkylene group, cycloalkylene group, or arylene group represented by X, ester group, an ether group, a carboxylic acid, an amide group, and a halogen are mentioned. It is more preferable that X is a C2-C6 alkylene group.

m and n are each independently an integer of 0-5, 0 or 1 is preferable, and the compound whose m = 0 and n = 0, or the compound whose m = 1 and n = 1 are especially preferable.

Specific examples of the dihydroxy compound of the present invention include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9 , 9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-n-propylphenyl) fluorene, 9,9-bis (4-hydroxy- 3-isopropylphenyl) fluorene, 9,9-bis (4-hydroxy-3-n-butylphenyl) fluorene, 9,9-bis (4-hydroxy-3-sec-butylphenyl) fluorene , 9,9-bis (4-hydroxy-3-tert-butylphenyl) fluorene, 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, 9,9-bis (4- Hydroxy-3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3 -Methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3 -Isobutylphenyl) fluorene, 9,9-bis (4- (2-high Hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis ( 4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene, 9,9-bis (4- (3-hydroxy-2,2-dimethylpropoxy) phenyl) fluorene Etc. are exemplified, preferably 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9 -Bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, and in particular, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene or 9 in the physical properties of the obtained polymer. Preference is given to, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, particularly preferably 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.

It is preferable that the polycarbonate resin of this invention is obtained using 18 mol% or more of dihydroxy compounds represented by the said General formula (1) as a raw material monomer with respect to all the dihydroxy compounds, More preferably, it is 20 mol% The above-mentioned, Especially preferably, it is 25 mol% or more, Most preferably, it is 30 mol% or more. Moreover, Preferably it is 90 mol% or less, More preferably, it is 70 mol% or less, Especially preferably, it is 50 mol% or less. When the usage-amount of the monomer which has this structural unit is too small, there exists a possibility that the obtained polycarbonate resin may not show desired optical performance. Moreover, when too much, the melt viscosity of the obtained polycarbonate resin will become high, the filtration using a small mesh filter will become difficult, and a foreign material may increase, or pelletization and film film manufacture may become difficult. In addition, if an excessively small mesh filter is used, the filter may be damaged, or the coloring or molecular weight reduction of the polycarbonate resin may be caused.

In addition, with the said desired optical performance, retardation etc. besides coloring and a foreign material which affect light transmittance are mentioned. In particular, when the polycarbonate resin of the present invention is used in a retardation film as a quarter wave plate, it is important to have a phase difference of about 1/4 of the wavelength in all wavelength ranges. In order to do so, the birefringence becomes smaller as the shorter wavelength and longer wavelength It is necessary to provide so-called birefringence reverse dispersion which becomes larger as it becomes. The birefringence wavelength dispersion produces a stretched film having a uniform thickness, measures a phase difference (R450) at a measurement wavelength of 450 nm and a phase difference (R550) at 550 nm, and obtains a ratio (R450 / R550) of R450 and R550. It can evaluate by doing. When this value is less than 1, it shows reverse wavelength dispersion (it may be called negative wavelength dispersion). Preferable R450 / R550 in this invention is 0.80-0.95, More preferably, it is 0.85-0.93, Especially preferably, it is 0.87-0.91. Reverse wavelength dispersibility is too much or too at least not attainable in the polycarbonate resin derived from the compound represented by the said General formula (1), On the other hand, it is influenced also by the structure and content rate of another structural unit.

In the manufacturing method of the polycarbonate resin of this invention, in addition to the dihydroxy compound represented by the said General formula (1) as a raw material monomer, the dihydroxy compound which has a site | part represented by following General formula (4) in a part of structure can be used. have.

[Formula 8]

(Except the case where the site represented by the general formula (4) is part of -CH ₂ -OH)

As a dihydroxy compound which has a site | part represented by the said General formula (4), Specifically, oxyalkylene glycol, such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Ryu; The compound which has cyclic ether structures, such as anhydrous sugar alcohol represented by the dihydroxy compound represented by following General formula (8), and spiroglycol represented by following General formula (9), is mentioned, In particular, Compounds having a cyclic ether structure, such as isosorbide and spiroglycol, in particular, compounds having two cyclic ether structures are preferable from the viewpoint of retardation and low photoelastic coefficient, and on the other hand, availability, handling, and polymerization Diethylene glycol and triethylene glycol are preferable from a viewpoint of reactivity, the color of the polycarbonate resin obtained, and the toughness at the time of shape | molding in the film. In addition, the compound having a cyclic ether structure is rigid and can increase the mechanical properties of the resulting polycarbonate resin, while being easily colored at high temperatures, but according to the method of the present invention, the effect of suppressing coloring is obtained. Especially when the compound which has two cyclic ether structures is used, the said effect becomes further larger. These dihydroxy compounds may be used alone or in combination of two or more according to the required performance of the polycarbonate resin obtained.

[Chemical Formula 9]

[Formula 10]

Examples of the dihydroxy compound represented by the general formula (8) include isosorbide, isomannide, and isoidide in a stereoisomer relationship. Among these dihydroxy compounds, isosorbide obtained by dehydrating and condensing sorbitol prepared from various starches which are present in abundance as resources and readily available is most preferable in terms of availability and preparation, optical properties, and moldability. Do.

In the present invention, the amount of use in the case of using a compound having a cyclic ether structure such as isosorbide or spiroglycol is not limited, but as the lower limit, preferably 10 mol% or more, based on the total hydroxy compound, More preferably, it is 20 mol% or more, Especially preferably, it is 30 mol% or more, Most preferably, it is 40 mol% or more. Moreover, as an upper limit, Preferably it is 82 mol% or less, More preferably, it is 75 mol% or less, More preferably, it is 70 mol% or less, Especially preferably, it is 60 mol% or less. When the usage-amount of the monomer which has this structural unit is too small, there exists a possibility that the polycarbonate resin obtained may not show desired optical performance. Moreover, even if it is too large, it may not only show desired optical performance, but it may adversely affect the thermal stability of the polycarbonate resin obtained, or it may become difficult to pelletize and produce a film film by high melt viscosity.

In the manufacturing method of the polycarbonate resin of this invention, the dihydroxy compound represented by General formula (5) can be used as a raw material monomer.

[Formula 11]

(In said general formula (5), R <_5> represents a C4-C20 substituted or unsubstituted cycloalkylene group.)

As a dihydroxy compound represented by the said General formula (5), It is some, such as 2, 6- decalin diol, 1, 5- decalin diol, 2, 3- decalin diol, tricyclo decane diol, pentacyclo pentadecane diol, etc. Compound having alicyclic structure, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl The compound containing the cycloalkylene group of monocyclic structures, such as -1, 4- cyclohexanediol and 1, 3- tetramethyl cyclobutanediol, is mentioned. By setting it as a monocyclic structure, the toughness at the time of using the polycarbonate resin obtained as a film can be improved. Moreover, the compound containing a 5-membered ring structure or a 6-membered ring structure is mentioned normally. 5-atom cyclic structure or 6-atom cyclic structure, the heat resistance of the resulting polycarbonate resin can be increased. The 6-membered ring structure may be fixed to the chair type or the boat type by covalent bonding. Moreover, as a substituent in the case of having a substituent, a C1-C4 alkyl group is preferable. Specific examples of the dihydroxy compound represented by the general formula (5) include 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1, 4- cyclohexanediol, 2-methyl-1, 4- cyclohexanediol, etc. are mentioned.

In the manufacturing method of the polycarbonate resin of this invention, the dihydroxy compound represented by General formula (6) can be used as a raw material monomer.

[Chemical Formula 12]

(In said general formula (6), R <_6> represents a C4-C20 substituted or unsubstituted cycloalkylene group.)

As a dihydroxy compound represented by the said General formula (6), 2, 3- norbornane dimethanol, 2, 5- norbornane dimethanol, adamantane dimethanol, decalin dimethanol, tricyclo tetradecane dimethanol, etc. And compounds containing monocyclic cycloalkylene groups such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and the like having a plurality of alicyclic structures. have. When the dihydroxy compound having a plurality of alicyclic structures is used, the heat resistance may be improved, and the toughness may be deteriorated, or the viscosity at the time of melting may be increased, thereby deteriorating fluidity. From the viewpoint of fluidity at the time of melting, a dihydroxy compound having a monocyclic structure, particularly a dihydroxy compound containing a 5-membered ring structure or a 6-membered ring structure is preferable. By being a 5-membered ring structure or a 6-membered ring structure, the heat resistance of the polycarbonate resin obtained can be improved. The 6-membered ring structure may be fixed to the chair type or the boat type by covalent bonding. Moreover, as a substituent in the case of having a substituent, a C1-C4 alkyl group is preferable. Specifically, 1, 2- cyclohexane dimethanol, 1, 3- cyclohexane dimethanol, 1, 4- cyclohexane dimethanol, etc. are mentioned.

Among the specific examples of the alicyclic dihydroxy compound described above, cyclohexanedimethanol is particularly preferable, and 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, from the viewpoint of availability and ease of handling, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol is preferable especially from a viewpoint of a polymerization reactivity and toughness improvement.

In the manufacturing method of the polycarbonate resin of this invention, the dihydroxy compound represented by General formula (7) can be used as a raw material monomer.

[Chemical Formula 13]

(In formula (7), R ₁₁ represents a chain alkylene group having 2 to 20 carbon atoms.)

Although the dihydroxy compound represented by the said General formula (7) may be linear or may have a branch, a linear alkylenediol is preferable. Specifically, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc. are mentioned, Among them, 1,3 -Propylene glycol, 1,4-butanediol and 1,6-hexanediol are preferred, and 1,6-hexanediol is most preferred because the molecular weight is small, the volatilization during the polymerization or the toughness imparting effect is small.

In the manufacturing method of the polycarbonate resin of this invention, you may use a bisphenol compound as a raw material monomer. As this bisphenol compound, For example, 2, 2-bis (4-hydroxyphenyl) propane [= bisphenol A], 2, 2-bis (4-hydroxy-3, 5- dimethylphenyl) propane, 2 , 2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4 -Hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4'-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) Methane, bis (4-hydroxy-5-nitrophenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis ( 4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4'-dihydroxy A didi ether, 4, 4'- dihydroxy-3, 3'- dichloro diphenyl ether, a 4, 4'- dihydroxy-2, 5- diethoxy diphenyl ether, etc. are mentioned.

The polycarbonate resin in this invention is a dihydroxy compound which has a site | part represented by the said General formula (4), the dihydroxy compound represented by the said General formula (5), and the dihydroxy compound represented by the said General formula (6). 5 mol, when the total dihydroxy compound is 100 mol% as one of the total of one or more dihydroxy compounds selected from the group consisting of dihydroxy compounds and bisphenol compounds represented by the general formula (7). It is preferable that it is obtained using% or more, More preferably, it is 25 mol% or more, More preferably, it is 30 mol% or more, Especially preferably, it is 35 mol% or more. Moreover, it is preferable that it is 82 mol% or less, More preferably, it is 75 mol% or less. In the dihydroxy compound which has a site | part represented by these said General formula (4), the dihydroxy compound represented by the said General formula (5), the dihydroxy compound represented by the said General formula (6), and the said General formula (7) When the usage-amount of the 1 or more types of dihydroxy compound chosen from the group which consists of the dihydroxy compound and bisphenol compound shown is too small, the toughness of the polycarbonate resin obtained may fall, and pelletization and film film manufacture may become difficult. On the other hand, when there are too many, the polycarbonate resin obtained may not show desired optical performance.

Among them, in the present invention, 9,9-bis (4-hydroxy-3- as a dihydroxy compound represented by the general formula (1) in the optical properties, heat resistance, toughness of the polymer obtained, and fluidity at the time of melting. Isosorbide and / or as a dihydroxy compound having methylphenyl) fluorene and / or 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and the moiety represented by the formula (4) The polycarbonate resin which copolymerized spiroglycol is preferable. In addition, for imparting toughness, at least one dihydroxy compound selected from diethylene glycol, triethylene glycol, polyethylene glycol, 1,4-cyclohexanedimethanol, and 1,6-hexanediol is used. 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and / or 9,9-bis (4- (2-hydroxyethoxy) phenyl) flu as a dihydroxy compound represented by Formula (1) It is preferable to set it as the polycarbonate resin which copolymerized orene and 3 or more types of monomers of isosorbide and / or spiroglycol as a dihydroxy compound which has a site | part represented by said Formula (4). Especially preferably, a copolymer of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and isosorbide, or in addition to diethylene glycol, triethylene glycol, polyethylene glycol, 1, The at least one dihydroxy compound selected from 4-cyclohexanedimethanol and 1,6-hexanediol is 30 mol% or less, more preferably 20 mol% or less, and preferably, based on the total dihydroxy compound. Is a polycarbonate resin copolymerized at 0.05 mol% or more, more preferably 0.1 mol% or more.

The polycarbonate resin in this invention can be obtained by interfacial polycondensation using the said dihydroxy compound and phosgene. In particular, when m = n = 0 or when a bisphenol compound is used among the compounds represented by the general formula (1) as the dihydroxy compound, an aqueous solution of the alkali metal salt of the dihydroxy compound and phosgene are methylene chloride or the like. It is preferable to obtain by the interfacial polycondensation method to react in presence of a solvent.

Moreover, when a dihydroxy compound is a structure which does not have a phenolic hydroxyl group, For example, the compound represented by the said General formula (1), the compound which has a site | part represented by the said General formula (4), and the said General formula ( In the case of using at least one of the dihydroxy compounds represented by 5), (6) and (7) in combination, the monohydroxy compound produced by transesterification of the dihydroxy compound and the diester carbonate in the presence of a catalyst to the outside of the system It is preferable to obtain by the transesterification method which increases molecular weight, removing.

(Carbonic acid diester)

As diester carbonate used by this invention, what is represented by the following general structural formula (10) is mentioned. These diester carbonate may be used individually by 1 type, or may mix and use 2 or more types.

[Formula 14]

(A ¹ and A ² are a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic group, and A ¹ and A ² may be the same or different).

Preferred of A ¹ and A ² are a substituted or unsubstituted aromatic hydrocarbon group, and more preferably an unsubstituted aromatic hydrocarbon group. Moreover, as a substituent of an aliphatic hydrocarbon group, ester group, an ether group, a carboxylic acid, an amide group, and a halogen are mentioned, As a substituent of an aromatic hydrocarbon group, alkyl groups, such as a methyl group and an ethyl group, are mentioned.

As diester carbonate represented by the said General formula (10), Substituted diphenyl carbonate, such as diphenyl carbonate and a tolyl carbonate, dimethyl carbonate, diethyl carbonate, di- t-butyl carbonate, etc. are illustrated, for example, Preferably they are diphenyl carbonate and substituted diphenyl carbonate, Especially preferably, they are diphenyl carbonate. In addition, since diester carbonate may contain impurities, such as chloride ion, and may inhibit a polymerization reaction or worsen the color of the polycarbonate resin obtained, what was refine | purified by distillation etc. is used as needed. It is desirable to.

In the method of this invention, polycarbonate resin is obtained by polycondensing the dihydroxy compound and diester carbonate containing the dihydroxy compound of this invention by a transesterification reaction. Although the raw material dihydroxy compound and diester carbonate can be transesterified even if it is dropped to the reactor independently, it can also mix uniformly before a transesterification reaction. 80 degreeC or more of this mixing temperature is good, Preferably it is 90 degreeC or more, The upper limit is 250 degrees C or less, Preferably it is 200 degrees C or less, More preferably, it is 150 degrees C or less. Especially, 100 degreeC or more and 130 degrees C or less are preferable. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often causing problems such as solidification. If the mixing temperature is too high, thermal deterioration of the dihydroxy compound may result. There exists a possibility that the color of the polycarbonate resin obtained may deteriorate.

In the method of this invention, 10 vol% or less of oxygen concentration of the operating environment which mixes the dihydroxy compound containing the dihydroxy compound of this invention which is a raw material, and the diester carbonate is preferable, Furthermore, 0.0001 vol%-10 It is preferable to implement in vol%, especially 0.0001 vol%-5 vol%, especially 0.0001 vol%-1 vol% from a viewpoint of color deterioration prevention.

In the present invention, the diester carbonate may be used in a molar ratio of 0.90 to 1.20 with respect to the total dihydroxy compound including the dihydroxy compound of the present invention used in the reaction, preferably 0.95 to 1.10, more preferably It is preferably 0.97 to 1.03, particularly preferably 0.99 to 1.02. When this molar ratio becomes small, the terminal hydroxyl group of the polycarbonate resin produced increases, the thermal stability of a polymer worsens, it causes coloring at the time of shaping | molding, the rate of transesterification reaction falls, or a desired high molecular weight body is not obtained. There is no possibility. On the other hand, when this molar ratio becomes large, the rate of transesterification reaction will fall, manufacture of polycarbonate of desired molecular weight will become difficult, the amount of diester carbonate remaining in a polycarbonate resin will increase, and generation | occurrence | production of gas at the time of extrusion or shaping | molding will increase. It may be caused. The decrease in the transesterification reaction rate may increase the thermal history during the polymerization reaction and deteriorate the color of the resulting polycarbonate resin.

Furthermore, when the molar ratio of diester carbonate to the total dihydroxy compound containing the dihydroxy compound of the present invention increases, the amount of remaining diester carbonate in the polycarbonate resin obtained increases, which becomes a gas during molding. It may not be preferable because it may lead to mold failure or bleed out of the product. The concentration of the diester carbonate remaining in the polycarbonate resin obtained by the method of the present invention is preferably 200 wtppm or less, more preferably 100 wtppm or less, particularly preferably 60 wtppm or less, and particularly 30 wtppm or less. Is preferred.

(catalyst)

In the method of the present invention, as described above, when a polycarbonate resin is produced by polycondensing a dihydroxy compound and a diester carbonate containing a dihydroxy compound of the present invention by a transesterification reaction, a transesterification catalyst (Hereinafter also referred to simply as "catalyst" or "polymerization catalyst").

In the process of the present invention, the transesterification catalyst (catalyst) can in particular affect the thermal stability of the polycarbonate resin or the yellow index (YI) value indicating the color. The transesterification catalyst to be used is not limited as long as it satisfies the thermal stability and the color of the polycarbonate resin, but is not limited to Group 1 or Group 2 (hereinafter, simply referred to as "Group 1" and "Group 2") in a long periodic table. Basic compounds, such as a metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound, are mentioned. Preferably, at least one of the Group 1 metal compound and the Group 2 metal compound is used, and more preferably at least one metal compound selected from the group consisting of metal and lithium of the long-period periodic table group 2 is used.

The form of the Group 1 metal compound and Group 2 metal compound is usually used in the form of hydroxides or salts such as carbonates, carboxylates, phenol salts, hydroxides, carbonates, acetates are preferred in the availability and ease of handling In view of color and polymerization activity, acetate is preferred.

Specific examples of the Group 1 metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bisulfate, cesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, and carbonic acid. Cesium, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium borohydride Potassium borohydride, lithium phenylborosilicate, cesium borohydride, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, sodium hydrogen phosphate, potassium dihydrogen phosphate, lithium lithium phosphate, cesium hydrogen phosphate, phenyl phosphate Disodium, dipotassium phenyl phosphate, dilithium phenyl phosphate, cesium phenyl phosphate, alcoholate of sodium, potassium, lithium, cesium, phenolate, disodium salt of bisphenol A, 2 Potassium salts, dilithium salts, cesium salts, etc. are mentioned, A lithium compound is especially preferable.

Moreover, as a specific group 2 metal compound, for example, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate Strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, and the like, among which magnesium compounds, calcium compounds, and barium compounds are preferable. More preferably, at least 1 type of metal compound chosen from the group which consists of a magnesium compound and a calcium compound from a viewpoint of a polymerization activity and the color of the polycarbonate resin obtained, Most preferably, it is a magnesium compound.

Moreover, although basic compounds, such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound, can also be used together with at least one of the said group 1 metal compound and the group 2 metal compound, it volatilizes during a polymerization reaction, Since it may cause trouble, it is especially preferable to use only at least one of a group 1 metal compound and a group 2 metal compound.

As said basic boron compound which can be used together, for example, tetramethylboric acid, tetraethylboric acid, tetrapropylboric acid, tetrabutylboric acid, trimethylethylboric acid, trimethylbenzylboric acid, trimethylphenylboric acid, triethylmethylboric acid, triethylbenzylboric acid Sodium salts such as triethylphenylboric acid, tributylbenzylboric acid, tributylphenylboric acid, tetraphenylboric acid, benzyltriphenylboric acid, methyltriphenylboric acid, butyltriphenylboric acid, potassium salt, lithium salt, calcium salt and barium salt And magnesium salts or strontium salts.

As said basic phosphorus compound which can be used together, a triethyl phosphine, a tri-n-propyl phosphine, a triisopropyl phosphine, a tri- n-butyl phosphine, a triphenyl phosphine, a tributyl phosphine, or And quaternary phosphonium salts.

As said combined basic ammonium compound, For example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzyl Ammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide Said, tetraphenylammonium hydroxide, benzyl triphenylammonium hydroxide, methyl triphenylammonium hydroxide, butyl triphenylammonium hydroxide, etc. are mentioned.

As said amine compound which can be used together, 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-meth Methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.

The amount of the catalyst used is preferably from 0.1 μmol to 300 μmol, preferably from 0.5 μmol to 100 μmol, preferably from 0.5 μmol to 50 μmol per 1 mol of the total dihydroxy compound used. Is 0.5 mol-20 mol, particularly preferably 1 mol-15 mol. Among them, in the case of using at least one metal compound selected from the metals of the long-period periodic table group 2 and lithium, the amount of metal per mol of all the dihydroxy compounds used is usually 0.1 μmol or more, preferably 0.5 mol or more, particularly preferably 0.7 mol or more. In addition, as an upper limit, 50 micromol, Preferably it is 30 micromol, More preferably, 20 micromol, Especially preferably, 15 micromol, Especially, 10 micromol is preferable.

When the usage-amount of the said catalyst is too small, a polycondensation reaction will not progress easily and there exists a possibility that the polycarbonate resin of a desired molecular weight may not be obtained. On the other hand, when the usage-amount of the said catalyst is too big | large, there exists a possibility that it may worsen the color of the polycarbonate resin obtained by an unwanted side reaction, or may cause a foreign material. In addition, when the Group 1 metal, especially sodium, is contained in a large amount of polycarbonate resin, there is a possibility that the color may be adversely affected, and the metal may be mixed not only from the catalyst used but also from the raw material or the reaction apparatus. The total amount of these compounds in the resin is usually 1 ppm by weight or less, preferably 0.8 ppm by weight or less, and more preferably 0.7 ppm by weight or less as the metal amount. The amount of metal in the polycarbonate resin can be measured using a method such as atomic emission, atomic absorption, or inductively coupled plasma (ICP) after the metal in the polycarbonate resin is recovered by a method such as wet painting.

In addition, the catalyst may be added directly to the reactor, may be added to the raw material control tank for mixing the dihydroxy compound and the diester carbonate in advance, and then may be present in the reactor, or added in the piping for supplying the raw material to the reactor. You may also When the amount of the catalyst used is too small, sufficient polymerization activity is not obtained and the progress of the polymerization reaction is slowed. Therefore, a polycarbonate resin having a desired molecular weight is hardly obtained, and a long history of heat is received, which may deteriorate color. have.

(Polycondensation Method by Ester Exchange Method)

In the method of the present invention, a method of polycondensing the dihydroxy compound and the diester carbonate to obtain a polycarbonate resin may be carried out in multiple stages using a plurality of reactors in the presence of the catalyst described above. The type of reaction may be any of batch, continuous, or a combination of batch and continuous, and in particular, from the viewpoint of quality stabilization, continuous is preferable. In the initial stage of the polymerization, it is preferable to obtain a prepolymer at a relatively low temperature and a low vacuum, and to increase the molecular weight to a predetermined value at a relatively high temperature and a high vacuum at the end of the polymerization. Proper selection of pressure is important in terms of color and thermal stability. For example, if any one of temperature and pressure changes too quickly before a polymerization reaction reaches a predetermined value, an unreacted monomer will flow out, shifting the molar ratio of a dihydroxy compound and diester carbonate, and superposing | polymerizing. There is a possibility that a decrease in speed or a polymer having a predetermined molecular weight or end group cannot be obtained, and as a result, the object of the present invention cannot be achieved.

Furthermore, in order to suppress the amount of monomer flowing out, it is effective to use a reflux condenser in the polymerization reactor, and the effect is particularly great in a reactor in the initial stage of polymerization with a large amount of unreacted monomer components. The temperature of the refrigerant introduced into the reflux cooler can be appropriately selected depending on the monomer used. Usually, the temperature of the refrigerant introduced into the reflux cooler is 45 to 180 ° C at the inlet of the reflux cooler, preferably 80 to 150 ° C. Especially preferably, it is 100-140 degreeC. If the temperature of the refrigerant is too high, the amount of reflux decreases, and the effect thereof is lowered. On the contrary, if the temperature of the refrigerant is too low, the distillation efficiency of the monohydroxy compound to be originally distilled off tends to decrease. Hot water, steam, fruit oil, etc. are used as a refrigerant | coolant, and steam and fruit oil are preferable.

It is important to select the type and amount of the catalyst described above in order to properly maintain the rate of polymerization, to suppress the outflow of monomers, to suppress the occurrence of foreign matters in the final polycarbonate resin, and not to impair color or thermal stability. . In this invention, it is preferable to manufacture by using the said catalyst and superposing | polymerizing in multistep using several reactor. The reason why the polymerization is carried out in a plurality of reactors is that in the initial stage of the polymerization reaction, since there are many monomers contained in the reaction solution, it is important to suppress the volatilization of the monomer while maintaining the required polymerization rate. In order to shift the equilibrium to the polymerization side, it is important to sufficiently distill off the by-produced monohydroxy compound, and preferred polymerization reaction conditions are different at the beginning and the end. In order to set such different polymerization reaction conditions, it is preferable to use the several polymerization reactor arrange | positioned in series from a viewpoint of production efficiency.

In the present invention, at least two or more reactors may be used as described above, but from the viewpoint of production efficiency and the like, three or more, preferably three to five, particularly preferably four. In the present invention, when there are two or more reactors, it is possible to set reaction conditions having different conditions in each reactor, and it is preferable to change the temperature and pressure continuously in each reactor, and to increase the temperature step by step for each reactor. It is more preferable to set it as the setting which reduced the pressure in steps.

In the present invention, the polymerization catalyst may be added to the raw material preparation tank, the raw material storage tank, or directly added to the polymerization tank, but from the viewpoint of supply stability and polymerization control, the catalyst is supplied in the middle of the raw material piping before being supplied to the polymerization tank. What is necessary is just to provide a piping, Preferably it supplies with aqueous solution.

When the temperature of the said polymerization reaction is too low, it will lead to a fall of productivity and the increase of the heat history with respect to a product, and when too high, it will not only cause the volatilization of a monomer but can also promote the decomposition and coloring of a polycarbonate resin.

Specific temperature is as follows. As for the reaction of the 1st stage, 140-270 degreeC is preferable as the maximum temperature of the internal temperature of a polymerization reactor, Preferably it is 110-1 Pa at 170-240 degreeC, More preferably, 180-210 degreeC, Preferably it is 70 It is performed while distilling off the by-produced monohydroxy compound out of a reaction system for 0.1 to 10 hours, Preferably it is 0.5 to 3 hours, under the pressure of 30 kPa or more (absolute pressure). The reaction of the first stage in the present invention refers to the reaction in the reactor at the most upstream of the process among the reactors in which 5% by weight or more of the monohydroxy compound flowing out through the entire polymerization reaction flows out.

After the second stage, the pressure of the reaction system is gradually lowered from the pressure of the first stage, and the monohydroxy compound generated continuously is removed outside the reaction system, and finally the pressure (absolute pressure) of the reaction system is 2 kPa or less, preferably Is 1 Pa or less, preferably 210 ° C. or higher, preferably 220 ° C. or higher, 270 ° C. or lower, preferably 250 ° C. or lower, more preferably 240 ° C. or lower, and preferably 0.1 to 10 hours, preferably 1 to It is carried out for 6 hours, particularly preferably 0.5 to 3 hours.

In particular, in order to suppress coloring or thermal degradation of the polycarbonate resin and obtain a polycarbonate resin having good color and thermal stability, the maximum temperature of the internal temperature in the entire reaction step is less than 260 ° C, preferably less than 250 ° C, particularly 245 ° C. It is preferable that it is less than 240 degreeC especially. Internal temperature here shows the temperature of a process liquid, and is measured by the thermometer using the thermocouple etc. which were normally equipped in the reactor. Moreover, in order to suppress the fall of the superposition | polymerization rate after a polymerization reaction, and to suppress deterioration by heat history to the minimum, it is preferable to use the horizontal reactor excellent in plug flow property and interface update property at the last stage of superposition | polymerization. However, in order to obtain the polycarbonate resin of a predetermined molecular weight, it is necessary to note that if the polymerization temperature is too high or the polymerization time is too long, the yellow index (YI) value indicating the color tends to be large.

It is preferable to use the monohydroxy compound by-produced and distilled off in the said reaction as a raw material of a fuel or a chemical goods from a viewpoint of resource effective utilization. In particular, it is preferable to recycle | reuse as raw materials, such as diphenyl carbonate and bisphenol A, after refine | purifying as needed.

(Process after polycondensation reaction)

It is preferable to filter the polycarbonate resin of this invention using a filter after performing the polycondensation reaction mentioned above. Especially, in order to remove the low molecular weight component contained in polycarbonate resin, and to carry out addition kneading | mixing of a heat stabilizer etc., the polycarbonate resin produced by polycondensation is introduce | transduced into an extruder, and the polycarbonate resin discharged from the extruder is then taken out. It is preferable to filter using a filter.

As a method of filtering and pelletizing the polycarbonate resin produced by polycondensation as mentioned above using a filter, the following method is mentioned, for example.

A method of extracting a polycarbonate resin in a molten state from a final polymerization reactor by using a gear pump, a screw or the like to generate a pressure necessary for filtration, and filtration with the filter;

A method of supplying polycarbonate resin to a single screw or twin screw extruder in a molten state from the final polymerization reactor by melt extrusion, filtering with the filter, cooling and solidifying in the form of strands, and pelletizing with a rotary cutter;

The polycarbonate resin was supplied to a single- or two-screw extruder in a molten state without being solidified from the final polymerization reactor and melt-extruded, and then cooled and solidified in the form of strands to be pelletized, and the pellet was introduced into the extruder again. A method of filtration with a filter, cooling and solidifying in the form of strands, and pelletizing;

Alternatively, the polycarbonate resin is extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand without passing through an extruder, and pelletized once, and then pellet-feeded into a single or biaxial extruder, followed by melt extrusion. Filtration with the said filter, the cooling solidification in the form of a strand, and pelletizing.

In particular, in order to suppress the thermal history to a minimum and to suppress thermal deterioration such as deterioration of color and lowering of molecular weight, the polycarbonate resin produced by polycondensation by a transesterification reaction is in a molten state without solidifying from the final polymerization reactor. After the resin is supplied to a single or two-screw extruder and melt-extruded, it is fed to the filter using a gear pump, filtered, discharged from a die, cooled and solidified in the form of strands, and pelletized by a rotary cutter or the like. This is preferred.

<One example of manufacturing apparatus>

An example of the apparatus which implements this invention which obtains polycarbonate resin from the raw material monomer described above is shown to the process diagram of FIG. 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and isosorbide (ISB) as the dihydroxy compound of the present invention which is a raw material monomer, and diphenyl carbonate (DPC) as diester carbonate It is assumed that magnesium acetate is used as the polymerization catalyst.

First, in the raw material preparation step, the molten liquid of DPC prepared at a predetermined temperature in a nitrogen gas atmosphere, and the powder of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene are supplied from the raw material supply port ( It is supplied continuously to the raw material mixing tank 2a from 1a). In addition, the melt of ISB and the melt of CHDM measured under a nitrogen gas atmosphere are continuously supplied to the raw material mixing tank 2a from the raw material supply ports 1b and 1c, respectively. And these are mixed by the stirring blade 3a in the raw material mixing tank 2a, and a uniform raw material mixing melt is obtained.

Next, the obtained raw material mixed melt is continuously supplied to the 1st male stirring reactor 6a via the raw material feed pump 4a and the raw material filtration filter 5a. In addition, the raw material catalyst is continuously supplied from the catalyst supply port 1d during the conveying piping of the raw material mixed melt as an aqueous solution.

In the polycondensation step of the manufacturing apparatus of FIG. 1, the first male stirring reactor 6a, the second male stirring reactor 6b, the third male stirring reactor 6c, and the fourth horizontal stirring reactor 6d are connected in series. Is formed. In each reactor, the liquid level is kept constant, and the polycondensation reaction is performed continuously, and the polymerization reaction liquid discharged | emitted from the tank bottom of the 1st water type stirring reactor 6a is continued to the 2nd water type stirring reactor 6b. The third condensation reaction reactor 6c is sequentially supplied to the fourth horizontal stirring reactor 6d and the polycondensation reaction proceeds. It is preferable to set reaction conditions in each reactor so that it may become high temperature, high vacuum, and a low stirring speed with progress of a polycondensation reaction.

Max blend blades 7a, 7b, 7c are formed in the first male stirring reactor 6a, the second male stirring reactor 6b, and the third male stirring reactor 6c, respectively. In addition, a biaxial spectacle type stirring blade 7d is formed in the fourth horizontal stirring reactor 6d. Since the reaction liquid to be conveyed becomes high viscosity after the third male stirring reactor 6c, the gear pump 4b is formed.

Since the calorific value of feed may increase especially in the 1st male stirring reactor 6a and the 2nd male stirring reactor 6b, internal heat exchangers 8a and 8b are formed so that a heating temperature may not become excessively high temperature, respectively. .

In addition, these four reactors are equipped with outlet pipes 11a, 11b, 11c, and 11d for discharging by-products and the like generated by the polycondensation reaction, respectively. Reflux coolers 9a and 9b and reflux tubes 10a and 10b are respectively formed for the first male stirred reactor 6a and the second male stirred reactor 6b to return a part of the effluent to the reaction system. The reflux ratio can be controlled by appropriately adjusting the pressure of the reactor and the fruit temperature of the reflux cooler, respectively.

The outlet pipes 11a, 11b, 11c, and 11d are connected to the condensers 12a, 12b, 12c, and 12d, respectively, and each reactor is brought into a predetermined reduced pressure state by the pressure reducing devices 13a, 13b, 13c, and 13d. maintain.

Moreover, by-products, such as a phenol (monohydroxy compound), are liquefied and collect | recovered continuously from the condenser 12a, 12b, 12c, and 12d attached to each reactor, respectively. Further, cold traps (not shown) are formed downstream of the condensers 12c and 12d attached to the third male stirring reactor 6c and the fourth horizontal stirring reactor 6d, respectively, and the by-products are solidified and recovered continuously. .

The reaction liquid raised to the predetermined molecular weight is taken out from the fourth horizontal stirring reactor 6d and transferred to the extruder 15a by the gear pump 4c. The pipe connecting the gear pump 4c and the extruder 15a is preferably a jacketed double pipe in which the fruit flows to the outside, and the temperature of the fruit is determined by the viscosity of the polycarbonate resin, the pressure loss of the pipe, Although it can determine suitably in consideration of thermal stability, when it is too high, it may cause deterioration of a polycarbonate resin and generation | occurrence | production of gas, and therefore it is usually 300 degrees C or less, Preferably it is 280 degrees C or less, More preferably, it is 260 degrees C or less, Especially Preferably it is 250 degrees C or less, especially 240 degrees C or less is optimal. On the other hand, if the pressure is too low, the pressure loss in the pipe is large, and the pipe diameter needs to be increased, but at the same time, the residence time of the polycarbonate resin in the pipe may be long, which may cause thermal deterioration. Preferably it is 180 degreeC or more, More preferably, it is 200 degreeC or more, Especially preferably, it is 210 degreeC or more, Above all, 220 degreeC or more is optimal.

The extruder 15a is equipped with a vacuum vent and removes the residual low molecular component in polycarbonate. Moreover, antioxidant, a light stabilizer, a coloring agent, a mold release agent, etc. are added as needed.

Resin is supplied from the extruder 15a to the filter 15b by the gear pump 4d, and a foreign material is filtered. The resin having passed through the filter 15b is extracted from the die 15c onto the strand, and after cooling and solidifying the resin with water in the strand cooling tank 16a, the resin is pelletized by the strand cutter 16b. The polycarbonate resin pellets thus obtained are mechanically transported by the air transfer blower 16c and transferred to the product hopper 16d. A predetermined amount of product is packed into the product bag by the meter 16e.

There is no restriction on the type of the gear pumps 4c and 4d, but among them, some polymer is led from the discharge side of the gear pump to the gland portion through the valve, and a constant pressure is applied to the shaft rod portion to form the inlet port. A self-circulating seal type gear pump having a turning circuit and not using gland packing on the seal portion is preferable from the viewpoint of foreign matter reduction.

<The details of the pellet manufacturing process after a polymerization reaction>

(Extruder)

In the present invention, the shape of the extruder is not limited, but a uniaxial or biaxial extruder is used. Especially, for the improvement of the devolatilization performance mentioned later and the uniform kneading | mixing of an additive, a biaxial extruder is preferable. In this case, the direction of rotation of the shaft may be two-way or the same direction, but from the viewpoint of kneading performance, the same direction is preferable. The use of an extruder can stabilize the supply of polycarbonate resin to the filter.

Moreover, in the polycarbonate resin produced by polycondensation as mentioned above, the raw material monomer which may adversely affect a product by color, thermal stability, bleed-out, etc., the monohydroxy compound and polycarbonate by-produced by a transesterification reaction Although low molecular weight compounds, such as an oligomer, remain | surviving in many cases, it is also possible to devolatilize and remove them by using the thing which has a vent port as said extruder, Preferably it is made to reduce pressure using a vacuum pump etc. from a vent port. In addition, a volatile liquid such as water may be introduced into the extruder to promote devolatilization. Although one or more vents may be sufficient as it, Preferably it is two or more.

Moreover, additives, such as a heat stabilizer, a mold release agent, and a coloring agent mentioned later, can also be kneaded using the said extruder.

Further, in order to suppress thermal deterioration of the polycarbonate resin in the extruder, the rotation speed of the shaft (hereinafter sometimes referred to as screw) provided in the extruder is 300 rpm or less, preferably 250 rpm or less, more preferably. To 200 rpm or less. When the rotation speed of the screw exceeds 300 rpm, the shear heat generation of the polycarbonate resin becomes large, leading to deterioration of color and reduction of molecular weight. On the other hand, if the rotation speed of the screw is too small, it is not only possible to deteriorate the devolatilization performance and the kneading performance of the additive, but also to reduce the throughput per unit time, resulting in deterioration of the productivity. The above is more preferably 70 rpm or more.

In addition, although the circumferential speed of the said screw is suitably determined by the screw diameter and rotation speed of the said extruder, in order to suppress thermal deterioration, such as coloring and molecular weight fall resulting from exothermic by the shear of polycarbonate resin, it is normally 1.0 m / Seconds or less, Preferably it is 0.6 m / sec or less, Especially preferably, it is 0.4 m / sec or less. On the other hand, when the circumferential speed is too small, there is a tendency to cause vent up during vacuum devolatilization or to reduce the devolatilization performance and the dispersing performance of the additive. Therefore, it is usually 0.05 m / sec or more, preferably 0.1 m / sec. That's it.

In general, the screw of the extruder is composed of a plurality of elements (screw elements) in order to have a variety of functions, generally for the purpose of kneading the full flight, resin consisting mainly of screw screw (flight) mainly for conveying the resin It is composed of a kneading disk, a sealing ring for the purpose of sealing the resin, and the like, and a reverse flight in which screws are arranged in the opposite direction to the conveying direction of the resin according to the purpose is also used. In addition, there are two tanks and three tanks according to the cutting method of the screw. In the present invention, the processing amount is largely obtained with respect to the screw diameter of the extruder, and the two-shape deep can suppress the shear heat generated by the screw rotation. Home type is preferred.

In this invention, although the structure of these screw elements is not limited, It is preferable that at least 1 of those elements is a kneading disk, Especially, it is preferable that the total length of the kneading disk is 20% or less of the total length of a screw, and more Preferably it is 15% or less, Most preferably, it is 10% or less. When the total length of the kneading disc is too long, local heat generation due to shearing of the resin increases, and problems such as color deterioration and molecular weight decrease of the polycarbonate resin are likely to occur. On the other hand, when the total length of the kneading disc is too short, since the performance at the time of kneading of the devolatilization and the additive mentioned above may fall, it is preferable that the total length of the kneading disc is 3% or more of the total length of the screw, 5% or more is more preferable.

As said kneading disc, there exist a forward transfer type | mold, orthogonal | vertical type, and a reverse feed type with respect to the conveyance direction of resin, and it can select suitably according to the viscosity of the resin used and the performance required.

As a material of the said screw element, it is preferable to make content of nickel etc. of a surface high, to suppress iron content low, or to perform the process which raises surface hardness by TiN or CrN.

In this invention, when W (kg / h) and the cross-sectional area of the barrel of the said extruder are made into S (m <2>) the weight of resin extruded per hour with the said extruder, following formula (2) is satisfied.

12000? W / S? (2)

When the W / S is too small, not only the size of the extruder becomes excessive with respect to the amount of polycarbonate resin to be treated, but also the residence time in the extruder increases, which may lead to deterioration of molecular weight of the polycarbonate resin, coloration, and the like. The lower limit thereof is preferably 15000, more preferably 20000, and particularly preferably 25000. On the other hand, if the W / S is too large, an excessive polycarbonate resin is supplied with respect to the size of the extruder, which may lead to a decrease in devolatilization efficiency and deterioration of the polycarbonate resin due to shear exotherm. Is 50000, more preferably 45000, particularly preferably 35000.

In the present invention, the temperature of the resin in the case of supplying the polycarbonate resin in the molten state to the extruder is usually 180 ° C or higher, preferably 200 ° C or higher, and particularly preferably 210 ° C or higher, particularly 220 ° C or higher. Do. Moreover, it is preferable that the upper limit is 250 degrees C or less, More preferably, it is less than 250 degreeC, Especially, it is preferable that it is less than 245 degreeC, especially less than 240 degreeC. If the temperature of the polycarbonate resin supplied to the extruder is too low, the melt viscosity of the polycarbonate resin may be high, or the load of the drive motor of the extruder may be excessive and the above formula (2) may not be satisfied. In addition, there is a possibility that the shear heat generation in the extruder increases, leading to deterioration of the polycarbonate resin. On the other hand, when the temperature is too high, deterioration of the polycarbonate resin is likely to occur, which tends to cause deterioration of color, lower molecular weight, and lower mechanical strength accompanying it.

The temperature of the polycarbonate resin supplied to the extruder, in addition to controlling the internal temperature of the final polymerization reactor, can be controlled by controlling the temperature of the pipe for supplying the polycarbonate resin to the extruder, or by forming a heat exchanger. .

In addition, in the present invention, the temperature of the polycarbonate resin discharged from the extruder is usually less than 300 ℃, particularly preferably less than 280 ℃, more preferably less than 270 ℃, particularly preferably less than 260 ℃. . When the temperature of the polycarbonate resin discharged from the extruder is too high, the polycarbonate resin tends to deteriorate, which tends to cause deterioration of color, a decrease in molecular weight, and a decrease in mechanical strength accompanying it. On the contrary, when the temperature of the polycarbonate resin discharged from the extruder is too low, the melt viscosity of the polycarbonate resin is high and the load on the extruder is increased, which causes the screw rotation to become unstable or causes an overload of the motor. Or more, more preferably 230 or more, and particularly preferably 240 or more. Usually, in the extruder, there is a heat generation due to the shear of the resin accompanying the rotation of the screw, and in general, the temperature of the polycarbonate resin discharged tends to be higher than the temperature of the polycarbonate resin supplied, and in particular, the molecular weight of the polycarbonate resin This tendency becomes remarkable when this is high and melt viscosity is high. When the temperature of the polycarbonate resin is increased, the melt viscosity decreases, and shear heat generation tends to be suppressed by that amount. However, when the temperature of the polycarbonate resin itself is high, deterioration is likely to occur, resulting in deterioration of color, decrease in molecular weight, and accompanying mechanical strength. Since it tends to cause the deterioration of the polycarbonate resin, it is not easy to perform the extrusion while preventing the deterioration of the high viscosity polycarbonate resin having poor thermal stability.

The temperature of the polycarbonate resin discharged from the extruder is usually controlled by the temperature of the polycarbonate resin supplied, the temperature of the heater attached to the barrel, the supply amount of the polycarbonate resin to the extruder or the screw rotation speed of the extruder, Since it may change also with the structure of a screw element, it is preferable to control these conditions also.

In the present invention, the type of the extruder is a plurality of heaters arranged in order to adjust the temperature of the barrel (sometimes referred to as an alias cylinder), and an extruder having a single shaft or a biaxial screw is used inside the barrel. desirable.

The polycarbonate resin supplied under the above conditions is extruded while heating or cooling the continuous barrel surrounding the screw from the outside with a plurality of heaters. In this invention, it is preferable that at least 1 heater set temperature is less than 250 degreeC, More preferably, it is 240 degrees C or less, More preferably, it is 220 degrees C or less. By setting the heater in this way, when the resin is heated at a higher temperature, the resin is cooled there, and the polycarbonate resin is suppressed from being deteriorated by heat. Although this invention can be implemented even if a part of heaters exceeds the upper limit of the said temperature, in order to prevent overheating more thoroughly, it is more preferable that all the heaters are less than said 250 degreeC.

On the other hand, the heater set to less than 250 degreeC for the purpose of preventing overheating needs to be at least 100 degreeC or more. If there is an excessively low temperature portion in the extruder barrel, the polycarbonate resin is quenched at the portion in contact with the barrel therein, the viscosity is increased, the shear heat is increased, and rather the motor which accelerates deterioration of the polycarbonate resin or rotates the screw. May increase the load. The set temperature of the heater is preferably 120 ° C or higher, more preferably 140 ° C or higher, particularly preferably 160 ° C or higher.

In the extruder, the resin tends to be hotter as the closer to the outlet, especially because of the shear heat generation. For this reason, it is preferable that the part of low temperature exists on an exit side more. That is, each heater is more preferably not set higher than the heater adjacent to the supply side of the polycarbonate resin, that is, higher than the heater adjacent to the supply side of the polycarbonate resin.

It is preferable that it is 5 degreeC or more lower than 10 degreeC or more in at least 1 combination than the heater setting temperature adjacent to the polycarbonate resin supply side of an extruder, and it is more preferable that it is 10 degreeC or more lower. However, when too rapidly quenched, the viscosity of the polycarbonate resin increases, which may result in local overheating. Therefore, the temperature difference with respect to the heater adjacent to the supply side is preferably 50 ° C or lower.

Especially preferably, the set temperature of the heater at the inlet side is 200 degreeC or more and less than 250 degreeC, and the set temperature of the heater at the outlet side is 100 degreeC or more and 220 degrees C or less.

Particularly, in polycarbonate resin having a high viscosity, the shear heat generation due to screw rotation increases and the temperature of the resin discharged increases with respect to the temperature of the supplied resin, while maintaining additive dispersion, devolatilization performance, productivity, and the like. In order to suppress deterioration of the polycarbonate resin due to the shear heat generation, selection of the rotation speed of the screw and the element configuration is important.

(filter)

In this invention, it is preferable to filter with a filter in order to remove foreign substances, such as the burning and a gel, in the polycarbonate resin produced by polycondensation. Especially, in order to remove residual monomer, a by-product phenol, etc. by the pressure reduction devolatilization with the twin-screw extruder which has a vent port, and to mix additives, such as a heat stabilizer and a mold release agent, after extruding a polycarbonate resin with an extruder, It is preferable to filter.

As a form of the said filter, a well-known thing, such as a candle type, a pleat type, and a leaf disc type, can be used, Among these, the leaf disc type which obtains large filtration area with respect to the storage container of a filter is preferable, and a filtration area is obtained large It is preferable to use in combination in plurality. The leaf disc filter is configured by combining a retaining member (also called a retainer) with a filtration member (hereinafter sometimes referred to as a media), and the filters (in some cases, a plurality of sheets) are stored in a storage container. Used in the form of a stored unit (sometimes called a filter unit).

In the present invention, it is preferable that the media of a plurality of meshes are superimposed so that the differential pressure (pressure loss) of the filter is reduced, and that the meshes are made fine in order from the intrusion direction of the resin, and the gel is crushed on the filter surface. The thing of the type which sintered the metal powder for the purpose can also be used.

In the present invention, the mesh of the filter has a filtration accuracy of 99%, preferably 50 µm or less, more preferably 30 µm or less, even more preferably 20 µm or less, and 15 µm or less for particularly reducing foreign matters. When the mesh is smaller, the pressure loss in the filter is increased, which may cause damage to the filter or deteriorate the polycarbonate resin due to shear heat generation, so that the filtration accuracy of 99% is 1 μm or more. It is preferable. In addition, a mesh defined here as 99% of filtration precision means the value of (x) when (beta) x value represented by following formula (11) determined based on ISO16889 is 100.

β χ = (number of primary particles larger than χ μm) / (number of secondary particles larger than χ μm). (11)

(In this case, the primary side means before filtration by a filter and the secondary side indicates after filtration)

The material of the filter media is not limited as long as it has strength and heat resistance necessary for filtration of the resin, but stainless steel such as SUS316 or SUS316L having a low iron content is preferred. Moreover, as a kind of textile, the collection part of the foreign material, such as a plain weave, a twill weave, a flat weave and a twill weave, becomes a regular weave, and a nonwoven fabric type can also be used. In this invention, the nonwoven fabric type with a high collection | capacitance of a gel is preferable, and the type which fixed and sintered the steel wire which comprises a nonwoven fabric among these is preferable.

Moreover, when iron filter is contained in the said filter, since it tends to deteriorate resin at the time of the filtration at the high temperature exceeding 200 degreeC, in the case of stainless steel as mentioned above, it is preferable that content of an iron component is small, It is desirable to passivate before use. The passivation treatment is a method of immersing the filter in an acid such as nitric acid or passing an acid through the filter to form a passivation on the surface, a method of roasting (heating) in the presence of water vapor or oxygen, and a method of using them in combination. These etc. are mentioned, Especially, it is preferable to perform both nitric acid treatment and roasting.

The temperature in the case of roasting the filter is usually 350 ° C to 500 ° C, preferably 350 ° C to 450 ° C, and the roasting time is usually 3 hours to 200 hours, preferably 5 hours to 100 hours. to be. If the temperature of the roasting is too low or the time is too short, the formation of the passivation becomes insufficient, which tends to deteriorate the polycarbonate resin during filtration. On the other hand, if the temperature of roasting is too high or the time is too long, damage to the filter media may be severe and the required filtration accuracy may not be obtained.

The concentration of nitric acid when the filter is treated with nitric acid is usually 5% by weight to 50% by weight, preferably 10% by weight to 30% by weight, and the temperature at the time of treatment is usually 5 ° C to 100 ° C, preferably Preferably 50 degreeC-90 degreeC and processing time are 5 minutes-120 minutes normally, Preferably they are 10 minutes-60 minutes. If the concentration of nitric acid is too low, the treatment temperature is too low, or the treatment time is too short, the formation of passivation is insufficient. If the concentration of nitric acid is too high, the treatment temperature is too high or the treatment time is too long, the filter media may be damaged. There is a possibility that this becomes severe and the necessary filtration precision does not come out.

When the said filter is stored in the storage container, since it becomes easy to advance a filtration and to apply a pressure, ensuring the required filtration area, it is preferable. The material of the containment container is not limited as long as it has strength and heat resistance that can withstand the filtration of the resin, but is preferably stainless steel such as SUS316 or SUS316L having a low iron content. When there is much iron content, there exists a possibility that polycarbonate resin may deteriorate similarly to the above.

In the container of the filter, the supply port and the outlet of the polycarbonate resin may be arranged substantially horizontally, may be arranged substantially vertically, or may be arranged obliquely. In order to suppress the retention of the polycarbonate resin and prevent deterioration of the polycarbonate resin, the supply port of the polycarbonate resin is disposed at the lower part of the filter storage container and the discharge port at the upper part, and the polycarbonate resin before the filtration is provided at the lower part of the storage container of the filter. It is preferable that the polycarbonate resin after being supplied from the filtration is discharged from the top of the storage container.

In addition, the value obtained by dividing the inner volume (m 3) of the filter containment vessel by the polycarbonate resin flow rate (m 3 / min) may be too small to increase the differential pressure of the filter, resulting in damage to the filter. Since it causes deterioration of resin, 1 minute-20 minutes are preferable, Preferably they are 2 minutes-10 minutes, More preferably, they are 3-8 minutes.

In this invention, it is preferable that the linear flux of molten resin in the said filter surface is 0.01-0.5 m / h. The flux of molten resin on the filter surface can be obtained by dividing the processing volume of the polycarbonate resin per hour by the filter area of the filter. If the flux is too small, the residence time during filtration may be prolonged, resulting in deterioration of the polycarbonate resin, which may cause coloration or foreign matter generation. If too large, the shear heat generation during filtration may increase, resulting in coloring or foreign matter generation. Since it may cause, Preferably it is 0.03-0.3 m / h, Especially preferably, it is 0.05-0.15 m / h.

In the method of the present invention, the temperature of the polycarbonate resin before filtration in the filter is usually less than 300 ° C, particularly preferably less than 280 ° C, more preferably less than 270 ° C, particularly preferably 265. It is preferable that it is less than 占 폚, and especially less than 260 占 폚. When the temperature before filtration with the said filter becomes too high, thermal deterioration in a filter unit tends to occur, and there exists a tendency which causes deterioration of a hue, a fall of molecular weight, and the fall of the mechanical strength accompanying it. On the contrary, if the temperature before filtration with the filter is too low, the melt viscosity of the polycarbonate is high, and the load on the filter is increased, which may cause breakage of the filter. Preferably it is 230 degreeC or more, Especially preferably, it is 240 degreeC or more.

In the method of the present invention, the filter unit is usually provided with a heater composed of a plurality of blocks on the outside thereof to control the temperature, but if the set temperature is too high, it may cause deterioration of the polycarbonate resin. Usually, it is set to 280 degrees C or less, Preferably it is 260 degrees C or less, Especially preferably, it is set to 250 degrees C or less. On the other hand, if the set temperature is too low, the melt viscosity becomes high and it becomes difficult to filter with a filter. Therefore, the temperature is usually 150 ° C or higher, preferably 180 ° C or higher, and particularly preferably 200 ° C or higher.

In addition, a pipe for guiding the polycarbonate resin discharged from the filter unit to the die is also usually provided with a heater on the outside thereof. If the set temperature is too high, deterioration of the polycarbonate resin may occur. It is set to 280 degrees C or less, Preferably it is 260 degrees C or less, Especially preferably, it is set to 250 degrees C or less. On the other hand, when the set temperature is too low, the melt viscosity becomes high and the pressure loss in the pipe becomes large. Therefore, the temperature is usually 150 ° C or higher, preferably 180 ° C or higher, particularly preferably 200 ° C or higher. In addition, when the residence time of the polycarbonate resin from the filter unit outlet to the die is long, deterioration of the polycarbonate resin may be caused, so it is usually 1 to 30 minutes, preferably 3 to 20 minutes.

In the method of the present invention, the temperature of the polycarbonate resin discharged from the die through filtration in the filter is preferably 200 ° C or higher, preferably 220 ° C or higher, more preferably 230 ° C or higher, and the upper limit is 280. It is preferably less than 占 폚, preferably less than 270 占 폚, more preferably less than 265 占 폚, particularly preferably less than 260 占 폚. If the temperature of the polycarbonate resin discharged from the die through filtration is too low, the melt viscosity becomes high and the strand formed by extrusion is not stable, which may make it difficult to pelletize with a rotary cutter or the like. On the other hand, when the temperature is too high, thermal deterioration of the polycarbonate resin is likely to occur, which may lead to generation of gas, deterioration of color, reduction of molecular weight, and reduction of mechanical strength accompanying it.

The die is usually provided with a heater, but if the set temperature is too high, it may cause deterioration of the polycarbonate resin. Therefore, the die is usually 280 ° C or lower, preferably 260 ° C or lower, particularly preferably 250 ° C or lower. Set it. On the other hand, when the set temperature is too low, the melt viscosity becomes high and the pressure loss in the pipe becomes large. Therefore, the temperature is usually 150 ° C or higher, preferably 180 ° C or higher, particularly preferably 200 ° C or higher.

Generally, when the polycarbonate resin is filtered through the filter having a small mesh, the temperature rises due to shear exotherm, and in the case of using an extruder, the shear exotherm due to screw rotation is also added, and thus the polycarbonate discharged from the die through filtration. In order to control the temperature of the resin, it is important to comprehensively control the mesh of the filter, the filtration area, the temperature setting, the molecular weight of the polycarbonate resin, the temperature setting of the filter unit, the temperature setting from the filter outlet to the die, and the like. Moreover, when using the said extruder for supply to the said filter, as mentioned above, selection of the throughput of the polycarbonate resin in the said extruder, the rotation speed of a screw, the circumferential speed, the structure of an element, etc. become important.

Moreover, in the method of this invention, it is preferable that the difference of the temperature of the polycarbonate resin before filtration with the said filter, and the temperature of the polycarbonate resin after filtration is within 50 degreeC, More preferably, it is within 30 degreeC, Most preferably, Is within 10 ° C. When the temperature difference of the polycarbonate resin before the filtration by the filter and the polycarbonate resin after the filtration becomes too large, especially when the filter unit is composed of a plurality of leaf disc type filters, the pressure balance on the supply side and the discharge side of the resin collapses. There is a possibility of causing damage to the filter.

Moreover, in the method of this invention, the reduced viscosity ((eta _sp / c) before filtering with the said filter of the polycarbonate resin produced by polycondensation by the said transesterification reaction is filtered using A and the said filter, and dice | dies It is preferable to satisfy the following formula (12) when discharging in the form of a strand from the form and setting the reduced viscosity (η _sp / c) of the polycarbonate resin obtained by using a cutter after cooling to B.

0.8 <B / A <1.1... (12)

More preferably, it is B / A> 0.85, More preferably, it is B / A> 0.9, Especially preferably, it is B / A> 0.95. When B / A is 0.8 or less, it exists in the tendency for the coloring component considered to be produced | generated by a side reaction, and the component used as a precursor of coloring to produce, and it is unpreferable. On the other hand, when the reduced viscosity rises in the polymer filter, since foreign substances such as gels and burns are generated, it is preferable that B / A ≤ 1.0. The measuring method of a reduced viscosity is mentioned later.

In addition, when providing the said extruder between the said polycondensation reactor and the said filter, when the reduced viscosity ((eta _sp / c)) of the polycarbonate resin supplied to the said extruder is set to a, following Formula (3) ) Is desirable.

0.8 <B / a <1.1... (3)

More preferably, it is B / a> 0.85, Especially preferably, it is B / a> 0.9. When B / a is 0.8 or less, it exists in the tendency for the coloring component considered to be produced | generated by a side reaction, and the component used as a precursor of coloring to produce, and it is unpreferable. On the other hand, when the reduced viscosity rises, generation of foreign matters such as gels or burns is increased, so it is preferable that B / a ≤ 1.0.

In order to make the change of the reduction viscosity in a polymer filter or an extruder into the said range, the temperature of the polycarbonate resin in a final reactor, the temperature of the polycarbonate resin which enters a polymer filter, the temperature of the polycarbonate resin discharged from a polymer filter, a polymer filter The throughput per unit time, the choice of mesh, the temperature control from the polymer filter to the die, the residence time, the temperature of the polycarbonate resin supplied to the extruder, the temperature of the polycarbonate resin discharged from the extruder, It is important to select the volatilization pressure, the presence or absence of water, the amount of water, the number of revolutions, the speed of the screw, and the element configuration.

Furthermore, when using the extruder, it is preferable to arrange a gear pump between the extruder and the filter in order to stabilize the supply amount of the polycarbonate resin to the filter. There is no restriction on the type of gear pump, but among them, there is a circuit for guiding a part of polymer from the discharge side of the gear pump to the gland portion through the valve, and applying a constant pressure to the shaft rod to return to the suction port. A self-circulating type that does not use a packing is preferable in view of foreign matter reduction.

In the present invention, at the time of stranding and pelletizing the polycarbonate resin directly in contact with the outside air, in order to prevent foreign matter from being mixed in from the outside air, Class 7, more preferably defined in JIS B 9920 (2002), is more preferable. Is preferably performed in a clean room with higher cleanliness than class 6.

The polycarbonate resin filtered by the filter is cooled and solidified and pelletized by a rotary cutter or the like. It is preferable to use cooling methods such as air cooling and water cooling at the time of pelletization. As the air used for air cooling, it is preferable to prevent reattachment of foreign matters in the air by using air in which foreign matters in the air have been previously removed by a hepa filter or the like. When using water cooling, it is preferable to use the water which removed metal powder in water with ion exchange resin etc., and removed the foreign material in water with the said filter further. It is preferable that the mesh of the filter to be used has a filtration accuracy of 99.9% removal of 10 to 0.45 탆.

In the present invention, heat stabilizers, neutralizing agents, ultraviolet absorbers, mold release agents, colorants, antistatic agents, lubricants, lubricants, plasticizers, compatibilizers, flame retardants, and the like, which are commonly known in the extruder, may be added and kneaded.

Especially, addition of a phosphite ester type and a hindered phenol type heat stabilizer is preferable because it can suppress the molecular weight fall and hue deterioration at the time of extrusion or filtration of the polycarbonate resin of this invention.

Specific examples of the phosphite ester heat stabilizer include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, Trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, mono octyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythryldiphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis (nonylphenyl) penta Erytrityl diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythryl diphosphite, distearyl pentaerythryl diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate , Diphenylmonortho Xenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4'-biphenylenediphosphine tetrakis (2,4-di-tert-butylphenyl), benzene phosphonate dimethyl, benzene phosph Diethyl fonate, benzene phosphonate dipropyl, etc. are mentioned. Among them, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerytrityl diphosphite, bis ( 2,6-di-tert-butyl-4-methylphenyl) pentaerytrityl diphosphite, benzenephosphonic acid dimethyl and the like are preferably used, and tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred. Do.

Specific examples of the hindered phenolic heat stabilizer include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-ste Arylthiopropionate, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerytrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4- Hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate , 4,4'-biphenylenediphosphinate tetrakis (2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert- Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10- tetraoxaspiro (5,5) undecane and the like or one or two or more kinds thereof may be mentioned. Preferably pentaerythryltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate, particularly preferably pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

These heat stabilizers may be used individually by 1 type, or may use 2 or more types together. When the compounding quantity of these heat stabilizers is 100 weight part of polycarbonate resin, 0.0001-1 weight part is preferable, 0.0005-0.5 weight part is more preferable, 0.001-0.2 weight part is more preferable.

(Filtration before polymerization)

On the other hand, in the method of this invention, in order to reduce the foreign material contained in the polycarbonate resin finally obtained, it is also effective to filter a raw material monomer with a raw material filtration filter before performing a polycondensation reaction.

The shape of the raw material filtration filter may be any type such as a basket type, a disc type, a leaf disc type, a tube type, a flat cylindrical type, a pleated cylindrical type, and the like. It is preferable. Moreover, as a filter material which comprises this raw material filtration filter, any of metal wind, a laminated metal mesh, a metal nonwoven fabric, a porous metal plate, etc. may be sufficient, A laminated metal mesh or a metal nonwoven fabric is preferable from a filtration precision viewpoint, and a metal is especially The thing of the type which sintered and fixed the nonwoven fabric is preferable.

There is no restriction | limiting in particular about the material of the raw material filtration filter, A metal, resin, ceramics, etc. can be used, From a viewpoint of heat resistance and color reduction, the metal filter whose iron content is 80% or less is preferable, and SUS304 and SUS316 are especially Stainless steels, such as SUS316L and SUS310S, are preferable.

Moreover, in order to extend the life of the said raw material filtration filter, while ensuring the filtration performance at the time of the filtration of a raw material monomer, it is preferable to use several filter unit, Especially, the mesh of the filter in the unit of the upstream side is C micrometer. In the case where the mesh of the filter in the unit on the downstream side is D μm, in at least one combination, it is preferable that C is larger than D (C> D). When this condition is satisfied, the raw material filtration filter is less likely to be blocked, and the replacement frequency of the raw material filtration filter can be reduced.

Although the mesh of the said raw material filtration filter does not have a restriction | limiting in particular, It is preferable that at least 1 said raw material filtration filter is 10 micrometers or less with 99.9% of filtration accuracy, and when several filter units which comprise the said raw material filtration filter are arrange | positioned. On the most upstream side, preferably, it is 8 micrometers or more, More preferably, it is 10 micrometers or more, On the most downstream side, Preferably it is 2 micrometers or less, More preferably, it is 1 micrometer or less. In addition, the mesh of the said raw material filtration filter here is also determined based on ISO16889 mentioned above.

In the present invention, there is no limitation on the temperature of the raw material fluid at the time of passing the raw material through the raw material filtration filter. However, if the raw material is too low, the raw material is solidified. If the raw material is too high, there is a problem such as thermal decomposition. ° C, preferably 100 ° C to 150 ° C.

In addition, in this invention, you may filter which raw material of multiple raw materials to use, and may filter all, The method is not limited, The raw material mixture of a dihydroxy compound and diester carbonate may be filtered separately. You may mix after filtering. Moreover, in the manufacturing method of this invention, the reaction liquid in the middle of polycondensation reaction can also be filtered with the same filter as the said raw material filtration filter.

(Polycarbonate resin obtained)

It is preferable that the yellow index value of the pellet obtained from the polycarbonate resin obtained by the method of this invention is 90 or less, More preferably, it is 70 or less, Especially preferably, it is 50 or less, Most preferably, it is 40 or less. In order to lower a yellow index value, when using monomer preparation conditions, polymerization reaction conditions, filtration conditions, and an extruder as mentioned above, selection of extrusion conditions, a screw element, etc. needs to be performed suitably.

In addition, the molecular weight of the polycarbonate resin obtained in the method of the present invention can be represented by a reduced viscosity (η _sp / c), the reduced viscosity is usually 0.2 dl / g or more, preferably 0.25 dl / g or more, Preferably it is 0.3 dl / g or more, Especially preferably, it is 0.4 dl / g or more, Usually it is 0.6 dl / g or less, Preferably it is 0.5 dl / g or less, Especially preferably, it is 0.45 dl / g or less. If the reduced viscosity of the polycarbonate resin is too low, there is a possibility that the mechanical strength of the molded article may be small, and when the stretching operation is performed after molding into a film, there is a possibility of causing a breakage in stretching. On the other hand, when too big | large, the fluidity | liquidity at the time of shaping | molding falls and there exists a tendency for not only to reduce productivity or moldability, but also deterioration may become severe by shear heat generation at the time of filtration and extrusion. The reduced viscosity is precisely weighed polycarbonate resin pellets, precisely prepared at 0.6 g / Pa using methylene chloride as a solvent, and measured using a Uberode viscosity tube at a temperature of 20.0 ° C ± 0.1 ° C.

A shear rate of 91.2 sec measured at 240 ℃ of the polycarbonate resin obtained by the method of the present ^invention melt viscosity at ¹ is typically 500 ㎩ · s or more, preferably 1000 ㎩ · s or more, and particularly preferably 1500 ㎩ · It is s or more, and the upper limit is 5000 Pa * s or less normally, Preferably it is 4000 Pa * s or less. If the melt viscosity is too low, the mechanical strength of the molded article tends to be lowered. If the melt viscosity is too high, the shear heat generation in the filter or the extruder may increase as described above, and the deterioration during filtration or extrusion may be severe. In addition, since the melt viscosity also varies depending on the molecular structure in addition to the molecular weight, it is important to select these according to the required performance and to control the above range.

Although there is no restriction | limiting in the glass transition temperature of the polycarbonate resin obtained by the method of this invention, Usually, it is 100 degreeC or more, Preferably it is 120 degreeC or more, and 130 degreeC or more is especially preferable. When glass transition temperature is too low, heat resistance will fall, and therefore, the reliability at the time of using an optical member may fall. On the other hand, when the glass transition temperature is high, the shear heat generation at the time of extrusion may cause deterioration of the polycarbonate resin, or the melt viscosity at the time of filtration with the filter may be too high, leading to deterioration of the polycarbonate resin. It is 160 degrees C or less, Preferably it is 150 degrees C or less, More preferably, it is 145 degrees C or less, Especially preferably, it is 140 degrees C or less. In addition, the glass transition temperature can be measured with a differential scanning calorimeter (DSC), and the temperature (Tig) at which the change in heat capacity at the lowest temperature is measured when measured at a temperature increase rate of 20 ° C / min using a sample of about 10 mg. It defines by the glass transition temperature in this invention.

In the transesterification reaction performed by this invention, when manufacturing the polycarbonate resin of this invention using substituted diphenyl carbonates, such as diphenyl carbonate and a tolyl carbonate, as diester carbonate represented by the said General formula (10), Aromatic monohydroxy compounds, such as a phenol and a substituted phenol, are byproduced and remain in a polycarbonate resin is unavoidable. Since the content of the aromatic monohydroxy compound contained in the polycarbonate resin may cause generation of gas at the time of filtration and odor at the time of molding, using an extruder having a vacuum vent, preferably less than 0.2% by weight, More preferably, it is preferably less than 0.1% by weight, in particular less than 0.08% by weight. However, it is difficult to remove these compounds industrially completely, and the lower limit of content of an aromatic monohydroxy compound is 0.0001 weight% normally.

Moreover, these aromatic monohydroxy compounds may have a substituent naturally depending on the raw material to be used, for example, may have a C5 or less alkyl group. When diphenyl carbonate is used as diester carbonate, an aromatic monohydroxy compound becomes a phenol.

The polycarbonate resin obtained by the method of the present invention can be formed into a molded article by commonly known methods such as an injection molding method, an extrusion molding method, and a compression molding method. Before carrying out various moldings, additives such as heat stabilizers, neutralizers, ultraviolet absorbers, mold release agents, colorants, antistatic agents, lubricants, lubricants, plasticizers, compatibilizers, and flame retardants may be added to the resin as needed. It can also mix with a type | mold blender, a Nauta mixer, a Banbury mixer, an extruder, etc. Moreover, after filtering on the said conditions, you may shape | mold directly into a film, without making into pellets.

Moreover, the polycarbonate resin obtained by the method of this invention has favorable film formability, and can obtain the polycarbonate resin film which is 20 micrometers-200 micrometers in thickness generally.

Since the polycarbonate resin with little coloring and few foreign matters is obtained by the method of this invention, the foreign material whose 25-micrometer or more of maximum length contained in the film of 35 micrometers +/- 5 micrometers thickness obtained by extrusion molding from this resin is preferable. Preferably it is 1000 piece / m <2> or less, More preferably, it is 500 piece / m <2> or less, Most preferably, it can be 200 piece / m <2> or less. Thus, the characteristic that there is little foreign material is especially preferable when using polycarbonate resin for an optical use.

The polycarbonate resin obtained by the method of the present invention is, for example, aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic resin, amorphous polyolefin, ABS, AS, synthetic resins One or two or more kinds of biodegradable resins such as lactic acid and polybutylene succinate and rubber may be kneaded and used as polymer alloys.

According to the present invention, it is possible to provide a polycarbonate resin that is excellent in thermal stability, color and mechanical strength, and has few foreign substances. In addition, in manufacture of a polycarbonate resin film, after manufacturing a polycarbonate resin pellet once in the above procedure, it is not only manufactured using this pellet, but may be manufactured by shape | molding into a film without passing a pellet state.

Example

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by the following example, unless the summary is exceeded. Hereinafter, the physical properties and properties of the polycarbonate were evaluated by the following methods.

(1) Measurement of the oxygen concentration in the polymerization reaction device

It measured using the oxygen meter (1000RS made from AMI company).

(2) reduced viscosity

The polycarbonate resin was dissolved using methylene chloride as a solvent to prepare a polycarbonate solution having a concentration of 0.6 g / dl. Using a Uberode-type viscosity tube (manufactured by Moritomo Chemical Co., Ltd.), the temperature was measured at a temperature of 20.0 ° C ± 0.1 ° C, and a relative viscosity η _rel was obtained from the following equation from the passage time t ₀ of the solvent and the passage time t of the solution,

η _rel = t / t ₀

From the relative viscosity, the specific viscosity η _sp was obtained from the following equation.

η _sp = (η-η ₀ ) / η ₀ = η _rel -1

The specific viscosity was divided by the concentration c (g / dl) to obtain a reduced viscosity η _sp / c. The higher this value, the larger the molecular weight.

(3) glass transition temperature of polycarbonate resin

The glass transition temperature of polycarbonate resin was measured using the differential scanning calorimeter (DSII62 manufactured by SII Nanotechnology Co., Ltd.). About 10 mg of polycarbonate resin samples were put into the aluminum pan of the company, and it sealed, and it heated up from room temperature to 250 degreeC at the temperature increase rate of 20 degree-C / min under 50 mL / min of nitrogen stream. After maintaining temperature for 3 minutes, it cooled to 30 degreeC at 20 degree-C / min. It hold | maintained at 30 degreeC for 3 minutes, and it heated up again at 200 degreeC at the speed | rate of 20 degree-C / min. The extrapolation glass transition start temperature was employ | adopted from the DSC data obtained by the temperature rising of the 2nd time.

(4) Measurement of the structural unit ratio derived from each dihydroxy compound in the polycarbonate resin

Structural unit ratio derived from each dihydroxy compound in polycarbonate resin weighs 30 mg of polycarbonate resins, melt | dissolves in about 0.7 ml of heavy chloroform, makes it a solution, and puts it into the tube for NMR of internal diameter 5mm, The ¹ H NMR spectrum was measured at room temperature using JNM-AL400 (resonant frequency 400 MHz) manufactured by Nippon Electronics Co., Ltd. The structural unit ratio derived from each dihydroxy compound was calculated | required from the signal intensity ratio based on the structural unit derived from each dihydroxy compound.

(5) Measurement of phenol content and DPC content in polycarbonate resin

After dissolving 1.00 g of polycarbonate resin samples in 5 ml of methylene chloride to form a solution, acetone was added so that the total amount was 25 ml, and reprecipitation treatment was performed. The solution was filtered through a 0.2 μm disk filter and quantified by liquid chromatography.

(6) Evaluation method of initial color of polycarbonate resin

The color of the polycarbonate resin was evaluated according to ASTM D1925 by measuring the yellow index (YI) value in the reflected light of the pellets. The apparatus used the spectrophotometer CM-5 by Konica Minolta Co., Ltd., and measurement conditions selected the measurement diameter of 30 mm and SCE. The calibration glass CM-A212 for a chalet measurement was put into a measurement part, and zero calibration was performed by covering the zero calibration box CM-A124 from it, and white calibration was performed using the built-in white calibration board. It measured using the white calibration plate CM-A210, and confirmed that L * became 99.40 ± 0.05, a * was 0.03 ± 0.01, b * was -0.43 ± 0.01, and YI was -0.58 ± 0.01. The pellet was measured by placing the pellet in a cylindrical glass container having an inner diameter of 30 mm and a height of 50 mm to a depth of 30 mm or more. After removing a pellet from a glass container, the operation which measures again was repeated twice and the average value of the measured value of 3 times in total was used. Smaller YI values indicate no yellowness and better quality.

(7) Measurement of melt viscosity (Pa · s)

The sample dried at 120 ° C for 6 hr was heated to 240 ° C using a capillary rheometer (manufactured by Toyo Seiki Co., Ltd.) equipped with a die having a capillary having a diameter of 1 mm φ x 10 mm length. And it measured between shear rate (gamma) = 9.12-1824 (sec- ¹ ), and melt viscosity in 91.2 sec ^{- 1} was read.

(8) wavelength dispersion of birefringence

Polycarbonate resin which was vacuum-dried at 80 degreeC for 5 hours, single-screw extruder (Isuzu Chemical Co., Ltd. make, screw diameter 25mm, cylinder set temperature: 220 degreeC), T die (width 200mm, set temperature: 220 degreeC), The film of thickness 100micrometer +/- 5micrometer was produced using the film film forming apparatus provided with the roll (setting temperature: 120-130 degreeC) and a winding machine. The sample of width 6cm and length 6cm was cut out from this film. This sample was drawn by a batch type biaxial stretching apparatus (manufactured by Toyo Co., Ltd.) at a stretching speed of 720 mm / min (strain rate of 1200% / min) at a glass transition temperature of + 15 ° C of polycarbonate resin, 1. Uniaxial stretching of x2.0 times was performed and the transparent film with a uniform thickness was obtained. At this time, extending | stretching was performed in the state (drawing ratio 1.0) which was perpendicular | vertical with respect to the extending | stretching direction.

The sample which cut out the said transparent film into 4 cm in width and 4 cm in length is measured by phase difference measuring apparatus (KOBRA-WPR by Oji Scientific Instruments Co., Ltd.), and measuring phase difference (R450) of 450 nm and phase difference (R550) of 550 nm. It was. And the ratio (R450 / R550) of the measured phase difference R450 and phase difference R550 was calculated. If the retardation ratio is greater than 1, the wavelength dispersion is positive, and less than 1 becomes negative (reverse dispersion). As the ratio of each phase difference is smaller than 1, negative wavelength dispersion is stronger.

(9) Evaluation method of foreign matter number

Manufactured by OPTICAL CONTROL SYSTEMS, using a single screw extruder (diameter 20 mm, single flight, L / D = 25), cast film die (150 mm width), chill roll, cylinder set temperature 250 ℃, roll temperature 133 ℃ A film having a thickness of 35 ± 5 μm was molded and a foreign matter of 25 μm or more was counted using a gel counter system (type FSA100).

(10) gas breaking frequency of strand

Continuous operation was carried out and the frequency at which the strands were cut off by gas was counted.

The symbol of the compound used in description of the following Example is as follows.

BHEPF: 9,9-bis (4- (2-hydroxyethoxy) -phenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd.)

BCF: 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd.)

ISB: isosorbide (made by rocket Frere, product name: POLYSORB PS)

PEG: Polyethylene glycol (manufactured by Sanyo Chemical Co., Ltd.)

DEG: Diethylene glycol (manufactured by Mitsubishi Chemical Corporation)

CHDM: 1,4-cyclohexanedimethanol (manufactured by Shin-Nihon Ewha Co., Ltd.)

1,6-HD: 1,6-hexanediol (manufactured by BASF)

SPG: Spiroglycol (nickname: 3,9-bis (1,1-dimethyl-2-methoxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane) (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

DPC: diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation)

In addition, the detailed conditions of Examples 1-14 and Comparative Example 1 were described in following Tables 1-3.

Example 1

In a raw material preparation preparation sufficiently nitrogen-substituted (oxygen concentration 0.0005 vol% to 0.001 vol%), the raw material prepared so that the molar ratio of BHEPF / ISB / PEG (average molecular weight 1000) / DPC was 43.2 / 55.6 / 1.2 / 99 was obtained. Aqueous solution from the catalyst supply pipe connected to the raw material supply pipe, while continuously supplying a constant amount to the first polymerization reactor having a thermal medium jacket, a thermal medium inner coil, and a stirring blade, an outlet pipe connected to a vacuum pump, and a condenser as a heat medium. The magnesium acetate tetrahydrate thus obtained was continuously fed so as to be 19 × 10 ⁻⁶ mol (magnesium metal atom equivalent) per 1 mol of all the dihydroxy compounds. After mixing the raw material and the aqueous catalyst solution in a pipe, two pleat-type cylindrical filtration filters were installed in the flow path until entering the first polymerization reactor, and the mesh of the upstream raw material filtration filter was 10 µm and downstream. The mesh of was set to 1 m. In the outflow pipe of the first polymerization reactor, hot water (inlet temperature) is used as the refrigerant between the reflux condenser and the vacuum pump in order to condense the reflux cooler using oil (inlet temperature 130 ° C.) as the refrigerant, and phenol which does not condense with the reflux condenser. 45 degreeC) was used for the condenser. While the rotation speed of the stirring blades of the first polymerization reactor was kept constant, the reaction liquid was continuously drawn out from the bottom of the reactor tank by controlling the temperature to be constant at an internal temperature of 196 ° C., a pressure of 26.3 kPa, and a residence time of 1.5 hours. Supplied. Similarly to the first polymerization reactor, the second polymerization reactor is equipped with a reflux condenser and a condenser in the heat medium jacket, the heat medium internal coil, the stirring vane, the outlet pipe connected to the vacuum pump, and the condenser. (Iii) The reaction solution was continuously taken out from the bottom of the reactor tank while being controlled to be constant at a residence time of 1 hour and fed to the third polymerization reactor. The third polymerization reactor was controlled to be constant at an internal temperature of 218 ° C., a pressure of 20.9 kPa, and a residence time of 1 hour, and then the polycondensation reaction was carried out while distilling off the by-product phenol, and the reaction solution was continuously self-circulated from the bottom of the tank. Extraction was carried out using a type seal gear pump and fed to a horizontal stirring reactor (fourth polymerization reactor) having two horizontal rotating shafts and discontinuous stirring vanes mounted at a right angle to the horizontal axis. In the fourth polymerization reactor, the polycondensation reaction was further performed while controlling the internal temperature near the inlet to 220 ° C., the internal temperature near the outlet to 240 ° C., the pressure to 1.4 kPa, and the residence time of 2 hours. The resulting polycarbonate resin has an additive supply port and three vent holes, and is self-circulating in a twin screw extruder having a length of 6% of the kneading disk, which accounts for L / D = 42, the length of the elements constituting the whole screw of the extruder. It was fed continuously using a seal gear pump. The pipe connecting the gear pump and the extruder was a jacket-type double pipe in which fruit flowed outward, and the temperature of the fruit was set at 250 ° C. The temperature of the resin supplied to the extruder was 248 degreeC as measured by the resin thermometer installed in the inlet of an extruder. 0.1% water is supplied to the polycarbonate resin to be treated in the extruder, and a side feeder is provided downstream of the water supply nozzle and the vent port following it, and pentaerythritol tetrakis [3- (3,5-di-) t-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010) to 0.1 part by weight based on 100 parts by weight of polycarbonate resin, tris (2,4-di-t-butylphenyl) phosphite (brand name: Adecastab 2112) was fed continuously to equal 0.05 parts by weight. The vent port was connected to a vacuum pump to remove volatile components contained in the polycarbonate resin. In the setting of the heater temperature of the barrel of the extruder, the upstream four blocks were 245 ° C and the downstream 6 blocks were 225 ° C, and the screw rotation speed was 274 rpm. At this time, the polycarbonate resin supplied to the extruder was temporarily extracted, and various analyzes were performed. The results are shown in Table 1.

The polycarbonate resin processed by the extruder was supplied to the filter unit in which the inlet of resin was lower part and the outlet was upper part using the self-circulating seal gear pump installed in the exit. The resin temperature measured by the resin thermometer provided at the inlet of the filter unit was 278 ° C. Table 1 shows various measured values of the resin sampled at the inlet of the filter unit. The inside of the filter unit was fitted with a leaf disc filter (manufactured by Nippon Pole Co., Ltd.) (material: stainless steel (SUS304, SUS316)) of a mesh of 7 m, to remove foreign substances in the polycarbonate resin. The filter is subjected to roasting treatment at 310 ° C. for 40 hours at 310 ° C. in a steam atmosphere and 52 hours at 420 ° C. in an air atmosphere before use, and then cooled to room temperature. It formed, and used what wash and dried. The filter unit was provided with the heater comprised from the some block, and set each temperature to 245 degreeC. On the outlet side of the filter unit, a die was provided through a polymer pipe having a heater composed of a plurality of blocks, and the heater temperature of the polymer pipe was set to 240 ° C and the heater of the die to 235 ° C. The resin temperature at the die exit was measured directly by inserting a thermometer into the die hole. The polycarbonate resin was extracted in the form of strands in a room maintained at a cleanness of class 10000 from the die, solidified in a water bath, and pelletized with a rotary cutter. The results are shown in Table 1.

[Example 2]

Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4-di-t-butylphenyl) phosphite are not added It carried out similarly to Example 1 except not having carried out. The results are shown in Table 1.

[Example 3]

The raw materials were prepared so that the molar ratio of BHEPF / ISB / PEG (average molecular weight 1000) / DPC was 40.3 / 59.4 / 0.3 / 99, the internal temperature of the first polymerization reactor was 194 ° C, the pressure was 27.8 kPa, and the internal temperature of the second polymerization reactor. 208 ℃, the pressure 25.8 kPa, the internal temperature of the third polymerization reactor 221 ℃, the pressure 23.0 kPa, the internal temperature near the inlet of the fourth polymerization reactor 225 ℃, the internal temperature near the outlet 239 ℃, the pressure to 1.3 kPa Then, it carried out similarly to Example 1 except having changed the screw rotation speed of the extruder, the polycarbonate resin extrusion amount / extruder barrel cross-sectional area, the filter setting of the heater, and the molten resin linear velocity in the filter surface as shown in Table 1. The results are shown in Table 1.

Example 4

Set the heater temperature of the barrel of the extruder to 240 ° C for the four blocks upstream and 220 ° C for the six blocks downstream, and change the screw rotation speed of the extruder, the heater set temperature of the filter, and the heater set temperature of the die as shown in Table 1. It carried out similarly to Example 2 except having carried out. The results are shown in Table 1.

[Example 5]

It carried out similarly to Example 1 except having removed some polycarbonate resin from the piping which supplies a polycarbonate resin to an extruder in a 4th polymerization reactor, and reduced the amount of supply resin to an extruder. The results are shown in Table 1.

[Example 6]

The raw materials were prepared so that the molar ratio of BHEPF / ISB / DPC was 40/60/100, the pressure of the first polymerization reactor was 33 kPa, the internal temperature of the second polymerization reactor was 201 deg. C, the pressure was 25 kPa, and the third polymerization reactor was The internal temperature was 241 ° C, the pressure was 18.3 kPa, the internal temperature near the inlet of the fourth polymerization reactor was 235 ° C, the internal temperature near the outlet was 250 ° C, and the pressure was 1.1 kPa. It carried out similarly to Example 1 except having changed the flow volume of the container volume / polycarbonate resin, and the molten resin linear velocity in the filter surface according to Table 1. The results are shown in Table 1.

[Example 7]

It carried out similarly to Example 1 except having made the length of the kneading disc 12% of the length of the element which comprises the whole screw of an extruder. The results are shown in Table 1.

[Example 8]

The internal temperature near the inlet of the fourth polymerization reactor was 220 ° C, the internal temperature near the outlet was 235 ° C, the pressure was 1.2 kPa, and the fruit temperature of the pipe connecting the gear pump and the extruder at the outlet of the fourth polymerization reactor was set to 230 ° C. Set the heater temperature of the barrel of the extruder to 240 ° C for the four blocks upstream and 220 ° C for the six blocks downstream, and set the screw rotation speed of the extruder, the heater set temperature of the filter, and the heater set temperature of the die as shown in Table 1. It carried out similarly to Example 1 except having changed. The results are shown in Table 1.

[Example 9]

As a raw material monomer, a raw material prepared so that the molar ratio of BHEPF / ISB / DEG / DPC is 37.0 / 52.7 / 10.3 / 101 is used, and as a catalyst, magnesium acetate tetrahydrate is 14 × 10 ^-6 mol per mol of all dihydroxy compounds ( Magnesium metal atom), and the supply amount per unit time of the raw material is increased than in Example 8, the residence time of the first polymerization reactor is 0.9 hours, the residence time of the second polymerization reactor is 0.6 hours, The residence time is 0.6 hours, the residence time of the fourth polymerization reactor is 1.1 hours, the pressure of the fourth polymerization reactor is 0.7 kPa, the mesh of the filter is 15 µm, and tris (2,4-di-t-butylphenyl is used. ) The same process as in Example 8 was carried out except that no phosphite (trade name: Adeka Stave 2112) was added.

[Example 10]

In Example 1, the heater temperature of the barrel of the extruder was set in the same manner as in Example 1 except that the upstream four blocks were 250 ° C and the downstream six blocks were 255 ° C. The results are shown in Table 1.

Comparative Example 1

It carried out similarly to Example 5 except having removed some polycarbonate resin from the piping which supplies a polycarbonate resin to an extruder in a 4th polymerization reactor, and reduced the amount of supply resin to an extruder. Molecular weight (melt viscosity) drop and coloring (pellet YI) were remarkable, and foreign material also increased. The results are shown in Table 1.

[Example 11]

As a raw material monomer, a raw material prepared so that the molar ratio of BCF / SPG / CHDM / DPC is 29.3 / 35.9 / 34.8 / 103 is used, and as a catalyst, calcium acetate monohydrate is 200 × 10 ^-6 mol per mol of all dihydroxy compounds ( It was carried out in the same manner as in Example 1 except that the temperature of the pipe connecting the gear pump and the extruder at the outlet of the fourth polymerization reactor was set to 240 ° C, and no thermal stabilizer was added. . The results are shown in Table 2.

[Example 12]

As a raw material monomer, a raw material prepared so that the molar ratio of BCF / SPG / 1,6-HD / DPC was 30.9 / 47.4 / 21.7 / 102 was used, and as a catalyst, calcium acetate monohydrate was 250 × 10 per mol of the total dihydroxy compound. ^It carried out similarly to Example 11 except having used to be ^-6 mol (calcium metal atom conversion). The results are shown in Table 2.

[Example 13]

Using the polycarbonate resin pellets obtained in Example 10, extrusion operation was performed using a biaxial extruder (LABOTEX30HSS) manufactured by Nippon Steel Mill Co., Ltd. having two vent holes, and the polycarbonate resin discharged from the extruder was stranded. Extracted in the form of, solidified in a water bath and pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump to remove the volatile components contained in the polycarbonate resin. In the setting of the heater temperature of the barrel of the extruder, the uppermost block was 100 ° C, the subsequent five blocks were 245 ° C, the downstream two blocks were 225 ° C, and the screw rotation speed was 200 rpm. The results are shown in Table 3.

[Example 14]

It carried out similarly to Example 13 except having used the polycarbonate resin pellet obtained in Example 11. The results are shown in Table 3.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. This application is based on a Japanese patent application filed on March 31, 2011 (Japanese Patent Application No. 2011-078707), and a Japanese patent application filed on March 31, 2011 (Japanese Patent Application No. 2011-078857). Its contents are hereby incorporated by reference.

1a: Raw material (diester carbonate) supply port
1b, 1c: raw material (dihydroxy compound) supply port
1d: catalyst supply port
2a: raw material mixing tank
3a: anchor type stir blade
4a: raw material feed pump
4b, 4c, 4d: gear pump
5a: raw material filtration filter
6a: first male stirred reactor
6b: second male stirred reactor
6c: third male stirred reactor
6d: fourth horizontal stirring reactor
7a, 7b, 7c: Max Blend Wings
7d: 2-axis spectacle stirring wing
8a, 8b: internal heat exchanger
9a, 9b: reflux cooler
10a, 10b: reflux tube
11a, 11b, 11c, 11d: outlet pipe
12a, 12b, 12c, 12d: condenser
13a, 13b, 13c, 13d: decompression device
14a: effluent recovery tank
15a: extruder
15b: polymer filter
15c: dice
16a: strand cooling tank
16b: strand cutter
16c: air transfer blower
16d: Product Hopper
16e: Meter
16f: product envelope (paper envelope, flexible container, etc.)

Claims (32)

A polycarbonate resin is obtained by a polycondensation reaction using at least a dihydroxy compound represented by the following general formula (1) as a raw material monomer, the resulting polycarbonate resin is fed to an extruder, kneaded, and then discharged from a die to be polycarbonate As a method of producing a resin, a polycarbonate that satisfies the following formula (2) when the weight of the resin extruded per hour by the extruder is W (kg / h) and the cross-sectional area of the barrel of the extruder is S (m 2). Method for producing a resin.
[Chemical Formula 1]

(In General Formula (1), R ₁ to R ₄ each independently represent a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 cycloalkyl group, or a substituted or unsubstituted group. A C6-C20 aryl group is represented, X is a substituted or unsubstituted C2-C10 alkylene group, a substituted or unsubstituted C6-C20 cycloalkylene group, or a substituted or unsubstituted C6-C20 aryl group A rene group, m and n each independently represent an integer of 0 to 5)
12000? W / S? (2) The method of claim 1,
The glass transition temperature of the polycarbonate resin discharged | emitted from the said dice is 120 degreeC or more and 150 degrees C or less,
The manufacturing method of polycarbonate resin whose temperature at the time of supplying to the said extruder is 180 degreeC or more and 250 degrees C or less. 3. The method according to claim 1 or 2,
The barrel which comprises the said extruder is equipped with some heater, The manufacturing method of the polycarbonate resin which makes at least one heater setting temperature of these heaters 100 degreeC or more and less than 250 degreeC. The method of claim 3, wherein
The manufacturing method of the polycarbonate resin which makes all the preset temperatures of the said some heater 100-100 degreeC or less. The method according to claim 3 or 4,
The manufacturing method of the polycarbonate resin which does not make each set temperature of the said some heater higher than the heater set temperature adjacent to the polycarbonate resin supply side of the said extruder. 6. The method according to any one of claims 1 to 5,
A method for producing a polycarbonate resin, wherein the reduced viscosity (η _sp / c) of the polycarbonate resin discharged from the die is 0.2 dl / g or more and 0.6 dl / g or less. 7. The method according to any one of claims 1 to 6,
A shear rate of 91.2 sec measured at 240 ℃ of the polycarbonate resin obtained is discharged from the die ^- the melt viscosity of from ¹ 1000 ㎩ · s at least 5000 ㎩ · s or less The method of the polycarbonate resin. The method according to any one of claims 1 to 7,
The manufacturing method of the polycarbonate resin which uses 18 mol% or more of dihydroxy compounds represented by the said General formula (1) as said raw material monomer with respect to all the dihydroxy compounds. The method according to any one of claims 1 to 8,
A method for producing a polycarbonate resin, wherein the temperature of the polycarbonate resin obtained by being discharged from the die is 230 ° C or more and less than 280 ° C. 10. The method according to any one of claims 1 to 9,
The screw of the said extruder is comprised from the some element, At least 1 of the said elements is a kneading disk, and the total length of the kneading disk is 20% or less of the said screw full length, The manufacturing method of the polycarbonate resin. 11. The method according to any one of claims 1 to 10,
The manufacturing method of the polycarbonate resin which performs the operation of kneading a heat stabilizer using the said extruder. 12. The method according to any one of claims 1 to 11,
After kneading with the extruder, the method of producing a polycarbonate resin is carried out in a molten state by using a filter having a mesh of 50 μm or less. 13. The method of claim 12,
The manufacturing method of polycarbonate resin whose line speed of molten resin in the said filter surface is 0.01-0.5 m / h. The method according to claim 12 or 13,
A method for producing a polycarbonate resin, wherein a gear pump is disposed between the extruder and the filter. 15. The method according to any one of claims 12 to 14,
The said filter is stored in the container, The value obtained by dividing the internal volume (m <3>) of the said storage container by the flow volume (m <3> / min) of the said polycarbonate resin is 2 to 10 minutes. 16. The method according to any one of claims 12 to 15,
The manufacturing method of the polycarbonate resin containing the metal in which the said filter prebaked at the temperature of 350 degreeC or more and 500 degrees C or less. 17. The method according to any one of claims 12 to 16,
The said filter is stored in the container, the polycarbonate resin before the said filtration is supplied from the lower part of the storage container of the said filter, and the polycarbonate resin after filtration is discharged from the upper part of the said storage container. 18. The method according to any one of claims 12 to 17,
A method for producing a polycarbonate resin, wherein the polycarbonate resin is supplied to the filter after performing an operation for devolatilization with a twin screw extruder having a vent port. 19. The method according to any one of claims 12 to 18,
The reduced viscosity (η _sp / c) of the polycarbonate resin supplied to the extruder is a,
When the filter is filtered using the filter, discharged from the die, and the reduced viscosity (η _sp / c) of the polycarbonate resin obtained after cooling is set to B,
The manufacturing method of polycarbonate resin which satisfy | fills following formula (3).
0.8 <B / a <1.1 ‥ (3) 20. The method according to any one of claims 1 to 19,
The manufacturing method of the polycarbonate resin obtained by polycondensing the dihydroxy compound and diester carbonate represented by the said General formula (1) by the transesterification reaction in the presence of a catalyst. 21. The method of claim 20,
A method for producing a polycarbonate resin, wherein the polycarbonate resin produced by polycondensation by the transesterification reaction is fed into the extruder and kneaded without being solidified. 22. The method according to claim 20 or 21,
A method for producing a polycarbonate resin, wherein the catalyst is at least one metal compound selected from the group consisting of metal and lithium of Group 2 of the long periodic table. 23. The method according to any one of claims 1 to 22,
The manufacturing method of the polycarbonate resin which uses the dihydroxy compound which has a site | part represented by following General formula (4) in a part of structure other than the dihydroxy compound represented by the said General formula (1) as a raw material monomer.
(2)

(Except the case where the site represented by the general formula (4) is part of -CH ₂ -OH) 24. The method of claim 23,
The dihydroxy compound which has a site | part represented by the said General formula (4) is a manufacturing method of the polycarbonate resin which is a compound which has a cyclic ether structure. 25. The method of claim 24,
The manufacturing method of the polycarbonate resin whose dihydroxy compound which has a site | part represented by the said General formula (4) is isosorbide. 26. The method according to any one of claims 1 to 25,
In addition to the dihydroxy compound represented by the said General formula (1) as a raw material monomer, the dihydroxy compound represented by the following General formula (5), the dihydroxy compound represented by the following General formula (6), and following General formula (7) The manufacturing method of the polycarbonate resin using 1 or more types of dihydroxy compounds chosen from the group which consists of dihydroxy compounds shown.
(3)

(In said general formula (5), R <_5> represents a C4-C20 substituted or unsubstituted cycloalkylene group.)
[Chemical Formula 4]

(In said general formula (6), R <_6> represents a C4-C20 substituted or unsubstituted cycloalkylene group.)
[Chemical Formula 5]

(In formula (7), R ₁₁ represents a chain alkylene group having 2 to 20 carbon atoms.) 27. The method according to any one of claims 1 to 26,
The manufacturing method of the polycarbonate resin whose content of the aromatic monohydroxy compound contained in the said polycarbonate resin is 0.0001 weight% or more and less than 0.2 weight%. The method according to any one of claims 1 to 27,
The manufacturing method of the polycarbonate resin which filters the said raw material monomer with a raw material filtration filter before performing a polycondensation reaction. The polycarbonate resin whose yellow index value obtained by the manufacturing method in any one of Claims 1-28 is 70 or less. The polycarbonate resin obtained by the production method according to any one of claims 1 to 28, or the polycarbonate resin according to claim 29, wherein the resin is molded into a film having a thickness of 35 μm ± 5 μm. The polycarbonate resin whose foreign material whose maximum length contained in a film is 25 micrometers or more is 1000 piece / m <2> or less. The polycarbonate resin film whose thickness obtained by shape | molding the polycarbonate resin of Claim 30 is 20 micrometers-200 micrometers. A polycarbonate resin is obtained by a polycondensation reaction using at least a dihydroxy compound represented by the following general formula (1) as a raw material monomer, the resulting polycarbonate resin is fed to an extruder, kneaded, and then discharged from a die to be polycarbonate As a method for producing a resin,
The glass transition temperature of the polycarbonate resin discharged | emitted from the said dice is 120 degreeC or more and 150 degrees C or less,
The temperature at the time of feeding to the said extruder is 180 degreeC or more and less than 250 degreeC,
The manufacturing method of polycarbonate resin which satisfy | fills following formula (2), when the weight of resin extruded per hour by the said extruder is W (kg / h), and the cross-sectional area of the barrel of the extruder is S (m <2>).
[Chemical Formula 6]

(In General Formula (1), R ₁ to R ₄ each independently represent a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 cycloalkyl group, or a substituted or unsubstituted group. A C6-C20 aryl group is represented, X is a substituted or unsubstituted C2-C10 alkylene group, a substituted or unsubstituted C6-C20 cycloalkylene group, or a substituted or unsubstituted C6-C20 aryl group A rene group, m and n each independently represent an integer of 0 to 5)
12000? W / S? (2)

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