KR101380522B1 - Method for manufacturing polycarbonate resin, polycarbonate resin, polycarbonate-resin film, and methods for manufacturing polycarbonate-resin pellets and polycarbonate-resin films - Google Patents

Abstract

The present invention relates to a method for producing a polycarbonate resin which is excellent in optical properties, thermal stability, color, and mechanical strength, and which produces polycarbonate resin pellets or polycarbonate resin films with little foreign matter efficiently and stably.

Description

METHOD FOR MANUFACTURING POLYCARBONATE RESIN, POLYCARBONATE RESIN, POLYCARBONATE-RESIN FILM, AND METHODS FOR MANUFACTURING POLYCARBONATE- RESIN PELLETS AND POLYCARBONATE-RESIN FILMS}

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 such advantages as transparency, heat resistance, or 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 or lens applications such as flat panel displays, which are rapidly spreading in recent years, more advanced optical properties such as low birefringence or low photoelastic coefficient are required, and aromatic polys having conventional bisphenols as monomer components. With carbonate resin, it became impossible to meet the demand.

In recent years, polycarbonate resins having a dihydroxy compound having a fluorene structure as a monomer have been proposed, and a retardation film (for example, Patent Documents 1 to 4) or a lens having a small birefringence (for example, expressing a specific phase difference) Application to Patent Documents 5 and 6 is proposed.

In applications in which such high optical properties are required, high optical reliability is required as compared with general injection molded parts or extrusion molded parts, and incorporation or coloring of foreign matters is a particularly serious problem. As a method for solving this problem, a method is disclosed in which a polycarbonate resin having a fluorene structure is extruded by an extruder and then filtered by a filter. (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, if the polycarbonate resin having a fluorene structure is to be filtered using a filter in a molten state, the melt viscosity is too high, resulting in a problem of deterioration of the resin due to shear heat generation during filtration.

In addition, if a filter having high filtration accuracy is used while suppressing deterioration due to shear heat generation, the throughput of the polycarbonate resin should be reduced, or the filtration area should be excessively increased. As a result, the time required for the filtration treatment is reduced. It becomes long and the problem which causes deterioration of a polycarbonate resin arises.

On the other hand, in order to reduce the melt viscosity of the polycarbonate resin in order to shorten the time required for the filtration treatment, it is necessary to lower the molecular weight of the polycarbonate resin itself or increase the filtration temperature.

However, if the molecular weight of the polycarbonate resin itself is lowered, the mechanical strength or the heat resistance is lowered. If the temperature at the time of filtration is increased, the resin is decomposed and degraded, so that a resin that satisfies physical properties such as mechanical strength cannot be obtained. In addition, there was a dilemma in that it was not possible to stably pelletize or form a film by encouraging coloring or causing gas breakage of the strands or silver-colored defects of the film by the decomposition gas.

Disclosure of Invention An object of the present invention is to solve the above-mentioned problems and to efficiently and stably produce a polycarbonate resin pellet or a polycarbonate resin film which is excellent in optical properties, thermal stability, color, and mechanical strength and has little foreign matter. Is to provide.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, after earnestly examining, in the method of manufacturing the pellet or the film of the polycarbonate resin which has a fluorene structure, by filtering a polycarbonate resin on specific conditions, an optical characteristic and a mechanical A method of stably producing a polycarbonate resin pellet or a polycarbonate resin film excellent in strength and color and having few foreign matters was found.

That is, the summary of this invention exists in the following [1]-[28].

[1] A polycarbonate resin obtained by polycondensation of a dihydroxy compound and a diester carbonate using a filter, and then filtered and solidified by cooling, wherein the dihydroxy compound is a general formula ( The polycarbonate resin is filtered so that at least the dihydroxy compound represented by 1) is contained, and the mesh of the said filter is 50 micrometers or less, and the temperature of the polycarbonate resin after filtering using the said filter is 200 degreeC or more and less than 280 degreeC. The manufacturing method of the polycarbonate resin characterized by the above-mentioned.

[Chemical Formula 1]

[The above general formula (1) of, R ₁ - R ₄ are each independently a hydrogen atom, a substituted or unsubstituted, having 1 to 20 carbon atoms an alkyl group, a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituted or beach A C6-C20 aryl group of the ring, X represents a substituted or unsubstituted C2-C10 alkylene group, a substituted or unsubstituted C6-C20 cycloalkylene group, or a substituted or unsubstituted C6-C20 Represents an arylene group, and m and n each independently represent an integer of 0 to 5;

[2] The method for producing a polycarbonate resin according to [1], wherein the glass transition temperature of the polycarbonate resin obtained by cooling and solidification is 50 ° C or more and less than 180 ° C.

[3] The method for producing a polycarbonate resin according to [1] or [2], wherein the reduced viscosity (ηsp / c) of the polycarbonate resin obtained by cooling and solidification is 0.2 dl / g or more and 0.6 dl / g or less.

[4] of the polycarbonate resin obtained by solidifying the cooling, a shear rate of 91.2 sec measured at 240 ℃ ^- in any of the melt viscosity of from ¹ 1000 Pa · s at least 5000 Pa · s less than or equal to [1] to [3] The manufacturing method of polycarbonate resin described.

[5] The polycarbonate resin obtained by cooling and solidifying is obtained by using 18 mol% or more of the dihydroxy compound represented by the general formula (1) as the raw material monomer with respect to all the dihydroxy compounds [1] to [4] The manufacturing method of polycarbonate resin in any one of].

[6] When the reduced viscosity (ηsp / c) before filtration with the filter of the polycarbonate resin is A and the reduced viscosity (ηsp / c) of the polycarbonate resin obtained by cooling and cooling is set to B, The manufacturing method of the polycarbonate resin in any one of [1]-[5] which satisfy | fills Formula (2).

[7] The claims [1] to [6, wherein the polycarbonate resin is obtained by polycondensing at least a dihydroxy compound represented by the general formula (1) and a diester carbonate by a transesterification reaction in the presence of a catalyst. The manufacturing method of polycarbonate resin in any one of].

[8] The method for producing a polycarbonate resin according to [7], wherein the polycarbonate resin obtained by polycondensation is fed to the filter and filtered while being in a molten state without solidifying.

[9] [7] or [8], wherein the polycondensation is carried out using a catalyst and the catalyst is at least one metal compound selected from the group consisting of metals and lithium of Group 2 of the long-period periodic table. The manufacturing method of polycarbonate resin described.

[10] In addition to the dihydroxy compound represented by the general formula (1), the polycarbonate resin uses a dihydroxy compound having a moiety represented by the following general formula (3) as part of the structure: [1] ] The manufacturing method of polycarbonate resin in any one of [9].

(2)

[Provided that the portion represented by the above general formula (3) except for a part of -CH ₂ -OH]

[11] The poly according to [10], wherein the dihydroxy compound having a moiety represented by General Formula (3) is a compound having a cyclic ether structure, and the moiety represented by General Formula (3) is part of a cyclic ether structure. Method for producing a carbonate resin.

[12] The dihydroxy compound represented by the following general formula (4), in addition to the dihydroxy compound represented by the general formula (1), wherein the polycarbonate resin is a raw material monomer. Polycarbonate in any one of [1]-[11] using the compound and the 1 or more types of dihydroxy compound chosen from the group which consists of a dihydroxy compound represented by the dihydroxy compound represented by following General formula (6). Method for producing a resin.

(3)

[In the general formula (4), R ₅ represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.

[Chemical Formula 4]

[In the general formula (5), R ₆ represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.

[Chemical Formula 5]

[In formula (6), R ₁₁ represents a chain alkylene group having 2 to 20 carbon atoms.]

[13] The filter is stored in a container, and the value obtained by dividing the inner volume (m 3) of the containing container by the flow rate (m 3 / min) of the polycarbonate resin to be filtered is 2 to 10 minutes [1] to [12] The manufacturing method of polycarbonate resin in any one of].

[14] The method for producing a polycarbonate resin according to any one of [1] to [13], wherein the flux of the molten resin on the filter surface is 0.01 to 0.5 m / h.

[15] The method for producing a polycarbonate resin according to any one of [1] to [14], wherein the content of the aromatic monohydroxy compound contained in the polycarbonate resin obtained by the cooling solidification is 0.0001 wt% or more and less than 0.2 wt%.

[16] The method for producing a polycarbonate resin according to any one of [1] to [15], wherein the raw material monomer is filtered with a raw material filtration filter before the polycondensation reaction is performed.

[17] The method for producing a polycarbonate resin according to any one of [1] to [16], wherein the filter is made of a metal which has been subjected to roasting treatment at a temperature of 350 ° C or higher and 500 ° C or lower in advance.

[18] The polycarbonate resin according to any one of [1] to [17], wherein the polycarbonate resin before filtration is supplied from the lower part of the storage container of the filter, and the polycarbonate resin after filtration is discharged from the upper part of the storage container. Method of preparation.

[19] Preparation of the polycarbonate resin according to any one of [1] to [18], wherein the polycarbonate resin is subjected to a devolatilization operation using a twin-screw extruder having a vent port, and then supplied to the filter and filtered. Way.

[20] The polycarbonate according to [19], wherein the screw of the extruder is composed of a plurality of elements, at least one of the elements being a kneading disk, and the length of the total of the kneading disks is 20% or less of the length of the entire screw. Method for producing a resin.

[21] 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), the following formula (7) is satisfied or The manufacturing method of polycarbonate resin as described in [20].

[22] The method for producing a polycarbonate resin according to any one of [19] to [21], wherein the temperature of the polycarbonate resin supplied to the extruder is 200 ° C or more and less than 250 ° C.

[23] The method for producing a polycarbonate resin according to any one of [19] to [22], wherein the temperature of the polycarbonate resin supplied to the filter is 230 ° C or more and less than 280 ° C.

[24] When the reduced viscosity (ηsp / c) of the polycarbonate resin supplied to the extruder is a and the reduced viscosity (ηsp / c) of the polycarbonate resin obtained by cooling and cooling is set to B, the following formula (8) The manufacturing method of polycarbonate resin in any one of [19]-[23] which satisfy | fills.

[25] The method for producing a polycarbonate resin according to any one of [19] to [24], wherein a gear pump is disposed between the extruder and the filter.

[26] A polycarbonate resin having a yellow index value of 70 or less obtained by the production method according to any one of [1] to [25].

[27] A film having a thickness of 20 µm to 200 µm obtained by extruding the polycarbonate resin obtained by the production method described in any one of [1] to [25] or the polycarbonate resin according to [26], the film. Polycarbonate resin film with a maximum length of 25 micrometers or more foreign substances contained in 1000 pieces / m <2> or less.

[28] A polycarbonate resin obtained by using a dihydroxy compound having a structural unit represented by the following General Formula (1) as a raw material monomer is filtered using a filter in a molten state, discharged from a die, and cooled, followed by poly A method for producing a carbonate resin pellet or a polycarbonate resin film, wherein the dihydroxy compound contains at least a dihydroxy compound having a moiety represented by the following general formula (1) in a part of the structure, and the mesh of the filter is 50 It is micrometer or less, and the temperature of resin discharged from the said dice is 200 degreeC or more and less than 280 degreeC, The manufacturing method of the polycarbonate resin pellet or polycarbonate resin film characterized by the above-mentioned.

[Chemical Formula 6]

[The above general formula (1) of, R ₁ - R ₄ are each independently a hydrogen atom, a substituted or unsubstituted, having 1 to 20 carbon atoms an alkyl group, a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituted or beach A C6-C20 aryl group of the ring, X represents a substituted or unsubstituted C2-C10 alkylene group, a substituted or unsubstituted C6-C20 cycloalkylene group, or a substituted or unsubstituted C6-C20 Represents an arylene group, and m and n each independently represent an integer of 0 to 5;

According to the present invention, a retardation film having excellent optical properties, mechanical strength and color, and less foreign matter, and furthermore, can be applied to optical fields such as lens applications such as camera lenses, finder lenses, lenses for CCD or CMOS, and the like. It becomes possible to manufacture the polycarbonate resin pellet or film which it has efficiently and stably.

1 is 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 behind that.

<Raw monomer and polymerization catalyst>

(Dihydroxy compound)

In the manufacturing method of the polycarbonate resin of this invention, although a dihydroxy compound is used as a raw material monomer, the specific dihydroxy compound which has a site | part represented by following General formula (1) in at least one paper structure of a dihydroxy compound. It is characterized by being (Hereinafter, it may be called "the dihydroxy compound of this invention.").

(7)

The general formula (1) of, R ₁ - R ₄ are each independently a hydrogen atom, an alkyl group, a substituted or unsubstituted, having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted, An aryl group having 6 to 20 carbon atoms, X represents a substituted or unsubstituted C2-C10 alkylene group, a substituted or unsubstituted C6-C20 cycloalkylene group, or a substituted or unsubstituted C6-C20 carbon An arylene group is represented and m and n are the integers of 0-5 each independently.

As a dihydroxy compound of this invention, it is a compound represented by the said General formula (1). In the formula, each of R ₁ to R ₄ independently represents a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 cycloalkyl group, or a substituted or unsubstituted C6-C20 An aryl group is shown.

Here, as a substituent, ester group, an ether group, a carboxylic acid, an amide group, and a halogen are mentioned, for example. Especially, a hydrogen atom, an unsubstituted C1-C4 alkyl group, an unsubstituted C5-C7 cycloalkyl group, or a phenyl group is preferable.

X is an unsubstituted or ester group, an ether group, a carboxylic acid, an amide group, an alkylene group having 2 to 10 carbon atoms substituted with a halogen, or the like, an unsubstituted or ester group, an ether group, a carboxylic acid, an amide group, a halogen, or the like. It is a C6-C20 cycloalkylene group substituted with the C6-C20 arylene group substituted by an unsubstituted or ester group, an ether group, a carboxylic acid, an amide group, a halogen, etc. It is preferable that it is an alkylene group.

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

As a dihydroxy compound of this invention, specifically, 9, 9-bis (4-hydroxyphenyl) fluorene, 9, 9-bis (4-hydroxy-3- methylphenyl) fluorene, for example. , 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-n-propylphenyl) fluorene, 9,9-bis (4-hydroxy 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-below) 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. can be mentioned.

Among these, Preferably, 9, 9-bis (4-hydroxy-3- methylphenyl) fluorene, 9, 9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, or 9, 9- Bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, and particularly preferably 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.

Among them, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene or 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene is preferable from the physical properties of the polymer obtained from the handling properties. Especially, 9, 9-bis [4- (2-hydroxyethoxy) phenyl] fluorene is preferable.

It is preferable that the polycarbonate resin of this invention is obtained using 18 mol% or more of specific dihydroxy compounds which have a structural unit represented by the said General formula (1) as a raw material monomer with respect to all the dihydroxy compounds, It is more preferable. Preferably it is 20 mol% or more, 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 the said 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 and filtration using a small mesh filter will become difficult, and a foreign material may increase and pelletization or 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.

Desired optical performances include coloration, foreign matters, or retardation that affect light transmittance. 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 near 1/4 of the wavelength in all wavelength ranges. In order to do so, it is necessary to have so-called birefringence reverse wavelength dispersion which becomes smaller as birefringence becomes shorter and becomes larger as longer wavelength.

The birefringence wavelength dispersion produced the stretched film which has a uniform thickness, measured the retardation (R450) of 450 nm and the retardation (R550) of 550 nm, and calculated | required the ratio (R450 / R550) of R450 and R550. It can evaluate by doing.

When the said value is less than 1, it shows reverse wavelength dispersion (it may be called negative wavelength dispersion). In the present invention, R450 / R550 is preferably 0.80 to 0.95, more preferably 0.85 to 0.93, particularly preferably 0.87 to 0.91. Inverse wavelength dispersibility cannot be at least achieved even if there are too many structural units represented by the said General formula (1), On the other hand, the structure or content rate of another structural unit is also influenced.

In the manufacturing method of the polycarbonate resin of this invention, the dihydroxy compound represented by General formula (3) can be used as a raw material monomer.

[Chemical Formula 8]

However, the region represented by the above general formula (3) except for a part of -CH ₂ -OH.

As the dihydroxy compound represented by the general formula (3), specifically, for example, oxyalkyl such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol Lenglycols; The compound which has cyclic ether structures, such as anhydrosugar alcohol represented by the dihydroxy compound represented by following General formula (9), and spiroglycol represented by following General formula (10), is mentioned.

Especially, diethylene glycol, triethylene glycol, or polyethylene glycol is preferable from a viewpoint of the availability, handling, the reactivity at the time of polymerization, and the color of the polycarbonate resin obtained.

From a heat resistant viewpoint, cyclic ether structures, such as anhydrous sugar alcohol represented by the dihydroxy compound represented by following General formula (9), or spiroglycol represented by following General formula (10) [Preferably, the said General formula ( And the moiety represented by 3) is a part of cyclic ether structure.

[Chemical Formula 9]

[Chemical formula 10]

Moreover, as a dihydroxy compound represented by the said General formula (9), isosorbide, isomannide, or isoidide which has a stereoisomer relationship, for example is mentioned. 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 view of availability and preparation, optical properties and moldability. .

In the present invention, the amount of use of the compound having a cyclic ether structure, such as isosorbide or spiroglycol, is not limited. However, the lower limit thereof is preferably 10 mol% or more, and more preferably 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 90 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 the said structural unit is too small, there exists a possibility that the obtained polycarbonate resin may not show desired optical performance. Moreover, too much may not only exhibit desired optical performance, but may also adversely affect the thermal stability of the obtained polycarbonate resin, or may increase melt viscosity, making pelletization or film film production difficult.

In the manufacturing method of the polycarbonate resin of this invention, the dihydroxy compound represented by General formula (4) can be used as a raw material monomer.

(11)

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

As a dihydroxy compound represented by the said General formula (4), for example, 2, 6- decalin diol, 1, 5- decalin diol, 2, 3- decalin diol, tricyclodecanediol, and pentacyclo Compounds having a plurality of alicyclic structures such as pentadecanediol, and 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4- The compound containing the cycloalkylene group of monocyclic structure, such as cyclohexanediol, 2-methyl- 1, 4- cyclohexanediol, and 1, 3- tetramethyl cyclobutanediol, is mentioned. By employing a monolithic structure, it is possible to improve the toughness when the obtained polycarbonate resin is used as a film.

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 obtained polycarbonate resin can be increased. The 6-membered ring structure may be fixed to a chair or a ship by a covalent bond.

Moreover, as a substituent in the case of having a substituent, a C1-C4 alkyl group is preferable.

As a dihydroxy compound represented by the said General formula (4), specifically, 1,2-cyclopentanediol, 1, 3- cyclopentanediol, 1,2-cyclohexanediol, 1,3, for example. -Cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, and the like.

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.

[Chemical Formula 12]

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

As a dihydroxy compound represented by the said General formula (5), For example, 2, 3- norbornane dimethanol, 2, 5- norbornane dimethanol, adamantane dimethanol, decalin dimethanol, and tricyclo tetradecane A compound having a plurality of alicyclic structures such as dimethanol, and a cycloalkylene group having a monocyclic structure such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol The compound can be mentioned.

When the dihydroxy compound having a plurality of alicyclic structures is used, heat resistance may be improved, while deterioration of toughness may be caused, or the viscosity at the time of melting may increase, thereby deteriorating fluidity. Therefore, from the viewpoint of improving the toughness and fluidity at the time of melting, a dihydroxy compound having a monocyclic structure, in particular, 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 a chair or a ship by a covalent bond.

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, for example.

Among the specific examples of the alicyclic dihydroxy compound described above, cyclohexanedimethanol is particularly preferable, and 1,4-cyclohexanedimethanol and 1,3-cyclo are preferred from the viewpoint of availability and ease of handling. Preference is given to hexanedimethanol or 1,2-cyclohexanedimethanol. Especially, 1, 4- cyclohexane dimethanol is preferable 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 (6) can be used as a raw material monomer.

[Chemical Formula 13]

In said general formula (6), R <_11> represents a C2-C20 linear alkylene group.

Although the dihydroxy compound represented by the said General formula (6) may be linear or may have a branch, a linear alkylene diol 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, for example.

Especially, 1, 3- propylene glycol, 1, 4- butanediol, and 1, 6- hexanediol are preferable. When the molecular weight is small, 1,6-hexanediol is most preferred because it is volatilized during polymerization or the effect of imparting toughness 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 the 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 And a di, diphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl ether, and the like.

The polycarbonate resin in this invention is a dihydroxy compound which has a site | part represented by the said General formula (3), the dihydroxy compound represented by the said General formula (4), and the dihydroxy compound represented by the said General formula (5). 25 or more dihydroxy compounds selected from the group consisting of a dihydroxy compound represented by the general formula (6) and a bisphenol compound as the total thereof are 100 mol%, It is preferable that it is obtained using mol% or more, More preferably, it is 30 mol% or more, More 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 (3), the dihydroxy compound represented by the said General formula (4), the dihydroxy compound represented by the said General formula (5), and the said General formula (6) 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 obtained polycarbonate resin may fall, and pelletization or film film manufacture may become difficult. . On the other hand, when there are too many, the obtained polycarbonate resin may not show desired optical performance.

Especially, in this invention, from the optical characteristic, heat resistance, the toughness of the obtained polymer, and the fluidity | liquidity at the time of melting, as a dihydroxy compound represented by the said General formula (1), it is 9,9-bis (4-hydroxy) Preference is given to -3-methylphenyl) fluorene and / or 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene. Moreover, as a dihydroxy compound represented by said Formula (4), the polycarbonate resin which copolymerized isosorbide and / or spiroglycol is preferable.

In order to impart toughness, at least one dihydroxy compound selected from diethylene glycol, triethylene glycol, polyethylene glycol, 1,4-cyclohexanedimethanol and 1,6-hexanediol may be used. It is preferable to set it as the polycarbonate resin which copolymerized the monomer.

Especially preferably, in addition to 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and isosorbide, diethylene glycol, triethylene glycol, polyethylene glycol, 1, 4- cyclohexane It is a polycarbonate resin which copolymerized 30 mol% or less, More preferably, 20 mol% or less of at least 1 sort (s) of dihydroxy compounds chosen from dimethanol or 1, 6- hexanediol.

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 an 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, ie, the compound which has a compound represented by the said General formula (1), and the site | part represented by the said General formula (3) and / or the said General formula (4) In the case of using together the dihydroxy compound represented by (5) or (6), the molecular weight of the dihydroxy compound and the diester carbonate are transesterified in the presence of a catalyst to remove the by-product monohydroxy compound out of the system. It is preferable to obtain by the transesterification method which increases the viscosity.

The polycarbonate resin which uses the dihydroxy compound which has a site | part represented by the said General formula (3), or the dihydroxy compound represented by the said General formula (4), (5), (6) as a monomer component is degradable at low temperature. If the filter tends to start easily and the filter is performed at a temperature at which the decomposition of the polycarbonate resin does not occur, the viscosity is too high, and the pressure loss in the filter becomes large in a typical filtration area, resulting in breakage of the filter or during filtration. There was a problem that the resin was deteriorated due to shear exotherm. On the contrary, in order to avoid breakage, it was necessary to use a filter having a low pressure loss and a low filtration accuracy (large mesh).

In addition, if a filter with high filtration accuracy is to be used while suppressing a filter breakage or deterioration due to shear heat generation of the resin, the filtration area must be excessively consequently, the time required for the filtration treatment is increased, resulting in a polycarbonate resin. There is a problem that causes deterioration.

Furthermore, if the melt viscosity of the polycarbonate resin is to be lowered in order to suppress the pressure loss in the filter and to shorten the time required for the filtration treatment, the molecular weight of the polycarbonate resin itself may be lowered or the filtration temperature may be increased. Although it is necessary to lower the molecular weight, the mechanical strength or the heat resistance is lowered, and if the temperature at the time of filtration is increased, the resin is decomposed and degraded, so that a resin that satisfies physical properties such as mechanical strength is not obtained. There was a problem that the coloring was promoted or the gas was broken in the strand by the decomposition gas, and pelletization was not obtained stably.

These problems arise well when a dihydroxy compound having a moiety represented by the general formula (3), and especially a dihydroxy compound having a cyclic ether structure, is used as the monomer component.

Therefore, when using the dihydroxy compound which has a site | part represented by the said General formula (3), or the dihydroxy compound represented by the said General formula (4), (5) or (6) as a monomer component, a filter is used. Temperature control of resin at the time of filtration is important, and this invention is especially useful.

(Carbonic acid diester)

As diester carbonate used by this invention, what is represented by following General formula (11) is mentioned. These diester carbonate may be used individually by 1 type, and may mix and use 2 or more types.

[Chemical Formula 14]

A <^1> , A <^2> is a substituted or unsubstituted C1-C18 aliphatic group or a substituted or unsubstituted aromatic group, and A <^1> and A <^2> may be same or different.

A ¹ and A ² are preferably 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, for example. As a substituent of an aromatic hydrocarbon group, alkyl groups, such as a methyl group and an ethyl group, are mentioned, for example.

As diester carbonate represented by the said General formula (11), substituted diphenyl carbonate, such as diphenyl carbonate and a tolyl carbonate, dimethyl carbonate, diethyl carbonate, di-t- butyl carbonate, etc. are mentioned, for example. . Among these, Preferably, they are diphenyl carbonate or 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 may deteriorate the color of the polycarbonate resin obtained, what was refine | purified by distillation etc. as needed. It is preferable to use.

In the method of this invention, polycarbonate resin can be obtained by polycondensing the dihydroxy compound and diester carbonate containing the dihydroxy compound of this invention by transesterification reaction.

Although the raw material dihydroxy compound and diester carbonate can be transesterified even if it is dropped to the reaction tank independently, it can also mix uniformly before a transesterification reaction.

80 degreeC or more is preferable, More preferably, it is 90 degreeC or more, The upper limit is 250 degrees C or less, More 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 temperature of the mixing is too low, the dissolution rate may be slow or the solubility may be insufficient, causing problems such as frequent solidification. If the temperature of the mixing is too high, thermal degradation of the dihydroxy compound may be caused. There is a possibility that the color of the resulting polycarbonate resin deteriorates.

In the method of the present invention, the oxygen concentration of the operating environment in which the dihydroxy compound containing the dihydroxy compound of the present invention as a raw material and the diester carbonate is mixed is preferably 10 vol% or less, and more preferably 0.0001 vol % -10 vol%, More preferably, it is 0.0001 vol%-5 vol%, Especially preferably, it is preferable from a viewpoint of prevention of color deterioration in 0.0001 vol%-1 vol%.

In this invention, it is preferable to use diester carbonate in the molar ratio of 0.90-1.20 with respect to all the dihydroxy compounds containing the dihydroxy compound of this invention used for reaction, More preferably, it is 0.95 -1.10, More preferably, it is 0.97-1.03, Especially preferably, it is 0.99-1.02.

When the molar ratio decreases, the terminal hydroxyl group of the produced polycarbonate resin increases, resulting in deterioration of the thermal stability of the polymer, causing coloring during molding, lowering the rate of transesterification reaction, or obtaining a desired high molecular weight body. There is no possibility.

On the other hand, when the molar ratio increases, the rate of transesterification reaction decreases, making polycarbonate of a desired molecular weight difficult, or the amount of diester carbonate remaining in the polycarbonate resin increases, and gas is generated during extrusion or molding. It may cause or cause. 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 is increased with respect to all the dihydroxy compounds containing the dihydroxy compound of this invention, the amount of remaining diester carbonate in the polycarbonate resin obtained will increase, and this will produce a gas at the time of shaping | molding. This may cause mold failure or bleed out of the product, which is undesirable.

The concentration of the diester carbonate remaining in the polycarbonate resin pellets or film obtained by the method of the present invention is preferably 200 ppm by weight or less, more preferably 100 ppm by weight or less, still more preferably 60 ppm by weight or less, particularly 30 Weight ppm or less is preferable.

(catalyst)

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

In the process of the invention, the transesterification catalyst (catalyst) can influence the yellow index (YI) value, which in particular indicates the thermal stability or color of the polycarbonate resin. The transesterification catalyst to be used is not limited as long as it satisfies the thermal stability and color of the polycarbonate resin. For example, Group 1 or Group 2 (hereinafter, simply referred to as "Group 1") in a long period type periodic table. And basic compounds such as a metal compound of "Group 2" and a basic boron compound, a basic phosphorus compound, a basic ammonium compound and an amine compound. Preferably Group 1 metal compounds and / or Group 2 metal compounds are used. More preferably, it is a metal compound of the metal selected from the group which consists of a metal of long-period periodic table group 2 and lithium.

The form of the Group 1 metal compound and / or the Group 2 metal compound is usually used in the form of a hydroxide or a salt such as a carbonate, carboxylate or phenol salt, but from the availability and ease of handling, Carbonates or acetates are preferred, and acetates are preferred in view of color and polymerization activity.

Specific examples of the Group 1 metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, and carbonic acid. Lithium, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, phenyl Sodium boron fluoride, potassium borohydride, lithium phenyl boride, sodium phenyl boron, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, disodium hydrogen phosphate, lithium lithium hydrogen phosphate, cesium hydrogen phosphate 2, sodium diphenyl phosphate, dipotassium phenyl phosphate, diphenyl phosphate, diphenyl phenyl phosphate, sodium, potassium, lithium, cesium alcoholate, phenolate, bisphenol A Sodium salt, dipotassium salt, dilithium salt, cesium salt and the like. Especially, a lithium compound is preferable.

As the Group 2 metal compound, specifically, 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 and strontium stearate.

Especially, a magnesium compound, a calcium compound, or a barium compound is preferable, At least 1 sort (s) of metal compound chosen from the group which consists of a magnesium compound and a calcium compound is more preferable from a viewpoint of a polymerization activity and the color of the polycarbonate resin obtained, and most Preferably it is a magnesium compound.

In addition, together with the Group 1 metal compound and / or the Group 2 metal compound, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound or an amine compound may be used together, but is volatilized during the polymerization reaction. Since there is a possibility of causing trouble, it is particularly preferable to use only Group 1 metal compounds and / or Group 2 metal compounds.

As said basic boron compound which can be used together, tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethyl benzyl boron, trimethylphenyl boron, triethyl methyl boron, triethylbenzyl Sodium salts such as boron, triethylphenylboron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron and butyltriphenylboron, potassium salt, lithium salt, calcium salt, barium Salts, magnesium salts and 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, for example And quaternary phosphonium salts.

As said basic ammonium compound which can be used together, it is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethyl, for example. Benzyl ammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide And a hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide.

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

As for the usage-amount of the said catalyst, 0.1 micromol-300 micromol are preferable per 1 mol of all the dihydroxy compounds used, More preferably, they are 0.5 micromol-100 micromol, More preferably, 0.5 micromol-50 micromol, Especially preferably, they are 0.5 micromol-20 micromol, Most preferably, 1 micromol-15 micromol.

Especially, when using the at least 1 sort (s) of metal compound chosen from the metal of group 2 of long-period type periodic table, and lithium, it is preferable that it is 0.1 micromol or more normally as a metal amount per 1 micromol of all the dihydroxy compounds used, More preferably, it is 0.5 micromol or more, More preferably, it is 0.7 micromol or more. Moreover, as an upper limit, it is preferable that it is 50 micromol normally, More 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 does not advance well and there exists a possibility that the polycarbonate resin of 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 deteriorate the color of the polycarbonate resin obtained by an unwanted side reaction, or may cause a foreign substance.

In addition, when a group 1 metal, especially sodium, is contained in a large amount of polycarbonate resin, it may adversely affect color, and the metal may be mixed not only from the catalyst used but also from a raw material or a reaction apparatus. Therefore, it is preferable that the total amount of these compounds in polycarbonate resin is 1 weight ppm or less normally as metal amount, More preferably, it is 0.8 weight ppm or less, More preferably, it is 0.7 weight ppm or less.

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.

Moreover, the said catalyst may be added directly to a reactor, may be added to the raw material adjustment tank which mixes a dihydroxy compound and diester carbonate beforehand, and may take the method which exists in a reactor after that, and in the piping which supplies a raw material to a reactor. You may add.

(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 form of the reaction may be any of batch, continuous, or combination of batch and continuous. Especially, a continuous type is preferable from a viewpoint of quality stabilization. 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 in the late polymerization.

It is preferable to select suitably the jacket temperature, internal temperature, and pressure in the reaction system at each molecular weight stage from the viewpoint of color and thermal stability. For example, if the polymerization reaction changes too quickly in either of the temperature and the pressure before reaching the predetermined value, the unreacted monomer flows out, disrupting the molar ratio of the dihydroxy compound and the diester carbonate, and polymerizing. There is a possibility that a decrease in speed or a polymer having a predetermined molecular weight or terminal 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 condenser can be appropriately selected depending on the monomer to be used.

Usually, it is preferable that the temperature of the refrigerant | coolant introduced into a reflux condenser is 45-180 degreeC in the inlet of this reflux cooler, More preferably, it is 80-150 degreeC, Especially preferably, it is 100-140 degreeC.

If the temperature of the coolant is too high, the amount of reflux decreases, and the effect is lowered. On the contrary, if the temperature of the coolant is too low, the distillation efficiency of the monohydroxy compound to be 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 above-described catalyst in order to maintain the rate of polymerization appropriately, to suppress the outflow of monomers, to suppress the generation of foreign substances in the final polycarbonate resin and not to inhibit the color or thermal stability. Do.

In this invention, it is preferable to manufacture by using a said catalyst and superposing | polymerizing in multistep using several reactor. In the initial stage of a polymerization reaction, since there are many monomers contained in a reaction liquid, it is preferable to suppress volatilization of a monomer, maintaining the required polymerization rate. Moreover, in the late stage of a polymerization reaction, in order to shift an equilibrium to the polymerization side, it is preferable to fully distill off the by-product monohydroxy compound. Therefore, it is preferable to perform superposition | polymerization by several reactor at the point which a preferable polymerization reaction condition differs at an early stage and a late stage. As described above, in order to set different polymerization reaction conditions, it is preferable to use a plurality of polymerization reactors arranged in series from the viewpoint of production efficiency.

In the present invention, as described above, the reactor used at the time of polymerization is preferably at least two or more, and from the viewpoint of production efficiency and the like, more preferably three or more, still more preferably three to five, Especially preferably, it is four.

In this invention, if there are two or more reactors, reaction conditions from which conditions differ can be set in each reactor, and temperature and pressure may be changed continuously in each reactor.

In the present invention, the polymerization catalyst may be added to the raw material preparation tank or the raw material storage tank, or may be added directly to the polymerization tank, but in view of the stability of the supply and the control of the polymerization, in the middle of the raw material piping before being supplied to the polymerization tank. It is preferable to provide a catalyst supply pipe, and more preferably, it is supplied in an aqueous solution.

When the temperature of the said polymerization reaction is too low, it will lead to the fall of productivity or 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 also may promote the decomposition or coloring of a polycarbonate resin.

Specific temperature is as follows. The reaction of the first stage is preferably 140 to 270 ° C, more preferably 170 to 240 ° C, still more preferably 180 to 210 ° C, and 110 to 1 Pa as the maximum temperature of the polymerization reactor internal temperature. , More preferably 70 to 5 kPa, still more preferably 30 to 10 kPa (absolute pressure) under pressure, preferably 0.1 to 10 hours, more preferably 0.5 to 3 hours, by-product monohydroxy compound The distillation is carried out outside the reaction system.

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 preferably 2 kPa or less. More preferably, it is 1 Pa or less, Preferably it is 210 degreeC or more, More preferably, it is 220 degreeC or more, Preferably it is 270 degrees C or less, More preferably, it is 250 degrees C or less, More preferably, it is 240 degrees C or less, Preferably 0.1 to 10 hours, more preferably 1 to 6 hours, particularly preferably 0.5 to 3 hours.

In particular, in order to suppress coloring or thermal degradation of the polycarbonate resin and to obtain a polycarbonate resin having good color or thermal stability, the maximum temperature of the internal temperature in the entire reaction step is preferably 260 ° C. or less, more preferably 250 ° C. Hereinafter, Especially preferably, it is 245 degrees C or less, Especially, it is preferable that it is 240 degrees C or less.

Internal temperature here shows the temperature of a process liquid, and is normally measured by the thermometer using the thermocouple etc. which were 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 when the polymerization temperature is high and the polymerization time is too long, the yellow index (YI) value indicating the color tends to increase.

It is preferable to use the monohydroxy compound by-produced and distilled off in said reaction as a raw material of a fuel or a chemical product 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)

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

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

For example, in order to generate | occur | produce the pressure required for filtration, the method of extracting a polycarbonate resin in a molten state using a gear pump, a screw, etc. from a final polymerization reactor, and filtering by the said filter;

A method of feeding a polycarbonate resin into a single screw or twin screw extruder from the final polymerization reactor in a molten state, melt extruding, filtering with the filter, cooling and solidifying in the form of a strand, and pelletizing with a rotary cutter or the like;

The polycarbonate resin was supplied to a single or biaxial extruder in a molten state without solidifying from the final polymerization reactor, melt-extruded, and then cooled and solidified in the form of a strand to pelletize, and the pellet was introduced into the extruder again. Filtering by the filter, cooling and solidifying in the form of strand, and pelletizing;

Alternatively, the polycarbonate resin is extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of strands without passing through an extruder, and once pelletized, and then pellets are supplied to a single screw or twin screw extruder, followed by melt extrusion. And filtering by the filter, cooling and solidifying in the form of strands and pelletizing.

Especially, in order to suppress thermal deterioration, such as deterioration of color or molecular weight deterioration, by suppressing the thermal history to the minimum, resin is supplied to a single- or two-screw extruder in the molten state without solidifying from the final polymerization reactor, and melt-extrusion Then, the method of supplying and filtering to the said filter using a gear pump, discharging | discharging from a dice, solidifying by cooling in the form of strand, and pelletizing with a rotary cutter etc. is preferable.

<One example of manufacturing apparatus>

An example of the apparatus which performs this invention which obtains the polycarbonate resin pellet obtained by cooling and solidifying from the raw material monomer described above (Hereinafter, "cooling-solidified polycarbonate resin" may only be called "polycarbonate resin".) It shows in 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, 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, a molten liquid of DPC prepared at a predetermined temperature under a nitrogen gas atmosphere is continuously supplied from the raw material supply port 1a to the raw material mixing tank 2a. In addition, a melt of ISB and a powder of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, which were metered in a nitrogen gas atmosphere, were mixed with raw materials from the raw material supply ports 1b and 1c, respectively. It is continuously supplied to the tank 2a. 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 in the middle of the transfer 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 in series. Is formed. In each reactor, the liquid level is kept constant, the polycondensation reaction is performed continuously, and the polymerization reaction liquid discharged | emitted from the tank bottom of the 1st water type stirring reaction tank 6a is continued to the 2nd water type stirring reaction tank 6b. The polycondensation reaction proceeds sequentially in the third male stirring reactor 6c and sequentially supplied to the fourth horizontal stirring reactor 6d. 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 1st male stirring reactor 6a, the 2nd male stirring reactor 6b, and the 3rd male stirring reactor 6c, respectively. In addition, 7d of biaxial spectacle type stirring blades are formed in 6d of 4th horizontal type stirring reaction tanks. Since the reaction liquid conveyed becomes high viscosity after the 3rd male stirring reactor 6c, the gear pump 4b is formed.

Since 1st type | mold stirring reactor 6a and 2nd type | mold stirring reactor 6b may supply especially large amount of heat supply, internal heat exchanger 8a, 8b is formed so that a fruit temperature may not become excessively high temperature, respectively. do.

In addition, these four reactors are each equipped with outlet pipes 11a, 11b, 11c, and 11d for discharging by-products and the like generated by the polycondensation reaction. Reflux coolers 9a and 9b and reflux tubes 10a and 10b are respectively formed in the first male stirred reactor 6a and the second male stirred reactor 6b in order 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 condenser, respectively.

Said outflow pipe 11a, 11b, 11c, 11d is connected to the condenser 12a, 12b, 12c, 12d, respectively, and each reactor is predetermined | prescribed by the pressure reduction apparatus 13a, 13b, 13c, 13d. It is kept at a reduced pressure.

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 respectively attached to the third male stirring reactor 6c and the fourth horizontal stirring reactor 6d, and the by-products are continuously solidified and recovered. .

The reaction liquid raised to the predetermined molecular weight is taken out from the fourth horizontal stirring reactor 6d, and the pipe connecting the extruder 15a by the gear pump 4c is a double pipe of a jacket form through which fruit flows to the outside. desirable.

The temperature of the fruit can be appropriately determined in consideration of the viscosity of the polycarbonate resin, the pressure loss of the pipe, and the thermal stability of the polycarbonate resin. However, if the temperature is too high, it may cause deterioration of the polycarbonate resin or generation of gas. It is preferable that it is C or less, More 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 are preferable.

On the other hand, if the temperature of the fruit is too low, the pressure loss in the pipe increases, 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. It is preferable that it is at least C, more preferably at least 180 C, still more preferably at least 200 C, particularly preferably at least 210 C, particularly preferably at least 220 C.

The extruder 15a is equipped with a vacuum vent and removes the residual low molecular component in polycarbonate. Moreover, antioxidant, an optical 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 is cooled and solidified by water in the strand cooling tank 16a to be pelletized by the strand cutter 16b. The polycarbonate resin pellets thus obtained are energized by the air blower 16c and sent to the product hopper 16d. A predetermined amount of product is packed into the product bag 16f by the meter 16e.

There is no restriction on the type of the gear pumps 4c and 4d, but among them, there is a circuit for inducing some polymer from the discharge side of the gear pump through the valve to return to the inlet by applying a constant pressure to the shaft rod, A self-circulating seal gear pump that does not use a 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, in order to improve the devolatilization performance mentioned later or the uniform kneading | mixing of an additive, a biaxial extruder is preferable. In this case, although the rotation direction of an axis may be a different direction or the same direction, the same direction is preferable from a kneading performance viewpoint. The use of an extruder can stabilize the supply of polycarbonate resin to the filter.

Moreover, in the polycarbonate resin obtained by polycondensation as mentioned above, the raw material monomer which may adversely affect a product by color or thermal stability, bleed-out, etc., the monohydroxy compound by-produced by a transesterification reaction, or poly Low molecular weight compounds, such as a carbonate oligomer, remain in many cases.

It is also possible to devolatilize and remove the low molecular weight compound by using the one having a vent port as the extruder, and preferably reducing the pressure using a vacuum pump or the like from the vent port. In addition, volatile liquids 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, you may knead the additives, such as a heat stabilizer, a mold release agent, or a coloring agent mentioned later, 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 a screw) provided in the extruder is preferably 300 rpm or less, more preferably 250 rpm or less, more preferably 200 rpm or less. By setting the rotation speed of the screw to 300 rpm or less, it is possible to suppress the increase in the shear heat generation of the polycarbonate resin and to prevent the deterioration of the color or the decrease of the molecular weight.

On the other hand, if the rotation speed of the screw is too small, it may not only lead to deterioration of the devolatilization performance or deterioration of the kneading performance of the additive, but also to reduce the throughput per unit time, resulting in deterioration of the productivity, preferably 50 rpm. 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 the rotation speed of the said extruder, in order to suppress thermal deterioration, such as coloring or the molecular weight fall resulting from exotherm by the shear of polycarbonate resin, it is normally 1.0 m / It is preferable that it is seconds or less, More 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 becomes too small, it may cause vent up during vacuum devolatilization, or the devolatilization performance or the dispersion performance of the additives tends to decrease, so it is usually preferably 0.05 m / sec or more, more preferably 0.1 m / sec. More than seconds.

Usually, the screw of an extruder is comprised from several element (screw element) in order to have various functions. Generally, it consists of the full flight which consists only of the spiral screw (flight) for conveyance of resin, the kneading disc for kneading of resin, or the sealing for the purpose of sealing resin. According to the objective, the reverse flight which arrange | positioned the screw in the reverse direction to the conveyance direction of resin is also used.

Moreover, although there are two tanks or three tanks according to the cutting method of the screw, in the present invention, the two tanks can take a large throughput with respect to the screw diameter of the extruder and can suppress the shear heat generated by the screw rotation. Deep groove type of is preferred.

In this invention, although the structure of these screw elements is not limited, It is preferable to have a kneading disk, Especially, it is preferable that the length of the sum total of the kneading disk is 20% or less of the length of the whole screw, More preferably, It is 15% or less, Most preferably, it is 10% or less. If the total length of the kneading disc is too long, the local heat generation due to the shearing of the resin is increased, so that the problem of deterioration of color of the polycarbonate resin or reduction of molecular weight occurs.

On the other hand, if the total length of the kneading disk is too short, since the performance at the time of the above-mentioned devolatilization or kneading of the additive may decrease, the total length of the kneading disk is preferably 3% or more of the entire length of the screw. , 5% or more is more preferable.

As said kneading disk, although there exist a forward transfer type, an orthogonal type, and a reverse transfer type with respect to the conveyance direction of resin, it can select suitably according to the viscosity of the resin used or the performance required.

As a material of the said screw element, it is preferable to carry out the process which raises content of nickel etc. of a surface, suppresses iron content low, or raises surface hardness with TiN or CrN.

In the present invention, 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), the following formula (7) is preferably satisfied. Do.

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 cause deterioration such as molecular weight reduction or coloring of the polycarbonate resin. Therefore, the lower limit is preferably 12000, more preferably 15000, still more preferably 20000, particularly preferably 25000.

On the other hand, when too large, an excessive polycarbonate resin may be 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 heat generation. Preferably 50000, more preferably 40000, 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 preferably 200 ° C. or higher, and particularly 210 or higher, particularly 220 ° C. or higher. Moreover, it is preferable that the upper limit is 250 degrees C or less, Especially, it is preferable that it is 245 degrees C or less, especially 240 degrees C or less.

If the temperature of the polycarbonate resin supplied to the extruder is too low, the melt viscosity of the polycarbonate resin becomes too high and the supply becomes unstable, or the load of the drive motor of the extruder becomes excessive, so that the above formula (7) cannot be satisfied. Not only that, but also the shear exotherm in the extruder may increase, resulting in deterioration of the polycarbonate resin. On the other hand, when the temperature is too high, deterioration of the polycarbonate resin occurs well, and there is a tendency that the deterioration of color or the molecular weight or the mechanical strength accompanying it is caused.

The temperature of the polycarbonate resin supplied to the extruder can be controlled by controlling the temperature of the final polymerization reactor and controlling the temperature of the pipe for supplying the polycarbonate resin to the extruder or by installing a heat exchanger.

In the present invention, the temperature of the polycarbonate resin discharged from the extruder is usually preferably less than 300 ° C, more preferably less than 280 ° C, still more preferably less than 270 ° C, particularly preferably less than 260 ° C. to be.

When the temperature of the polycarbonate resin discharged from the extruder is excessively high, the polycarbonate resin deteriorates well, and there is a tendency that the deterioration of color or the molecular weight and the mechanical strength accompanying it occur.

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, the load on the extruder is increased, and screw rotation becomes unstable or causes an overload of the motor. Preferably it is 220 degreeC or more, More preferably, it is 230 degreeC or more, Especially preferably, it is 240 degreeC 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 there are many and a 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. However, when the temperature of the polycarbonate resin itself is high, deterioration occurs well, and color deterioration or molecular weight decrease, or mechanical accompanying it. Since there is a tendency to cause a decrease in strength, it is not easy to prevent deterioration of a high viscosity polycarbonate resin having poor thermal stability and to perform extrusion.

The temperature of the polycarbonate resin discharged from the extruder is usually controlled by the temperature of the polycarbonate resin to be supplied or the temperature of the heater that is associated with the barrel, but according to the supply amount of the polycarbonate resin to the extruder or the screw rotation speed of the extruder. Since they may change, it is preferable to also control these conditions together.

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

(filter)

In this invention, it filters with a filter in order to remove foreign substances, such as soot or a gel, in the polycarbonate resin obtained by polycondensation. Especially, in order to remove residual monomer, by-product phenol, etc. by pressure devolatilization, and to mix additives, such as a heat stabilizer or a mold release agent, it is preferable to extrude polycarbonate resin with an extruder, and to filter with a 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, is mentioned, for example. Especially, the leaf disc type which can take large filtration area with respect to the container of a filter is preferable, and it is preferable to use in combination in multiple numbers so that a filtration area can be enlarged.

The leaf disc type filter is configured by combining a holding member (also called a retainer) with a filtration member (hereinafter sometimes referred to as a media), and these filters (in some cases, a plurality of sheets) are stored in a container. Used in the form of a unit (sometimes called a filter unit) stored in.

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

In this invention, the mesh of the said filter is 50% or less as 99% of filtration accuracy, Preferably it is 30 micrometers or less, More preferably, it is 20 micrometers or less. In order to reduce the foreign matter in particular, 15 µm or less is preferable. However, when the mesh is smaller, the pressure loss in the filter increases, which may cause damage to the filter or deteriorate the polycarbonate resin due to shear heating. Since it exists, it is preferable that it is 1 micrometer or more as 99% of filtration accuracy.

In addition, the mesh defined here as 99% of filtration precision means the value of (x) when (beta) value shown by following formula (12) determined based on ISO16889 (2008) is 100.

 β × = (number of primary particles larger than χ μm) / (number of secondary particles larger than χ μm)... (12)

(Here, the primary side means before filtration by the 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. Among them, stainless steel such as SUS316 or SUS316L having a low iron content is preferable.

Moreover, as a kind of textile, the collection part of the foreign material, such as a plain weave, a twill weave, a flat weave or 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 there exists a tendency 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 iron component is small, Moreover, it is preferable to passivate before use.

As the passivation treatment, for example, a method of forming a passivation on the surface by immersing the filter in an acid such as nitric acid or passing an acid through the filter, and roasting (heating) in the presence of water vapor or oxygen The method and the method of using these together are mentioned. Especially, it is preferable to perform both nitric acid treatment and roasting.

It is preferable that the temperature at the time of roasting process with respect to the said filter is 350 degreeC-500 degreeC, More preferably, it is 350 degreeC-450 degreeC, It is preferable that roasting time is 3 hours-200 hours normally, More preferably, it is Preferably it is 5 hours-100 hours.

If the temperature of the roasting is too low or the time is too short, the formation of the passivation is 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 violent and the necessary filtration accuracy may not be obtained.

Moreover, it is preferable that the density | concentration of nitric acid at the time of processing the said filter with nitric acid is 5 weight%-50 weight% normally, More preferably, it is 10 weight%-30 weight%, and the temperature at the time of treatment is 5-100 degreeC normally. It is preferable that it is ° C, More preferably, it is preferable that they are 50 degreeC-90 degreeC, and processing time is 5 minutes-120 minutes normally, More 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 becomes insufficient, the concentration of nitric acid is too high, the treatment temperature is too high, or the treatment time is too long. There is a possibility that the damage of the filter media may be violent and the necessary filtration precision may not be obtained.

When the said filter is stored in the storage container, since it becomes easy to advance filtration by applying 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, but the gas and the polycarbonate resin in the storage container may be arranged. In order to suppress retention and to prevent deterioration of the polycarbonate resin, it is preferable that the supply port of the polycarbonate resin is disposed below the filter storage container and the discharge port above.

In addition, the value obtained by dividing the inner volume (m 3) of the filter containment container by the polycarbonate resin flow rate (m 3 / min) is too small to increase the differential pressure of the filter, which may cause damage to the filter. Since deterioration of a carbonate resin is caused, 1 minute-20 minutes are preferable, More 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 filtration area of the filter. If the flux is too small, the residence time at the time of filtration becomes long, which may cause deterioration of the polycarbonate resin and cause coloration or foreign matter generation.

Moreover, when the said flux is too large, the shear heat generation at the time of filtration becomes large and it may cause coloring or a foreign material generation, More 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 supplied to the filter is usually preferably less than 300 ° C, more preferably less than 280 ° C, still more preferably less than 270 ° C, particularly preferably 265 ° C. Less than 260 degreeC is especially preferable.

If the temperature before filtration with the filter becomes too high, thermal deterioration in the filter unit occurs well, which tends to cause deterioration of color or a decrease in molecular weight or a decrease in mechanical strength accompanying it.

On the contrary, if the temperature before filtration with the filter becomes too low, the polycarbonate resin supplied to the filter may have a high melt viscosity of the polycarbonate and a large load on the filter, which may cause breakage of the filter. The temperature of is preferably at least 220 ° C, more preferably at least 230 ° C, particularly preferably at least 240 ° C.

Moreover, in this invention, the temperature of the polycarbonate resin after filtration is 200 degreeC or more, Preferably it is 220 degreeC or more, More preferably, it is 230 degreeC or more. When the temperature of the polycarbonate resin after filtering using the said filter is too low, melt viscosity becomes high and the strand formed by extrusion is not stabilized, and it tends to become difficult to pelletize with a rotary cutter or the like.

On the other hand, the temperature of polycarbonate resin after filtration is less than 280 degreeC, Preferably it is less than 270 degreeC, More preferably, it is less than 265 degreeC, More preferably, it is less than 260 degreeC. If the temperature of the polycarbonate resin after filtration using the filter is too high, thermal deterioration of the polycarbonate resin is likely to occur, which tends to cause deterioration of color or a decrease in molecular weight or a decrease in mechanical strength accompanying it. .

As a measuring method of the resin temperature after said filtration, the method of taking out the resin discharged | emitted from a filter and measuring it directly, the method of installing and measuring a sensor inside the piping of a filter outlet flow path, etc. are mentioned, for example.

When the sensor is installed inside the pipe of the filter outlet flow path and measured, it is sometimes difficult to measure the correct resin temperature under the influence of a heater provided outside the pipe around the sensor. An apparatus for discharging resin such as a die is provided near the filter outlet, and when the temperature of the resin discharged therefrom can be regarded as equivalent to the resin temperature at the filter outlet side, The temperature may be the resin temperature after filtration of the present invention.

In addition, for the purpose of increasing the accuracy of the resin temperature after filtration, both a method of installing and measuring a sensor inside the pipe of the filter outlet flow path and a method of measuring the resin temperature discharged from a die or the like provided near the filter outlet are performed. You may.

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. However, if the set temperature is too high, deterioration of the polycarbonate resin may be caused. Preferably it is set to 280 degrees C or less, More 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 preferably 150 ° C or higher, more 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 a die is also usually provided with a heater outside thereof, but if the set temperature is too high, deterioration of the polycarbonate resin may occur. 280 degrees C or less, More preferably, it is set to 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, more preferably 180 ° C or higher, and 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, and therefore it is usually preferably 1 to 30 minutes, more 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, more preferably 220 ° C or higher, still more preferably 230 ° C or higher, and an upper limit. Silver is preferably less than 280 ° C, more preferably less than 270 ° C, still more preferably less than 265 ° C, particularly preferably less than 260 ° C.

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, and it may be 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 occurs well, which may lead to deterioration of color or lower molecular weight, or lowering of mechanical strength accompanying it.

Usually, a heater is installed in the die, but if the set temperature is too high, it may cause deterioration of the polycarbonate resin. Therefore, the temperature is preferably 280 ° C or lower, more preferably 260 ° C or lower, particularly preferably 250 ° C Set to:

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, more preferably 180 ° C or higher, and particularly preferably 200 ° C or higher.

Generally, when the polycarbonate resin is filtered by the filter having a small mesh, the temperature rises due to shear heat generation. When an extruder is used, shear heat generation due to screw rotation is also added. In order to control the temperature of the carbonate resin, it is important to comprehensively control the mesh, the filtration area, the temperature setting, the molecular weight of the polycarbonate resin, the temperature setting of the filter unit or the temperature setting from the filter outlet to the die.

In addition, when the extruder is used for feeding the filter, selection of the throughput of the polycarbonate resin in the extruder, the number of revolutions or speed of the screw, or the constitution of the element becomes important as described above.

Moreover, in the method of this invention, it is preferable that the difference of the temperature of the polycarbonate resin before filtering 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 of the polycarbonate resin before filtration with the filter and the temperature difference between the polycarbonate resin after filtration become too large, particularly when the filter unit is constituted by a plurality of leaf disc filters, the pressure balance at the supply side and the discharge side of the resin becomes There is a possibility that it may collapse and cause damage to the filter.

In the method of the present invention, the reduced viscosity (? Sp / c) of the polycarbonate resin obtained by the polycondensation by the transesterification reaction before filtration with the filter is filtered using the filter A, It is preferable to satisfy following formula (2), when discharging in the form of and after making cooling, the reduction viscosity ((eta) sp / c) of the polycarbonate resin pellet obtained using the cutter as B.

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 more than 0.8, it is preferable to suppress the generation of a coloring component or a coloring precursor component which is thought to be generated by side reactions. On the other hand, when the reduced viscosity rises in the polymer filter, since foreign matters such as gel or soot are generated, it is more preferable that B / A ≦ 1.0. The measuring method of a reduced viscosity is mentioned later.

In the case where the extruder is provided between the polycondensation reactor and the filter, when the reduced viscosity (? Sp / c) of the polycarbonate resin supplied to the extruder is represented by a, It is preferable to satisfy Formula (8).

More preferably, it is B / a> 0.85, Especially preferably, it is B / a> 0.9. When B / a is more than 0.8, generation of a coloring component, which is thought to be produced by the side reaction or a component to be a coloring precursor, can be suppressed, which is preferable. On the other hand, when the reduced viscosity is increased, generation of foreign matter such as gel or soot arises, so that B / a? 1.0 is more preferable.

In order to change the reduction viscosity in the polymer filter or the extruder in the above range, the temperature of the polycarbonate resin in the final reactor, the temperature of the polycarbonate resin entering the polymer filter, the temperature of the polycarbonate resin discharged from the polymer filter, the polymer filter Selection of throughput or mesh per unit time, temperature control or residence time from polymer filter to die, temperature of polycarbonate resin supplied to extruder, temperature of polycarbonate resin discharged from extruder, devolatilization when using extruder The choice of pressure, the presence or absence of water, the number of revolutions of the screw or the speed of the screw, or the configuration of the elements is important.

Furthermore, in the case of 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. Although there is no restriction | limiting in the kind of gear pump, Among these, it has a circuit which guide | induces a some polymer from the discharge side of a gear pump to a grand part via a valve, and applies a constant pressure to a shaft rod, and returns it to a suction port, A self-circulating type that does not use a packing is preferable in view of foreign matter reduction.

In the present invention, when stranding or pelletizing the polycarbonate resin directly in contact with the outside air, in order to prevent foreign matter from entering from the outside air, it is preferable to use Class 7 as defined in JIS B 9920 (2002) Preferably, it is 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. However, it is preferable to use a cooling method such as air cooling or 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 water cooling is used, it is preferable to use water obtained by removing metal particles in water with an ion exchange resin or the like, and removing foreign matters in water with the above filter. 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, releasing agents, coloring agents, antistatic agents, lubricants, lubricants, plasticizers, compatibilizers or flame retardants 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 fall of the molecular weight at the time of extrusion or filtration of the polycarbonate resin of this invention, or deterioration of color tone.

Specific examples of the phosphorous ester thermal stabilizer include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, Trioctyl phos- phite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyldiphenyl phosphite, Phenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerytrityldiphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis (2,4-di-tert-butylphenyl) pentaerythrityl diphosphite, distearylpentaerythritol diphosphite, tributylphosphate, triethylphosphate, trimethyl Phosphate, Triphenyl Phosphate, Dipe (2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphosphate, dimethyl benzenephosphonate, diisopropyl phosphate, Diethyl benzene phosphonate, dipropyl benzene phosphonate, 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) pentaerythryldiphosphite or benzene phosphonic acid dimethyl is preferable, and tris (2,4-di-tert-butylphenyl) phosphite is more preferable. .

Specific examples of the hindered phenolic thermal stabilizer include pentaerythrityl tetrakis (3-mercaptopropionate), pentaerythrityl tetrakis (3-laurylthiopropionate), pentaerythrityl tetrakis Glycerol-3-stearylthiopropionate, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), 3,5-di-tert- Butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) Cyanurate, 4,4'-biphenylenediphosphinate tetrakis (2,4-di-tert-butylphenyl) and 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 etc. 1 type (s) or 2 or more types are mentioned. .

Among them, pentaerythryl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] or octadecyl-3- (3,5-di-tert is preferable. -Butyl-4-hydroxyphenyl) propionate, particularly preferably pentaerythryltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

These heat stabilizers may be used alone or in combination of two or more. 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 the present invention, it is also effective to preliminarily filter raw material filtration filters before polycondensation of the raw material monomers in order to further reduce the impurities contained in the finally obtained polycarbonate resin pellets.

The shape of the raw material filter may be any of a basket type, a disc type, a leaf disc type, a tube type, a flat type cylindrical type, or a pleats type cylindrical type. Among them, a pleat Type is preferred.

Moreover, as a filter material which comprises the said raw material filtration filter, any of a metal wind, a laminated metal mesh, a metal nonwoven fabric, or a porous metal plate may be sufficient, but a laminated metal mesh or a metal nonwoven fabric is preferable from a filtration precision viewpoint, and a metal nonwoven fabric is especially preferable. It is preferable that the type is sintered and fixed.

There is no particular limitation on the material of the raw material filter. A metallic filter made of resin or ceramic can be used. From the viewpoint of heat resistance and reduction in coloring, a metal filter having an iron content of 80% or less is preferable. Among them, SUS304, SUS316, Stainless steels, such as SUS316L or SUS310S, are preferable.

It is preferable to use a plurality of filter units in order to increase the service life of the raw material filtration filter while ensuring filtration performance at the time of filtration of raw material monomers. Among them, the mesh of the filter in the upstream- , It is preferable that C is larger than D (C &gt; D) in at least one combination when the mesh of the filter in the unit on the downstream side is D mu m. 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 (2008) mentioned above.

In the present invention, there is no limitation on the temperature of the raw material fluid when the raw material is passed through the raw material filter. However, if the raw material is too low, the raw material is solidified. -200 degreeC, More preferably, it is 100 degreeC-150 degreeC.

Moreover, in this invention, any raw material may be filtered out of the raw material used by multiple types, and all may be filtered, The method is not limited, The raw material mixture of a dihydroxy compound and diester carbonate may be filtered. After filtering separately, you may mix. In the production method of the present invention, the reaction liquid in the middle of the polycondensation reaction may be filtered with the same filter as the raw material filtration filter.

(Polycarbonate resin obtained)

It is preferable that the yellow index value of the polycarbonate resin pellet 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 reduce a yellow index value, as mentioned above, when using monomer preparation conditions, polymerization reaction conditions, filtration conditions, and an extruder, it is necessary to appropriately select an extrusion condition or a screw element.

The molecular weight of the polycarbonate resin obtained in the method of the present invention can be expressed by a reduced viscosity (? Sp / c), and the reduced viscosity is preferably 0.2 dl / g or more, more preferably 0.25 dl / g or more, More preferably, it is 0.3 or more, It is preferable that it is 0.6 dl / g or less, More 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 that the stretching breakage may be caused. On the other hand, if it is too large, the fluidity at the time of molding tends to deteriorate, and the productivity or formability tends to be lowered. In addition, there is a possibility that the deterioration is intensified due to shearing heat generation during filtration or extrusion.

The reduced viscosity was measured by precisely weighing the polycarbonate resin pellets, precisely adjusting the amount of methylene chloride as a solvent to 0.6 g / dl, and using a Ubelode 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 the melt viscosity of from ^1, preferably at least 500 Pa · s, more preferably 1000 Pa · s or more, particularly preferably 1500 It is Pa * s or more, It is preferable that the upper limit is 5000 Pa * s or less, Preferably it is 4000 Pa * s or less.

If the melt viscosity is too low, the mechanical strength of the molded product tends to be inferior. If the melt viscosity is too high, the shearing heat generation in the filter or extruder becomes large as described above, and there is a possibility that the deterioration upon filtration or extrusion becomes intense. In addition, since the melt viscosity varies depending on the molecular structure in addition to the molecular weight, it is important to select them in accordance with the required performance and to control them in the above range.

The glass transition temperature of the polycarbonate resin obtained by the method of the present invention is not limited, but is preferably 50 占 폚 or higher, more preferably 110 占 폚 or higher, even more preferably 120 占 폚 or higher, and particularly preferably 130 占 폚 or higher. When glass transition temperature is too low, heat resistance is inferior, and there exists a possibility that the reliability at the time of using an optical member may be inferior.

On the other hand, if the glass transition temperature is high, the polycarbonate resin may deteriorate due to shear heat generation at the time of extrusion, or the melt viscosity at the time of filtration with a filter may become excessively high, which may lead to deterioration of the polycarbonate resin. It is preferable that it is less than 180 degreeC, More 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, glass transition temperature can be measured with a differential scanning calorimeter (DSC), and when it measures with the temperature increase rate of 20 degree-C / min using about 10 mg of sample, it saw the temperature (Tig) which changes in heat capacity at the lowest temperature. It defines as glass transition temperature in invention.

In the transesterification carried out in the present invention, when the polycarbonate resin of the present invention is produced by using a substituted diphenyl carbonate such as diphenyl carbonate or ditolyl carbonate as the carbonic acid diester represented by the general formula (11) , An aromatic monohydroxy compound such as phenol or substituted phenol is produced as a by-product to remain in the polycarbonate resin.

Since the aromatic monohydroxy compound may cause generation of gas at the time of filtration or odor at the time of shaping | molding, using the extruder with a vacuum vent, Preferably it is less than 0.2 weight%, More preferably, 0.1 weight It is preferable to set it as less than%, especially less than 0.08 weight%. However, it is difficult to industrially completely remove these compounds, and the lower limit of the content of the aromatic monohydroxy compound is usually 0.0001 wt%.

In addition, these aromatic monohydroxy compounds may have a substituent, of course, 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 a commonly known method such as an injection molding method, an extrusion molding method, or a compression molding method. Prior to carrying out various molding, additives such as a heat stabilizer, a neutralizer, an ultraviolet absorber, a releasing agent, a colorant, an antistatic agent, a lubricant, a lubricant, a plasticizer, a compatibilizing agent or a flame retardant are added to a resin in a tumbler, a super mixer, Or a V-type blender, a Nauter mixer, a Banbury mixer or an extruder. Moreover, after filtering on the said conditions, you may shape | mold directly into a film, without making into pellets.

Since the polycarbonate resin having little discoloration and a small amount of foreign matter can be obtained by the method of the present invention, a foreign substance having a maximum length of 25 mu m or more contained in the film having a thickness of 35 mu m +/- 5 mu m obtained by extrusion molding from the resin is preferably Can be 1000 pieces / m 2 or less, more preferably 500 pieces / m 2 or less, and most preferably 200 pieces / 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 pellets obtained by the method of the present invention can be obtained by using a polycarbonate resin such as a synthetic resin such as aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic resin, amorphous polyolefin, ABS or AS, One or two or more kinds of biodegradable resins, such as polylactic acid and polybutyrene succinate, or rubber, may be kneaded and used as polymer alloys.

According to the present invention, it is possible to provide a polycarbonate resin pellet or a polycarbonate resin film which is excellent in thermal stability, color, and mechanical strength and has little foreign matter. 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

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. Hereinafter, the physical properties and properties of the polycarbonate were evaluated by the following methods.

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 (made by AMI: 1000RS).

(2) Reduction viscosity

The polycarbonate resin was dissolved in methylene chloride as a solvent to prepare a polycarbonate solution having a concentration of 0.6 g / dl. The measurement was carried out at a temperature of 20.0 ° C ± 0.1 ° C using a Ubero's type viscometer (manufactured by Mori-Tomyo Chemical Industry Co., Ltd.), and the relative viscosity η rel was determined from the passage time t 0 of the solvent and the passage time t of the solution,

? rel = t / t0

From relative viscosity, specific viscosity (eta) sp was calculated | required by the following formula.

ηsp = (η-η0) / η0 = ηrel-1

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

(3) glass transition temperature of polycarbonate resin

The glass transition temperature of the polycarbonate resin was measured using a differential scanning calorimeter (DSC6220 manufactured by SII Nanotechnology Co., Ltd.). About 10 mg of the polycarbonate resin sample was sealed in an aluminum pan manufactured by the manufacturer, and the temperature was raised from room temperature to 250 DEG C at a heating rate of 20 DEG C / min under a flow of nitrogen gas of 50 ml / min. After maintaining temperature for 3 minutes, it cooled to 20 degree-C / min to 30 degreeC. It held at 30 degreeC for 3 minutes, and heated up at 200 degreeC / min further to 200 degreeC. The extrapolation glass transition start temperature was employ | adopted from the DSC data obtained by the 2nd temperature increase.

(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 resin, melt | dissolves in about 0.7 ml of heavy chloroform, it makes it a solution, puts it in the NMR tube of 5 mm internal diameter, Japan The 1H NMR spectrum was measured at room temperature using JNM-AL400 (resonance frequency 400 MHz) manufactured by Electronic Co., Ltd .. The structural unit ratios derived from the respective dihydroxy compounds were determined 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 with a 0.2 mu m 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 the measurement conditions were 30 mm of measurement diameters, and SCE. Calibration glass CM-A212 for challe measurement was inserted into the measuring part, zero calibration box CM-A124 was placed thereon, zero calibration was performed, and white calibration was carried out using the built-in white calibration plate.

The measurement was performed using the white calibration plate CM-A210, and it was confirmed that L * was 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 taking out a pellet from a glass container, the operation which measures again was repeated twice and the average value of the measured value of three times in total was used. The smaller the YI value, the more yellowish color is indicative of better quality.

(7) Melt viscosity

Melt Viscosity (Pas):

The sample dried for 6 hours at 120 ° C. 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 mmφ × 10 mml. 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

The polycarbonate resin vacuum-dried at 80 degreeC for 5 hours was made into a single screw extruder (Isuzu Chemical Co., Ltd. make, screw diameter 25mm, cylinder set temperature: 220 degreeC), T die (width 200mm, set temperature: 220 degreeC), chill roll ( Set film: 120-130 degreeC) The film of thickness 100micrometer +/- 5micrometer was produced using the film film manufacturing apparatus provided with the winding machine.

The sample of width 6cm and length 6cm was cut out from the said film. This sample was placed in a batch biaxial stretching apparatus (manufactured by Toyo Seiki Co., Ltd.) at a stretching speed of 720 mm / min (strain rate of 1200% / min) at a glass transition temperature of +15 deg. 2.0 times uniaxial stretching was performed and the uniform thickness film was obtained. At this time, stretching was performed in a state where the direction perpendicular to the stretching direction was maintained (drawing ratio 1.0).

A sample cut out to a width of 4 cm and a length of 4 cm was measured for the retardation (450 nm) at a wavelength of 450 nm and the retardation (R 550) at 550 nm by a phase difference measuring apparatus (KOBRA-WPR manufactured by Oji Paper Measuring Instruments) It was. And the ratio (R450 / R550) of the measured phase difference R450 and phase difference R550 was calculated. When the phase difference ratio is larger than 1, the wavelength dispersion is positive and when it is smaller than 1, the wavelength dispersion is negative (reverse dispersion). It shows that the negative wavelength dispersion property is so strong that the ratio of each phase difference is less than one.

(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 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 performed to count the frequency at which the strands were broken off by gas.

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 (trade name: POLYSORB PS, manufactured by Rocket Fluorescence)

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

DEG: diethylene glycol (manufactured by Mitsubishi Chemical Corporation)

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

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

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)

[Example 1]

In a sufficiently nitrogen-substituted (oxygen concentration of 0.0005 vol% to 0.001 vol%) raw material preparation, the raw material prepared so that the molar ratio of BHEPF / ISB / PEG (average molecular weight 1000) / DPC is 43.2 / 55.6 / 1.2 / 99 is oil. From the catalyst supply piping connected to the raw material supply pipe while supplying a constant amount continuously to the first polymerization reactor having a heat medium jacket comprising a heat medium, a heat medium inner coil, a stirring blade, an outlet pipe connected to a vacuum pump, and a condenser, Magnesium acetate tetrahydrate which was made into aqueous solution was continuously supplied so that it might become 19 * 10 <^-6> mol (magnesium metal atom conversion) per 1 mol of all 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 reactor, and the mesh of the upstream raw material filtration filter was 10 µm and downstream. The mesh was made 1 micrometer.

In the outflow pipe of the first polymerization reactor, a reflux condenser using oil (inlet temperature: 130 ° C) as a refrigerant and further a hot water as a refrigerant between the reflux condenser and the vacuum pump for condensing phenol or the like not condensed by the reflux condenser Condenser using a temperature of 45 ° C.). While keeping the rotation speed of the stirring blade of a 1st polymerization reactor constant, it controls so that it may become constant at internal temperature 196 degreeC, pressure 26.3 kPa, and residence time 1.5 hours, and extracts a reaction liquid continuously from the bottom of a tank, and a 2nd polymerization reactor Supplied to.

Similarly to the first polymerization reactor, the second polymerization reactor is equipped with a reflux condenser and a condenser in the outflow pipe and the outflow pipe connected to the heat medium jacket, the heat medium inner coil, the stirring vane, and the vacuum pump, and have an internal temperature of 207 ° C., a pressure of 23.9 kPa, It controlled so that it might become a fixed residence time of 1 hour, and the reaction liquid was continuously taken out from the bottom of a reactor tank, and it supplied to the 3rd 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 the polycondensation reaction was carried out while distilling off the by-product phenol, thereby continuously circulating the reaction solution from the bottom of the tank. Type sealing gear pump, and supplied to a horizontal type stirring reactor (fourth polymerization reactor) having two horizontal rotary shafts and substantially perpendicular to the horizontal shafts and having stirring wings discontinuous with each other.

In the fourth polymerization reactor, the inner temperature in the vicinity of the inlet was controlled to 220 ° C, the inner temperature in the vicinity of the outlet was controlled to 240 ° C, the pressure to 1.4 ㎪, and the residence time to 2 hours, and further polycondensation reaction proceeded.

The obtained polycarbonate resin had an additive feed port and three vent holes, and had a ratio L / D = 42, a kneading disk length (kneading element ratio) occupying 6% of the length of the elements constituting the entire screw of the extruder, It was fed continuously using a self-circulating seal gear Xp. The pipe connecting the gear pump and the extruder was a double tube type jacket in which the heat flowed to the outside, 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. In the extruder, 0.1% of water was supplied to the polycarbonate resin to be treated, and the vent hole was connected to a vacuum pump to remove volatile components contained in the polycarbonate resin.

The heater temperature of the barrel of the extruder was set at 245 DEG C for four blocks upstream and 225 DEG C for six downstream blocks, and the number of screw revolutions 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.

In addition, in Table 1, a kneading element ratio says the value computed from the following formula.

Kneading element ratio (%) = (total length of kneading disc / length of whole screw × 100

The polycarbonate resin treated with the extruder was supplied to the filter unit having the resin inlet at the bottom and the outlet at the top via the gear pump installed at the outlet thereof. Table 1 shows the temperature of the resin sampled immediately before the filter unit and various measured values.

Inside the filter unit, a leaf disk filter (manufactured by Nippon Pole Co., Ltd.) having a mesh of 7 占 퐉 (stainless steel (SUS304, SUS316)) was attached to remove foreign matters in the polycarbonate resin. The filter was subjected to roasting at 310 DEG C for 40 hours in an atmosphere of water vapor and then at 420 DEG C for 52 hours in an air atmosphere before use, cooled to room temperature, and then immersed in a 30 wt% nitric acid aqueous solution for 30 minutes, The oxide film was formed and the thing wash | cleaned and dried was used.

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 provided with a heater composed of a plurality of blocks. The set temperature of the heater of the polymer pipe was set to 240 캜, and the temperature of the die heater was set to 235 캜.

A sensor for measuring the resin temperature was installed in the outlet flow path of the filter unit. The temperature of the polycarbonate resin discharged from the dice was measured using a thermometer. The resin temperature at the die exit was measured directly by inserting a thermometer into the die hole. The polycarbonate resin was taken out from the dies in the form of strands in a room kept at a cleanliness of class 10000, solidified in a water tank, and pelletized with a rotary cutter. The analysis values are shown in Table 1.

[Example 2]

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. The inner temperature of the third polymerization reactor was 221 DEG C, the pressure was 23.0 DEG C, the inner temperature of the vicinity of the inlet of the fourth polymerization reactor was 225 DEG C, the inner temperature of the outlet was 239 DEG C, and the pressure was 1.3 DEG C , The screw rotation speed of the extruder, the extrusion amount of the polycarbonate resin / the cross-sectional area of the barrel of the extruder, the heater setting temperature of the filter, and the molten resin flux rate on the filter surface were changed as shown in Table 1. The analysis values are shown in Table 1.

[Example 3]

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 to 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 2 except having changed. The analysis values are shown in Table 1.

[Example 4]

The same procedure as in Example 1 was carried out except that a part of the polycarbonate resin was withdrawn from the piping for feeding the polycarbonate resin from the fourth polymerization reactor to the extruder to reduce the amount of resin fed to the extruder.

[Example 5]

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 inner temperature was 241 캜, the pressure was 18.3 ㎪, the inner temperature around the inlet of the fourth polymerization reactor was 235 캜, the inner temperature around the outlet was 250 캜, and the pressure was 1.1,. The polycarbonate resin extrusion / extruder barrel cross- Example 1 was repeated except that the inner volume of the container / the flow rate of the polycarbonate resin, and the molten resin linear velocity on the filter surface were changed as shown in Table 1. The analysis values are shown in Table 1.

[Example 6]

A side feeder is installed downstream of the vent port, and pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010) is a polycarbonate resin. Except that 0.1 part by weight and 100 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (trade name: Adecastab 2112) were continuously fed in an amount of 0.05 part by weight in the same manner as in Example 2 It was carried out.

[Example 7]

The length of the kneading disk which occupies for the length of the element which comprises the whole screw of an extruder shall be 12%, and a side feeder is provided downstream of a vent port, and pentaerythritol tetrakis (3, 5- di-t-butyl- 4-hydroxyphenyl) propionate] (trade name: IRGANOX1010) with respect to 100 parts by weight of polycarbonate resin, 0.1 part by weight of tris (2,4-di-t-butylphenyl) phosphite (brand name: Adecastab 2112 ) Was similarly carried out in the same manner as in Example 1 except that it was continuously fed to 0.05 parts by weight.

[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. Then, the heater temperature of the barrel of the extruder is set to 240 ° C for the four blocks upstream and 220 ° C for the six blocks downstream, and the screw rotation speed of the extruder, the heater setting temperature of the filter, and the heater setting temperature of the die are shown in Table 1 Changed to

A side feeder is installed downstream of the vent port, and pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010) is a polycarbonate resin. Except that 0.1 part by weight and 100 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (trade name: Adecastab 2112) It carried out similarly.

[Example 9]

As a raw material monomer, a raw material prepared so that the molar ratio of BHEPF / ISB / DEG / DPC was 37.0 / 52.7 / 10.3 / 101 was used, and magnesium acetate tetrahydrate was used as a catalyst, and 14 × 10 ^-6 per mol of the total dihydroxy compound. It used to become mol (magnesium metal atom conversion), and the supply amount per unit time of a raw material is increased than Example 8, the residence time of a 1st polymerization reactor is 0.9 hours, the residence time of a 2nd polymerization reactor is 0.6 hours, and 3rd polymerization The residence time of the reactor was 0.6 hours, the residence time of the fourth polymerization reactor was 1.1 hours, the pressure of the fourth polymerization reactor was 0.7 kPa, the mesh of the filter was 15 µm, and tris (2,4-di-t- It carried out similarly to Example 8 except not adding butylphenyl) phosphite (brand name: adecastab 2112).

[Example 10]

As a raw material monomer, a raw material prepared so that the molar ratio of BCF / SPG / CHDM / DPC was 29.3 / 35.9 / 34.8 / 103 was used, and calcium acetate monohydrate was used as a catalyst for 200 × 10 ^-6 per mol of the total dihydroxy compound. It is the same as Example 1 except having used so that it might become mol (calcium metal atom conversion), and set the fruit temperature of the piping which connects the gear pump and extruder of the 4th polymerization reactor exit to 240 degreeC, and did not add a heat stabilizer. It was carried out.

[Example 11]

As a raw material monomer, the raw material prepared so that the molar ratio of BCF / SPG / 1,6-HD / DPC might be 30.9 / 47.4 / 21.7 / 102 was used, and calcium acetate monohydrate was used as a catalyst at 250 per 1 mol of all dihydroxy compounds. It carried out similarly to Example 10 except having used so that it might become x ^10-6 mol (calcium metal atom conversion).

[Comparative Example 1]

Same as Example 1 except that the ratio of the kneading element of the extruder to the extruder was set to 12%, the number of screw rotations of the extruder was set to 285 rpm, the heater setting temperature of the filter, the heater setting temperature of the polymer pipe, It was carried out. The pressure difference at the inlet / outlet of the filter was lowered and it became easy to filtrate, but the pellets and film obtained were remarkably colored and the foreign matter was increased.

The results are shown in Tables 1 and 2.

In addition, all or part of the specification of the JP Patent application 2011-78639, the claim, drawing, and summary, and the content disclosed in the patent document quoted here etc. are referred here, and the indication of this specification is disclosed. It is taken as content.

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 mixed liquid transfer pump
4b, 4c, 4d: gear pump
5a: raw material filtration filter
6a: 1st male stirring reactor
6b: 2nd male stirring reactor
6c: third male stirring reactor
6d: 4th horizontal stirring reactor
7a, 7b, 7c: Maxblend 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 blower
16d: Product Hopper
16e: Meter
16f: product envelope (envelope, flexible container, etc.)

Claims (28)

The polycarbonate resin obtained by polycondensing a dihydroxy compound and a diester carbonate is supplied to an extruder in a molten state, and melt-extruded, and is supplied to a filter, and it is filtered using this filter, and is poly As a manufacturing method of a carbonate resin,
The dihydroxy compound represented by following General formula (1) and the dihydroxy compound represented by following General formula (9), or the dihydroxy compound represented by following General formula (1), and the following general formula ( It consists of a dihydroxy compound represented by 10),
The extruder has a screw composed of a plurality of elements, at least one of the elements being a kneading disc, the length of the total of the kneading discs being 20% or less of the entire length of the screw,
When the mesh of the said filter is 50 micrometers or less, and 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>), following formula (7) Method of producing a polycarbonate resin that satisfies.
[Chemical Formula 1]

(In said general formula (1), R <_1> -R <_4> represents a hydrogen atom, a C1-C20 alkyl group, a C6-C20 cycloalkyl group, or a C6-C20 aryl group each independently, and X Represents an alkylene group having 2 to 10 carbon atoms, a cycloalkylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and m and n each independently represent an integer of 0 to 5)
(2)

(3)

The method according to claim 1 ,
The said filter is stored in the container, The value which divided | segmented the internal volume (m <3>) of this storage container by the flow volume (m <3> / min) of the said polycarbonate resin to filter is 2 to 10 minutes. 3. The method according to claim 1 or 2,
The manufacturing method of the polycarbonate resin which filters at least 1 chosen from the said dihydroxy compound and diester carbonate by a raw material filtration filter before performing a polycondensation reaction. 3. The method according to claim 1 or 2,
The manufacturing method of the polycarbonate resin which consists of a metal which the said filter prebaked at the temperature of 350 degreeC or more and 500 degrees C or less. 3. The method according to claim 1 or 2,
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. 3. The method according to claim 1 or 2,
The glass transition temperature of the polycarbonate resin obtained by the said cooling solidification is a manufacturing method of the polycarbonate resin which is 50 degreeC or more and less than 180 degreeC. 3. The method according to claim 1 or 2,
The polycarbonate resin obtained by the said cooling solidification is obtained by using 18 mol% or more of dihydroxy compounds represented by the said General formula (1) as a raw material with respect to all the dihydroxy compounds. 3. The method according to claim 1 or 2,
The polycarbonate resin as a raw material
The dihydroxy compound represented by the said General formula (1), the dihydroxy compound represented by the said General formula (9), or the dihydroxy compound represented by the said General formula (1), and the dihydroxy represented by the said General formula (10) Oxy compound; And
Selected from the group consisting of a dihydroxy compound represented by the following general formula (4), a dihydroxy compound represented by the following general formula (5), and a dihydroxy compound represented by the dihydroxy compound represented by the following general formula (6) 1 or more dihydroxy compounds
Method for producing a polycarbonate resin using.
[Chemical Formula 4]

(In General Formula (4), R ₅ represents a cycloalkylene group having 4 to 20 carbon atoms.)
[Chemical Formula 5]

(In formula (5), R ₆ represents a cycloalkylene group having 4 to 20 carbon atoms.)
[Chemical Formula 6]

(In formula (6), R ₁₁ represents a chain alkylene group having 2 to 20 carbon atoms.) delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

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