JP2014169397A - Method for producing polycarbonate resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polycarbonate resin, in which the obtained polycarbonate resin has constant copolymer composition and an excellent color tone and at the polycarbonate resin production step of which the handling suitability of a dihydroxy compound having a fluorene group is improved drastically.SOLUTION: In the method for producing the polycarbonate resin, the polycarbonate resin is produced by a melt polycondensation reaction of dihydroxy compounds, which contain the dihydroxy compound having the fluorene group at the least, with a carbonate diester. The dihydroxy compound having the fluorene group has 6,000-12,000 mass ppm moisture content.

Description

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

  Polycarbonate resins are generally produced using raw materials derived from petroleum resources. However, in recent years, there is a concern about the exhaustion of petroleum resources, and there is a demand for providing polycarbonate resins using raw materials obtained from biomass resources such as plants. In addition, the global warming due to the increase and accumulation of carbon dioxide emissions will lead to climate change, and the development of polycarbonate resins made from plant-derived monomers that are carbon neutral even after disposal after use has been developed. It has been demanded.

For this reason, for example, it has been proposed to use isosorbide as a plant-derived monomer and obtain a polycarbonate resin by a transesterification reaction with diphenyl carbonate (see, for example, Patent Document 1).
On the other hand, a polycarbonate resin containing isosorbide as a raw material has high transparency, a low photoelastic coefficient, and heat resistance, so that it is proposed to be used for optical applications such as a phase difference plate and a substrate of a liquid crystal display device. (For example, refer to Patent Document 2). In addition, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (hereinafter referred to as BHEPF) and isosorbide as raw materials have a low photoelastic coefficient, excellent heat resistance and moldability, and are suitable for optical applications. Polycarbonate resins have been proposed (see, for example, Patent Documents 3 and 4).

  Further, paying attention to the amount of phenoxyethanol contained in BHEPF, it is disclosed that when the amount of phenoxyethanol exceeds 500 ppm, it acts as a terminal terminator, making it difficult to obtain a desired polymer (for example, Patent Document 5). reference). In addition, the manufacturing method and purification method of the said BHEPF are well-known (for example, refer patent document 6, 7).

British Patent 1,079,686 JP 2006-28441 A JP 2004-67990 A Japanese Patent Laying-Open No. 2005-29744 JP 2012-77266 A JP 7-165657 A JP 2008-222708 A

In recent years, in the field of transparent films including optical films used in liquid crystal display devices and mobile devices, the resin is melted hot without using a solvent from the conventional solution casting method using a solvent to reduce costs. Thus, it is desired to form a film by a melt film forming method.
On the other hand, polycarbonate transparent films used in such fields generally use polycarbonate resins copolymerized with multiple diol components to ensure required properties such as refractive index, heat resistance, and toughness. Therefore, it is necessary to keep the copolymer composition constant. However, in general, a diol having a fluorene ring is a fine powder and easily scatters. Also, if a large amount of the liquid component remains, the fluidity deteriorates and easily deposits on pipes and silos, resulting in a polycarbonate resin. The composition of is difficult to be constant. Moreover, since the visibility of a display screen is inferior when the color tone generally deteriorates, an optical film having a good color tone is desired.

  An object of the present invention is to solve the above-mentioned conventional problems, and in addition to having a uniform copolymer composition of the obtained polycarbonate resin and good color tone, the handling ability of the BHEPF is greatly improved in the production process of the polycarbonate resin. An improved method for producing polycarbonate resin is provided.

  As a result of repeated studies to solve the above problems, the present inventors have found that a polycarbonate resin containing a structural unit derived from a dihydroxy compound having a fluorene ring, specifically, a dihydroxy compound represented by the formula (1) described later. In the production method, by using a dihydroxy compound having a fluorene ring containing moisture in the range of 6000 mass ppm to 12000 mass ppm, the copolymer composition is constant and the color tone is good, and in the production process of the polycarbonate resin, the BHEPF It has been found that the handling aptitude of is greatly improved. The present invention has been accomplished based on these findings.

That is, the gist of the present invention resides in the following [1] to [5].
[1] In a method for producing a polycarbonate resin by melt polycondensation of a dihydroxy compound containing at least a dihydroxy compound represented by the following formula (1) and a carbonic acid diester, the dihydroxy compound represented by the formula (1) is water. The manufacturing method of polycarbonate resin characterized by including the amount of 6000 mass ppm or more and 12000 mass ppm or less.

(In the above formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein X ¹ and X ² are each independently a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, substituted or unsubstituted carbon; A cycloalkylene group of 6 to 20 or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms, m and n each independently represents an integer of 0 to 5)
[2] The dihydroxy compound represented by the formula (1) is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene or 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene. The method for producing a polycarbonate resin according to [1], which is characterized in that it exists.
[3] The method for producing a polycarbonate resin according to [1] or [2], wherein the dihydroxy compound represented by the formula (1) is previously substituted with nitrogen and then subjected to a melt polycondensation reaction.
[4] The method for producing a polycarbonate resin according to [3], wherein the dihydroxy compound represented by the formula (1) is substituted with nitrogen in a silo having a capacity of 0.01 m ³ or more and 20 m ³ or less.
[5] The method for producing a polycarbonate resin according to [3] or [4], wherein the dihydroxy compound represented by the formula (1) is charged into the silo at 25 kg or more and 10,000 kg or less and substituted with nitrogen. .

  According to the method of the present invention, a polycarbonate resin having a uniform copolymer composition and a good color tone can be obtained. In addition, in the process of producing a polycarbonate resin, the compound of formula (1) is suitable for handling. Is greatly improved. That is, according to the present invention, an efficient method for producing a high-quality polycarbonate resin can be provided.

Hereinafter, the present invention will be described in more detail. The present invention is not limited to the embodiments described below, and can be implemented with various modifications within the scope of the gist.
The present invention is a method for producing a polycarbonate resin containing at least a structural unit derived from a dihydroxy compound represented by the following formula (1), and at least one of the dihydroxy compounds used as a raw material has a water content of 6000 mass ppm. It is a dihydroxy compound represented by the following formula (1) containing 12000 ppm by mass or more.

(In the above formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein X ¹ and X ² are each independently a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, substituted or unsubstituted carbon; A cycloalkylene group of 6 to 20 or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms, m and n each independently represents an integer of 0 to 5)
The polycarbonate resin was selected from the group consisting of dihydroxy compounds represented by the following formulas (2) to (6) as necessary, in addition to the structural unit derived from the dihydroxy compound represented by the above formula (1). Structural units derived from one or more dihydroxy compounds can be included.

HO—R ⁵ —OH (3)
(In the above formula (3), R ⁵ represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.)
HO—CH ₂ —R ⁶ —CH ₂ —OH (4)
(In the above formula (4), R ⁶ represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.)
H- (O-R < ⁷ >) _p- OH (5)
(In the above formula (5), R ⁷ represents a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, and p is an integer of 2 to 100.)
HO—R ⁸ —OH (6)
(In the above formula (6), R ⁸ represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a group represented by the following formula (7).)

In the following, the carbon number of various groups means the total number of carbon atoms including the carbon number of the substituent when the group has a substituent.
[Dihydroxy Compound Represented by Formula (1)]
The polycarbonate resin according to the present invention includes a structural unit derived from a dihydroxy compound represented by the following formula (1).

In the above formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, Or a substituted or unsubstituted C6-C20 aryl group is shown.
Among these, each of R ^{1 to} R ⁴ is preferably independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 15 carbon atoms. It is more preferably a substituted alkyl group having 1 to 6 carbon atoms.

Here, the substituent in R ^{1 to} R ⁴ is preferably any group or atom selected from an ester group, an ether group, a carboxylic acid, an amide group, and a halogen. Specific examples of the substituent include an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group, and an aryl group such as a phenyl group and a naphthyl group.
Further, among R ^{1 to} R ⁴ , it is particularly preferable that R ¹ and R ² are unsubstituted alkyl groups, R ³ and R ⁴ are hydrogen atoms, or R ^{1 to} R ⁴ are all hydrogen atoms. preferable. When R ^{1 to} R ⁴ are substituents other than a hydrogen atom, it is preferably bonded to the 3rd or 5th position with respect to the bonding position of the benzene ring to the fluorene ring. A methyl group or an ethyl group is preferred.

On the other hand, in the above formula (1), X ¹ and X ² are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 6 to 20 carbon atoms, or , A substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and m and n are each independently an integer of 0 to 5;
Among them, the X ¹ and X ² each independently is preferably a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms.

Here, the substituent in X ¹ and X ² in the formula (1) is preferably any group or atom selected from an ester group, an ether group, a carboxylic acid, an amide group, and a halogen atom. Specific examples of the substituent include an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group, and an aryl group such as a phenyl group and a naphthyl group.
X ¹ and X ² are more preferably an unsubstituted alkylene group having 1 to 4 carbon atoms, particularly preferably an unsubstituted methylene group, an unsubstituted ethylene group, or an unsubstituted propylene group.

Note that X ¹ and X ² are preferably the same.
M and n are each independently preferably an integer of 0 to 2, particularly preferably 0 or 1. Note that m and n are preferably the same.
In particular, the dihydroxy compound represented by the formula (1) preferably has a bilaterally symmetric structure with the symmetry axis of the fluorene ring as the symmetry axis.

  Specific examples of the dihydroxy compound represented by the formula (1) include 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-n-propylphenyl) fluorene, 9,9-bis (4-hydroxy-3-isopropyl) Phenyl) 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-propylphenyl) 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-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 and the like.

  Among these, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4- (2- Hydroxyethoxy) phenyl) fluorene and 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene may be mentioned as preferred examples, but are not limited to these dihydroxy compounds. The dihydroxy compound represented by the formula (1) is particularly preferably 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (BCF) or 9,9-bis (4- (2-hydroxy). Ethoxy) phenyl) fluorene (BHEPF).

Since the dihydroxy compound represented by the formula (1) has a fluorene skeleton, when it is handled as a raw material for producing a polycarbonate resin, it usually contains a solid state to improve handleability. In addition, when the diameter is reduced by pulverization or the like, it tends to be scattered.
In the present invention, the amount of water contained in the dihydroxy compound represented by the formula (1) is usually 6000 mass ppm or more, preferably 7000 mass ppm or more, and more preferably 8000 mass ppm or more. If the amount of water is too small, it tends to be scattered during charging, or it may be easy to distill when evacuated for nitrogen replacement. On the other hand, the content of the compound is usually 12000 ppm by mass or less, preferably 11900 ppm by mass or less, and more preferably 11800 ppm by mass or less. If the amount of water is too large, the fluidity of the dihydroxy compound powder represented by the above formula (1) is deteriorated, and moisture remains in the inner wall of the flexible container when the silo wall surface or piping, especially the package is a flexible container. As a result, the copolymer composition of the resulting polycarbonate resin is less likely to meet the target.

The water content of the dihydroxy compound represented by the formula (1) can be controlled by a known method such as drying before use or packaging in an aluminum packaging material after drying.
On the other hand, the amount of water contained in the dihydroxy compound represented by the formula (1) can be controlled by drying. However, if the drying temperature is too high or the drying time is too long, the formula (1) The dihydroxy compound represented by this tends to deteriorate and the color tone of the resulting polycarbonate resin tends to deteriorate.

Here, the lower limit of the drying temperature is usually preferably 100 ° C. or more from the viewpoint of drying efficiency, more preferably 105 ° C. or more, and particularly preferably 110 ° C. or more. Moreover, as an upper limit, it is preferable to carry out normally at 155 degrees C or less from the point which prevents decomposition | disassembly of a raw material, 150 degrees C or less is further more preferable, and 145 degrees C or less is especially preferable.
The drying pressure is preferably carried out under reduced pressure from the viewpoint of drying efficiency, and the upper limit is usually preferably 1000 Pa or less, more preferably 500 Pa or less, and particularly preferably 300 Pa or less. Moreover, as a minimum, it is 10 Pa or more normally.

The lower limit of the drying time is usually 1 hour or longer from the viewpoint of drying efficiency, more preferably 5 hours or longer, and particularly preferably 8 hours or longer. Further, the upper limit is usually preferably 100 hours or less from the viewpoint of productivity, more preferably 80 hours or less, and particularly preferably 60 hours or less.
In order to increase the amount of water, the dihydroxy compound represented by the formula (1) is exposed to steam for 1 hour or more and less than 10 hours, or is allowed to absorb moisture in an environment of 50% humidity or more for 10 days or more after drying. There is a method of adding a certain amount of water after charging the dihydroxy compound represented by the formula (1) into a raw material hopper.

  According to the method for producing a polycarbonate resin of the present invention, the dihydroxy compound represented by the formula (1) is controlled by controlling the water content contained in the dihydroxy compound represented by the formula (1) within a specific range. The compound can be handled without scattering or adhering to the container regardless of the scale.

In the case where the raw material charging equipment is automated, the above effect becomes more remarkable as the scale becomes larger. The capacity of the silo to inject dihydroxy compound is preferably 0.01 m ³ (10L) or ^more, more preferably at least 0.1 m 3 (100L), more preferably 0.5 m ^3, 1 m ³ is especially preferred. On the other hand, from the viewpoint of practical size according to the scale of the plant, 20 m ³ or less is preferable, 10 m ³ or less is more preferable, and 5 m ³ is particularly preferable. Further, the amount of the dihydroxy compound charged into the silo is preferably 25 kg or more, more preferably 50 kg or more, further preferably 100 kg or more, and particularly preferably 200 kg or more. On the other hand, from the viewpoint of a practical input according to the scale of the plant, it is preferably 10,000 kg (10 t) or less, more preferably 5000 kg (5 t) or less, and particularly preferably 1000 kg (1 t) or less.

According to the method for producing a polycarbonate resin of the present invention, by controlling the amount of water contained in the dihydroxy compound represented by the formula (1) within a specific range, for example, to a silo of 0.5 m ³ or more. Even when 150 kg or more of the dihydroxy compound is charged and nitrogen substitution is performed and then discharged from the silo, the dihydroxy compound is quantitatively detected without being scattered in large quantities, adhering to the silo, or blocking the piping. The desired weight can be used for the polymerization reaction.

In the present invention, the polycarbonate resin may contain only one type of structural unit derived from the dihydroxy compound represented by the formula (1), or may contain two or more types.
[Dihydroxy Compound Represented by Formula (2)]
In this invention, polycarbonate resin can contain the structural unit derived from the dihydroxy compound represented by following formula (2) as needed.

  Examples of the dihydroxy compound represented by the above formula (2) include isosorbide, isomannide, and isoide which are in a stereoisomeric relationship. These may be used individually by 1 type, and may be used in combination of 2 or more types. Among these dihydroxy compounds, isosorbide obtained by dehydrating condensation of sorbitol produced from various starches that are abundant as resources and are readily available is easy to obtain and manufacture, optical properties, moldability From the viewpoint of

[Dihydroxy compounds represented by formulas (3) to (6)]
In the present invention, the polycarbonate resin may contain a structural unit derived from one or more dihydroxy compounds selected from the group consisting of dihydroxy compounds represented by the following formulas (3) to (6) as necessary. .

HO—R ⁵ —OH (3)
(In the above formula (3), R ⁵ represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.)
HO—CH ₂ —R ⁶ —CH ₂ —OH (4)
(In the above formula (4), R ⁶ represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.)
H- (O-R < ⁷ >) _p- OH (5)
(In the above formula (5), R ^{7 represents a} substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, and p is an integer of 2 to 100.)
HO—R ⁸ —OH (6)
(In the above formula (6), R ⁸ represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a group represented by the following formula (7).)

<Dihydroxy compound represented by Formula (3)>
HO—R ⁵ —OH (3)
(In the above formula (3), R ⁵ represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.)
The dihydroxy compound represented by the formula (3) is an alicyclic dihydroxy compound having 4 to 20 carbon atoms, preferably 4 to 18 carbon atoms, having a substituted or unsubstituted cycloalkylene group at R ⁵ . Here, when R ⁵ has a substituent, examples of the substituent include a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Specific examples include a methoxy group, an ethoxy group, and a propoxy group. Examples thereof include aryl groups such as an alkoxy group, a phenyl group, and a naphthyl group.

The dihydroxy compound of the above formula (3) has a ring structure derived from the cycloalkylene group of R ⁵ , thereby making it possible to increase the toughness of the molded product when the resulting polycarbonate resin is molded. Toughness can be increased.
The R ⁵ cycloalkylene group is not particularly limited as long as it is a hydrocarbon group having a ring structure, and may be a bridged structure having a bridgehead carbon atom. From the viewpoint that production of the dihydroxy compound is easy and the amount of impurities can be reduced, the dihydroxy compound represented by the formula (3) is a compound having a 5-membered ring structure or a 6-membered ring structure, that is, R ⁵ is A dihydroxy compound which is a substituted or unsubstituted cyclopentylene group or a substituted or unsubstituted cyclohexylene group is preferred. If it is such a dihydroxy compound, the heat resistance of the polycarbonate resin obtained can be made high by including a 5-membered ring structure or a 6-membered ring structure. The 6-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond.

Among them, the dihydroxy compound represented by the formula (3) is preferably various isomers in which R ⁵ is represented by the following formula (8). Here, in formula (8), R ¹¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. When R ¹¹ is a C 1-12 alkyl group having a substituent, examples of the substituent include alkoxy groups such as a methoxy group, an ethoxy group, and a propoxy group, and aryl groups such as a phenyl group and a naphthyl group. It is done.

(In the above formula (8), R ¹¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.)
More specifically, as the dihydroxy compound represented by the formula (3), tetramethylcyclobutanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3 -Cyclohexanediols such as cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol; tricyclodecanediols; pentacyclodiols, etc., but are not limited thereto is not.
These may be used individually by 1 type and may use 2 or more types together.

<Dihydroxy compound represented by Formula (4)>
HO—CH ₂ —R ⁶ —CH ₂ —OH (4)
(In the above formula (4), R ⁶ represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.)
The dihydroxy compound represented by the formula (4) is an alicyclic dihydroxy compound having 4 to 20 carbon atoms, preferably 3 to 18 carbon atoms, having a substituted or unsubstituted cycloalkylene group at R ⁶ . Here, when R ⁶ has a substituent, examples of the substituent include a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Specific examples include a methoxy group, an ethoxy group, and a propoxy group. Examples thereof include aryl groups such as an alkoxy group, a phenyl group, and a naphthyl group.

The dihydroxy compound of the above formula (4) has a ring structure derived from the cycloalkylene group of R ⁶ , thereby making it possible to increase the toughness of the molded product when the resulting polycarbonate resin is molded. Toughness can be increased.
The cycloalkylene group for R ⁶ is not particularly limited as long as it is a hydrocarbon group having a ring structure, and may be a bridge structure having a bridgehead carbon atom. From the viewpoint that production of the dihydroxy compound is easy and the amount of impurities can be reduced, the dihydroxy compound represented by the formula (4) is a compound containing a 5-membered ring structure or a 6-membered ring structure, that is, R ⁶ is A dihydroxy compound which is a substituted or unsubstituted cyclopentylene group or a substituted or unsubstituted cyclohexylene group is preferred. If it is such a dihydroxy compound, the heat resistance of the polycarbonate resin obtained can be made high by including a 5-membered ring structure or a 6-membered ring structure. The 6-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond. Among them, the dihydroxy compound represented by formula (4) is preferably a variety of isomers in which R ⁶ is the formula (8).

More specifically, as the dihydroxy compound represented by the formula (4), cyclohexanediols such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol; 8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2.6 ] decane, 3,9-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2.6 ] decane, 4,8- Spiroalkanes such as bis (hydroxymethyl) tricyclo [5.2.1.0 ^2.6 ] decane and 4,9-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2.6 ] decane. However, it is not limited to these.

These may be used alone or in combination of two or more. That is, although these dihydroxy compounds may be obtained as a mixture of isomers for production reasons, they can be used as they are as an isomer mixture. For example, 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2.6 ] decane, 3,9-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2.6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2.6 ] decane and a mixture of 4,9-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2.6 ] decane Can be used.
Of the specific examples of the dihydroxy compound represented by the formula (4), cyclohexanedimethanols are particularly preferable. From the viewpoint of easy availability and ease of handling, 1,4-cyclohexanedimethanol, 1 1,3-cyclohexanedimethanol and 1,2-cyclohexanedimethanol are preferred.

<Dihydroxy compound represented by Formula (5)>
H- (O-R < ⁷ >) _p- OH (5)
(In the above formula (5), R ⁷ represents a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, and p is an integer of 2 to 100.)
The dihydroxy compound represented by the formula (5) is a dihydroxy compound having a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms, in R ⁷ . Here, p is an integer of 2 to 100, preferably 6 to 50, more preferably 12 to 40.

Specific examples of the dihydroxy compound represented by the formula (5) include diethylene glycol, triethylene glycol, and polyethylene glycol (molecular weight: 150 to 4000), but are not limited thereto. The dihydroxy compound represented by the formula (5) is preferably polyethylene glycol having a molecular weight of 300 to 2000, and more preferably polyethylene glycol having a molecular number of 600 to 1500.
These may be used individually by 1 type and may use 2 or more types together.

<Dihydroxy compound represented by formula (6)>
HO—R ⁸ —OH (6)
(In the above formula (6), R ⁸ represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a group represented by the following formula (7).)

Dihydroxy the dihydroxy compound represented by formula (6) the number of carbon atoms of the substituted or unsubstituted on R ⁸ 2 to 20, preferably having a group shown in the alkylene group having 2 to 10 carbon atoms, or the formula (7) A compound. When the alkylene group for R ⁸ has a substituent, examples of the substituent include an alkyl group having 1 to 5 carbon atoms.
Among the dihydroxy compounds represented by the above formula (6), specific examples of the dihydroxy compound in which R ⁸ is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms include ethylene glycol, propylene glycol, 1, Examples include 4-butanediol and 1,6-hexanediol, but are not limited thereto.

Moreover, spiroglycol etc. are mentioned as a dihydroxy compound whose R < ⁸ > is an acetal ring group shown in the said Formula (7).
Among these dihydroxy compounds, 1,3-propanediol, 1,6-propanediol are preferred from the viewpoint of availability, ease of handling, high reactivity during polymerization, and hue of the obtained polycarbonate resin. Hexanediol is preferred. From the viewpoint of heat resistance, spiroglycol having an acetal ring is preferable. These may be used alone or in combination of two or more depending on the required performance of the polycarbonate resin to be obtained.

  In the present invention, the polycarbonate resin is represented by the formula (4) and / or the formula (5) among the structural units derived from the dihydroxy compound represented by the formulas (3) to (6). It preferably contains a structural unit derived from a dihydroxy compound, and more preferably contains a structural unit derived from the dihydroxy compound represented by the formula (5).

[Other dihydroxy compounds]
In this invention, polycarbonate resin contains the structural unit derived from the other dihydroxy compound as needed other than the structural unit derived from the dihydroxy compound represented by said Formula (1)-(6). Also good.
Examples of other dihydroxy compounds include bisphenols.

  Examples of bisphenols include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and 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-hydroxy) Roxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3 Examples include '-dichlorodiphenyl ether and 4,4'-dihydroxy-2,5-diethoxydiphenyl ether.

  However, since the dihydroxy compound having an aromatic ring in the structure may adversely affect the optical properties except for those represented by the formula (1), the content ratio of the structural unit derived from such a dihydroxy compound However, it is preferably 50 mol% or less, more preferably 20 mol% or less, still more preferably 5 mol% or less, based on the total of structural units derived from the dihydroxy compound in the polycarbonate resin. In particular, the polycarbonate resin in the present invention preferably does not contain a structural unit derived from a dihydroxy compound having an aromatic ring in the structure, except for the one represented by the formula (1).

[Content Ratio of Structural Units Derived from Dihydroxy Compounds Represented by Formulas (1) to (6)]
In the present invention, the content ratio of the structural unit derived from the dihydroxy compound represented by the formula (1) is 40% by mass with respect to the total of the structural units derived from the dihydroxy compound contained in the polycarbonate resin. The above is preferable, 42 mass% or more is more preferable, and 44 mass% or more is further more preferable. When the content ratio of the structural unit is excessively small, characteristics when using the polycarbonate resin as an optical film may not be preferable. On the other hand, the content is preferably 95% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less. When the content ratio of the structural unit is excessively large, when a polycarbonate resin is used as an optical film, the glass transition temperature is too high, and film formation may be difficult or brittle, and the characteristics are preferable. It may not be possible.

In the present invention, when the polycarbonate resin contains a structural unit derived from the dihydroxy compound represented by the formula (2), the above formula is used for the total of the structural units derived from the dihydroxy compound contained in the polycarbonate resin. The content ratio of the structural unit derived from the dihydroxy compound represented by (2) is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more. When the content ratio of the structural unit is excessively small, the glass transition temperature is low when used as an optical film, and deformation or the like is likely to occur when the film is formed, and the surface hardness is likely to be reduced and may be easily damaged. On the other hand, it is preferably 60% by mass or less, more preferably 58% by mass or less, and still more preferably 56% by mass or less. When the content ratio of the structural unit is excessively large, the glass transition temperature of the polycarbonate resin becomes excessively high and film formation may be difficult.

  When the polycarbonate resin contains a structural unit derived from one or more dihydroxy compounds selected from the group consisting of the dihydroxy compounds represented by the above formulas (3) to (6), the content of the polycarbonate resin is polycarbonate resin. Is preferably 0.001% by mass or more, more preferably 0.0015% by mass or more, and still more preferably 0.002% by mass or more with respect to the total of structural units derived from the dihydroxy compound contained in. On the other hand, the content is preferably less than 1% by mass, more preferably 0.1% by mass or less, and still more preferably 0.01% by mass or less. When the structural unit derived from the dihydroxy compound represented by the above formulas (3) to (6) is contained in the polycarbonate resin in the above lower limit value or more, when the polycarbonate resin is melted and molded, foreign matter or bubbles due to heat Generation of the resin can be prevented, and coloring of the polycarbonate resin can be prevented. However, if the number of structural units is excessively large, the glass transition temperature is low, and deformation tends to occur when the film is formed. Therefore, when the ratio is less than the upper limit, a film having good heat resistance can be obtained. Can do.

  In the present invention, the polycarbonate resin contains only the structural unit derived from the dihydroxy compound represented by any one of the structural units derived from the dihydroxy compound represented by the formulas (3) to (6). It may contain, and may contain a structural unit derived from a dihydroxy compound represented by two or more formulas, but it is determined whether any structural unit derived from a dihydroxy compound includes a polycarbonate resin. It is determined appropriately so as to satisfy the required characteristics according to the application. In particular, the structural unit derived from the dihydroxy compound represented by the formula (5), preferably polyethylene glycol having a molecular weight of 300 to 2000, particularly preferably polyethylene glycol having a molecular weight of 600 to 1500 is derived from the dihydroxy compound in the polycarbonate resin. It is preferable to contain 0.001% by mass or more, particularly 0.0015% by mass or more, and 1% by mass or less, particularly 0.01% by mass or less, based on the total of the structural units.

  In the present invention, the polycarbonate resin contains only the structural unit derived from the dihydroxy compound represented by any one of the structural units derived from the dihydroxy compound represented by the formulas (3) to (6). It may contain, and may contain a structural unit derived from a dihydroxy compound represented by two or more formulas, but it is determined whether any structural unit derived from a dihydroxy compound includes a polycarbonate resin. It is determined appropriately so as to satisfy the required characteristics according to the application. In particular, the structural unit derived from the dihydroxy compound represented by the formula (5), preferably polyethylene glycol having a molecular weight of 300 to 2000, particularly preferably polyethylene glycol having a molecular weight of 600 to 1500 is derived from the dihydroxy compound in the polycarbonate resin. It is preferable to contain 0.5% by mass or more, particularly 1% by mass or more, and 4% by mass or less, particularly 3% by mass or less, based on the total of the structural units.

[Production method of polycarbonate resin]
In the present invention, the polycarbonate resin can be produced by a commonly used polymerization method known per se, and the polymerization method may be any of a solution polymerization method using phosgene and a melt polymerization method in which it reacts with a carbonic acid diester. Good. More specifically, for example, one or more selected from the group consisting of the dihydroxy compound represented by the formula (1) and, if necessary, the dihydroxy compound represented by the formulas (2) to (6). A melt polymerization method is preferred in which the dihydroxy compound is further reacted with another dihydroxy compound used as necessary with a carbonic acid diester in the presence of a polymerization catalyst.

<Carbonated diester>
Examples of the carbonic acid diester used in this melt polymerization method include those represented by the following formula (10).

(In the above formula (10), A ¹ and A ² are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 18 carbon atoms. .)
Examples of the carbonic acid diester represented by the formula (10) include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carnate, and bis (biphenyl) carbonate. Diaryl carbonates; dialkyl carbonates represented by dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and the like. Of these, diaryl carbonates are preferably used, and diphenyl carbonate is particularly preferably used.

These carbonic acid diesters may be used alone or in combination of two or more.
The molar ratio of the carbonic acid diester used in the reaction is preferably 0.90 or more, more preferably 0.96 or more, based on all dihydroxy compounds. When this molar ratio is less than 0.90, the terminal hydroxyl group of the produced polycarbonate resin increases, and the thermal stability of the polymer may deteriorate, or the desired high molecular weight product may not be obtained. On the other hand, the molar ratio is preferably 1.10 or less, and more preferably 1.04 or less. If this molar ratio is greater than 1.10, the rate of transesterification reaction decreases under the same conditions, and it becomes difficult to produce a polycarbonate resin having a desired molecular weight. The amount of carbonic acid diester increases, and this residual carbonic acid diester may cause odor during molding or in the molded product.

Moreover, the polyester carbonate by which a part of carbonate bond of this said polycarbonate was substituted by the dicarboxylic acid structure can also be used. Examples of the dicarboxylic acid compound forming the dicarboxylic acid structure include terephthalic acid, phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 4 , 4′-diphenoxyethanedicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid; 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, Examples include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. From the viewpoint of heat resistance and thermal stability of the obtained polymer, Preferably dicarboxylic acids, especially from handling and easy availability, terephthalic acid, isophthalic acid are preferred, with preference terephthalic acid. These dicarboxylic acid components can be used as the raw material for the polymer of the present invention as dicarboxylic acid itself, but depending on the production method, dicarboxylic acid esters such as methyl ester and phenyl ester, and dicarboxylic acids such as dicarboxylic acid halides can be used. An acid derivative can also be used as a raw material.

<Polymerization catalyst>
In the present invention, a polycarbonate resin is produced by transesterifying the dihydroxy compound containing the dihydroxy compound represented by the formula (1) and the carbonic acid diester represented by the formula (10) as described above. More specifically, it can be obtained by transesterification and removing by-product monohydroxy compounds and the like out of the system. In this case, polycondensation is usually carried out by transesterification in the presence of a transesterification catalyst. The polymerization catalyst (transesterification catalyst) in the melt polymerization is not particularly limited as long as it does not cause a significant decrease in physical properties. However, a long-period type periodic table (Nomenclature of Ino) can be used normally.
The metal compounds of “Group 1 element” and / or “Group 2 element” (hereinafter simply referred to as “Group 1 metal compound” and “Group 2 metal compound”) in the Rangic Chemistry IUPAC Recommendations 2005) are used. The In addition to the group 1 metal compound and / or the group 2 metal compound, a basic compound such as a basic borate compound, a phosphine compound, a basic phosphonium compound, an amine compound, or a basic ammonium compound may be used in combination. Although possible, it is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.

  Examples of the Group 1 metal compound used as the polymerization catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, and carbonic acid. Potassium, lithium carbonate, 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, sodium tetraphenylborate, potassium tetraphenylborate, lithium tetraphenylborate, cesium tetraphenylborate, sodium benzoate, potassium benzoate, lithium benzoate , Cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenyl phosphate, dipotassium phenyl phosphate, dilithium phenyl phosphate, phenyl phosphate Sodium, potassium, lithium, cesium alcoholate, phenolate; bisphenol A disodium salt, dipotassium salt, dilithium salt, dicesium salt, etc., among which lithium compounds are preferred.

  Examples of the Group 2 metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, carbonate Examples include magnesium, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.

These Group 1 metal compounds and / or Group 2 metal compounds may be used alone or in combination of two or more.
Examples of the basic borate compound used in combination with the Group 1 metal compound and / or the Group 2 metal compound include tetramethyl boric acid, tetraethyl boric acid, tetrapropyl boric acid, tetrabutyl boric acid, and trimethylethyl boric acid. , Trimethylbenzyl boric acid, trimethylphenyl boric acid, triethylmethyl boric acid, triethylbenzyl boric acid, triethylphenyl boric acid, tributylbenzyl boric acid, tributylphenyl boric acid, tetraphenyl boric acid, benzyltriphenyl boric acid, methyltriphenyl Examples thereof include sodium salts such as boric acid and butyltriphenylboric acid, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, and strontium salts.

Examples of the phosphine compound or basic phosphonium compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts. .
Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.

  Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide Sid, butyl triphenyl ammonium hydroxide, and the like.

These basic compounds may be used alone or in combination of two or more.
When using the group 1 metal compound and / or the group 2 metal compound, the polymerization catalyst is preferably used in an amount of 0.1 μmol or more as a metal conversion amount with respect to 1 mol of all dihydroxy compounds used in the reaction. 0.5 μmol or more is more preferable, and 1 μmol or more is even more preferable. If the amount of the polymerization catalyst used is too small, the polymerization activity necessary to produce a polycarbonate resin having a desired molecular weight tends to be difficult to obtain. On the other hand, it is preferable to use a polymerization catalyst of 100 μmol or less, more preferably 50 μmol or less, and further preferably 25 μm or less. If the amount of polymerization catalyst used is too large, the hue of the resulting polycarbonate resin will deteriorate, and by-products will be generated, resulting in a decrease in fluidity and the generation of gels. Can be difficult.

  Moreover, when obtaining a polyester carbonate, transesterification catalysts, such as a titanium compound, a tin compound, a germanium compound, an antimony compound, a zirconium compound, a lead compound, an osmium compound, are used together with or without the above basic compound. Can also be used. The amount of these transesterification catalysts used is usually in the range of 10 μmol to 1000 μmol, preferably in the range of 20 μmol to 800 μmol, particularly preferably in terms of metal relative to 1 mol of all dihydroxy compounds used in the reaction. Is 50 μmol to 500 μmol.

<Polymerization reaction process>
In the production of the polycarbonate resin, the dihydroxy compound represented by the formula (1) may be supplied as a solid or may be heated and supplied in a molten state.
Furthermore, the dihydroxy compound represented by the formula (2), the dihydroxy compound represented by the formula (3), the dihydroxy compound represented by the formula (4), and the dihydroxy compound represented by the formula (5) And each of the one or more dihydroxy compounds selected from the group consisting of the dihydroxy compounds represented by the formula (6) may be supplied as solids or heated and supplied in a molten state. If it is soluble in water, it may be supplied as an aqueous solution. The same applies to other dihydroxy compounds.

  In the present invention, the dihydroxy compound represented by the formula (1) and, if necessary, the dihydroxy compound represented by the formula (2), the dihydroxy compound represented by the formula (3), the formula (4) ), One or more dihydroxy compounds selected from the group consisting of the dihydroxy compound represented by the formula (5) and the dihydroxy compound represented by the formula (6), and further if necessary. The method of reacting the other dihydroxy compound to be used with a carbonic acid diester in the presence of a polymerization catalyst is usually carried out in a multistage process of two or more stages.

The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.
Specifically, the first stage reaction is carried out at a temperature of 140 ° C. to 220 ° C., preferably 150 ° C. to 200 ° C. for 0.1 hour to 10 hours, preferably 0.5 hour to 3 hours. In the second and subsequent stages, the reaction temperature is gradually raised from the pressure in the first stage while gradually lowering the reaction temperature, and at the same time, monohydroxy compounds such as phenol that are generated at the same time are removed from the reaction system. Performs a polycondensation reaction under a temperature range of 210 ° C. to 280 ° C. under a reaction system pressure of 200 Pa or less.

<Addition of phosphoric acid compound and phosphorous acid compound>
When a polycarbonate resin is produced by a melt polymerization method, a phosphoric acid compound, a phosphorous acid compound, or a metal salt thereof can be added during polymerization for the purpose of preventing coloring.
As the phosphoric acid compound, one or more of trialkyl phosphates such as trimethyl phosphate and triethyl phosphate are preferably used. These are preferably added in an amount of 0.0001 mol% or more, more preferably 0.0003 mol% or more, based on the total dihydroxy compound used in the reaction. When the addition amount of the phosphoric acid compound is less than the above lower limit, the coloration preventing effect may be reduced. On the other hand, these are preferably added in an amount of 0.005 mol% or less, more preferably 0.003 mol% or less, based on all dihydroxy compounds used in the reaction. When the amount is more than the above upper limit, the haze of the polycarbonate resin may be increased, and conversely, coloring may be promoted or heat resistance may be reduced.

  Phosphite compounds include trimethyl phosphite, triethyl phosphite, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-). One or more of tert-butylphenyl) pentaerythritol diphosphite can be suitably used. These phosphorous acid compounds are preferably added in an amount of 0.0001 mol% or more, more preferably 0.0003 mol% or more, based on the total dihydroxy compound used in the reaction. When the addition amount of the phosphorous acid compound is less than the above lower limit, the coloring prevention effect may be reduced. On the other hand, these are preferably added in an amount of 0.005 mol% or less, more preferably 0.003 mol% or less, based on all dihydroxy compounds used in the reaction. When the amount is more than the above upper limit, the haze of the polycarbonate resin may be increased, and conversely, coloring may be promoted or heat resistance may be reduced.

Phosphoric acid compounds, phosphorous acid compounds or their metal salts can be added in combination, but the amount added in that case is the total amount of phosphoric acid compounds, phosphorous acid compounds or their metal salts as the total amount of dihydroxy compounds. 0.0001 mol% or more is preferable with respect to the compound, and 0.0003 mol% or more is more preferable. When this addition amount is less than the above lower limit, the coloring prevention effect may be reduced. On the other hand, the addition amount is preferably 0.005 mol% or less, and more preferably 0.003 mol% or less. When this addition amount is more than the above upper limit, it may cause the haze of the polycarbonate resin to be increased, or conversely promote the coloring or reduce the heat resistance.
In addition, as a metal salt of a phosphoric acid compound and a phosphorous acid compound, these alkali metal salt and zinc salt are preferable, and zinc salt is especially preferable. Among these zinc phosphate salts, a long-chain alkyl phosphate zinc salt is more preferable.

[Physical properties of polycarbonate resin]
<Glass transition temperature>
In the present invention, the glass transition temperature of the polycarbonate resin is preferably 90 ° C. or higher, more preferably 110 ° C. or higher, and particularly preferably 120 ° C. or higher. If the glass transition temperature is excessively low, the heat resistance tends to deteriorate, and there is a possibility of causing a dimensional change after film formation. On the other hand, the glass transition temperature is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, 1
60 ° C. or lower is particularly preferable. If the glass transition temperature is excessively high, the molding stability at the time of film molding may deteriorate, and the transparency of the film may be impaired.

Furthermore, the fluctuation range of the glass transition temperature of the polycarbonate resin is preferably within 3 ° C, preferably within 2 ° C, and more preferably within 1 ° C. The fluctuation range refers to fluctuations in the glass transition temperature of the polycarbonate resin when the obtained polycarbonate resin is arbitrarily sampled. If the fluctuation range is large, the load on the extruder or injection molding machine may fluctuate during molding, or the peeling state to the cooling roll may change during film molding, and a uniform molded product cannot be obtained. There is.
The glass transition temperature of the polycarbonate resin can be measured by the method described in the Examples section below.

<Copolymerization composition>
In the present invention, the fluctuation range of the copolymer composition of the polycarbonate resin is defined as follows.
Copolymerization composition fluctuation range: | F _{(1) g} -F _{(1) p} |
F _{(1) g} : molar fraction of the compound of formula (1) with respect to all charged dihydroxy compounds F _{(1) p} : derived from all dihydroxy compounds in a plurality of samples arbitrarily collected from the obtained polycarbonate resin The molar fraction of the structural unit derived from the compound of formula (1) with respect to the structural unit The fluctuation range of the copolymer composition is preferably 0.003, more preferably 0.002, and further preferably 0.001. If the copolymer composition varies greatly, optical characteristics and melt viscosity may fluctuate in a plurality of samples arbitrarily collected from the obtained polycarbonate resin, and a uniform molded product may not be obtained.

  In the present application, when the water content is less than 6000 mass ppm in the dihydroxy compound represented by the formula (1), the dihydroxy compound represented by the formula (1) is scattered, and the water content is 12000 mass. When it contains more than ppm, it is presumed that the copolymer composition varies due to the dihydroxy compound represented by the formula (1) adhering to the silo or the wall of the pipe.

<Reduced viscosity>
In the present invention, the molecular weight of the polycarbonate resin can be represented by a reduced viscosity. As described in the Examples section below, the reduced viscosity of the polycarbonate resin was adjusted to a polycarbonate resin concentration of 0.6 g / dL precisely using methylene chloride as a solvent, and the temperature was 20.0 ° C. ± 0. It can be determined by measurement using an Ubbelohde viscosity tube at 1 ° C.

  Although there is no restriction | limiting in particular in the reduced viscosity of polycarbonate resin, 0.30 dL / g or more is preferable and 0.33 dL / g or more is more preferable. If the reduced viscosity of the polycarbonate resin is smaller than the above lower limit, there may be a problem that the mechanical strength of the molded product becomes small. On the other hand, the upper limit of the reduced viscosity is preferably 1.20 dL / g or less, more preferably 1.00 dL / g or less, and even more preferably 0.80 dL / g or less. If the reduced viscosity is larger than the above upper limit, the fluidity during molding is lowered, resulting in a decrease in productivity, and it is difficult to remove foreign matters in the polycarbonate resin by filtration, thereby reducing foreign matters. There is a possibility that the quality of the molded product is deteriorated due to difficulty or bubbles mixed during molding.

<Melt viscosity>
In the present invention, the polycarbonate resin has a melt viscosity at a temperature of 240 ° C. and a shear rate of 91.2 sec ⁻¹ of preferably 500 Pa · sec or more, more preferably 800 Pa · sec or more, and particularly preferably 900 Pa · sec or more. If the melt viscosity of the polycarbonate resin is smaller than the above lower limit, there may be a problem that the mechanical strength of the molded product is reduced. On the other hand, it is preferably 2500 Pa · sec or less, more preferably 2300 Pa · sec or less, and particularly preferably 2000 Pa · sec or less. If the melt viscosity is larger than the above upper limit, the flowability during molding is reduced, resulting in a problem that productivity is lowered, or bubbles are mixed in the molded product at the time of molding, and the appearance of the molded product is deteriorated. Or it may be difficult to remove foreign substances in the polycarbonate resin by filtration or the like.

The melt viscosity of the polycarbonate resin was 120 ° C., and the sample dried for 6 hours was heated to 240 ° C. using a capillary rheometer (manufactured by Toyo Seiki Co., Ltd.) equipped with a die having a capillary with a diameter of 1 mmφ × length of 10 mmL. and measurable between shear rates γ = 9.12~1824 ^{(sec -1),} it is possible to obtain as a value obtained by reading the melt viscosity at 91.2sec ^-1.

<Pellet YI>
In the invention, the pellet YI, which is an index indicating the coloration of the polycarbonate resin, is preferably less than 50, preferably less than 45, and more preferably less than 40. If the pellet YI is too large, the yellowness of the film obtained by molding tends to deteriorate, and the visibility tends to deteriorate when used for display applications.

[Polycarbonate resin pellets]
Polycarbonate resin obtained by polycondensation is usually extracted in the form of a strand from an extraction port provided at the bottom of the polycondensation tank, and is cooled with water or after water cooling and then cut with a cutter to form pellets, chips, etc. It is made a body. Here, in the present invention, “pellet” means a resin cut into granular bodies. Further, as will be described later, pellets in the present invention include pellets, chips, and the like that are formed after various additives are added to the polycarbonate resin and melt-kneaded. In the present invention, the pellets of the polycarbonate resin in a granular form may be referred to as “polycarbonate resin pellets” or simply “polycarbonate resin”.

[Additive]
In the present invention, the polycarbonate resin can be blended with a heat stabilizer in order to prevent a decrease in molecular weight and a deterioration in hue during molding.
Examples of such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. More specifically, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite Phyto, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl -4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphos Ite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl Examples thereof include phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), benzenephosphonic acid dimethyl, benzenephosphonic acid diethyl, and benzenephosphonic acid dipropyl.

Among them, trisnonyl phenyl phosphite, trimethyl phosphate, tris (2,
4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol Diphosphite and dimethyl benzenephosphonate are preferably used.

These heat stabilizers may be used individually by 1 type, and may use 2 or more types together.
The heat stabilizer may be added by adding the heat stabilizer after obtaining a polycarbonate resin without adding a phosphoric acid compound, a phosphorous acid compound, or a salt thereof during melt polymerization. At the time of polymerization, a phosphoric acid compound, a phosphorous acid compound, or a salt thereof may be added, and in addition, the heat stabilizer may be further added. In other words, blending an appropriate amount of phosphorous acid compound or phosphoric acid compound to obtain a polycarbonate resin, and then blending a phosphorous acid compound further suppresses haze increase, coloring, and heat resistance degradation of the polycarbonate resin. However, more heat stabilizers can be blended, and hue deterioration can be prevented. The heat stabilizer may be formed by adding the heat stabilizer and other additives to the extruder, for example, when forming a film or the like using an extruder such as a melt extrusion method, The heat stabilizer and other additives may be added to the resin in advance using an extruder to form a pellet or the like and used for subsequent molding.

The blending amount of these heat stabilizers is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and further preferably 0.001 parts by mass or more when the polycarbonate resin is 100 parts by mass. On the other hand, it is preferably 1 part by mass or less, more preferably 0.5 part by mass or less, and further preferably 0.2 part by mass or less.
In the present invention, the polycarbonate resin may be blended with an antioxidant generally known for the purpose of antioxidant.

  Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), 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, -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5 -Di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4'-biphenylenediphosphinic acid tetrakis (2,4 -Di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2, One type or two or more types such as 4,8,10-tetraoxaspiro (5,5) undecane may be mentioned.

These antioxidants may be used alone or in combination of two or more.
The blending amount of these antioxidants is preferably 0.0001 parts by mass or more and 0.5 parts by mass or less when the polycarbonate is 100 parts by mass.
Furthermore, normally used nucleating agents, flame retardants, inorganic fillers, impact modifiers, foaming agents, dyes and pigments, other resins, and the like can be added to the polycarbonate resin as long as the effects of the present invention are not impaired. . These additives are commonly used and known per se.

In the present invention, polycarbonate resin pellets blended with the above additives are, for example,
Mixing the polycarbonate resin and the above additives simultaneously or in any order with a tumbler, V-type blender, Nauter mixer, Banbury mixer, etc. after melt-kneading, or with a mixer such as a kneading roll or extruder Then, as described above, it can be produced by drawing it into a strand and cutting it into granules.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded. In addition, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the value of the upper limit or the lower limit. It may be a range defined by a combination of values of the following examples or values of the examples.

In the following description, the abbreviations of the compounds are as follows.
BHEPF; 9,9-bis (4- (2-hydroxyethoxy) -phenyl) fluorene (Osaka Gas Chemical Co., Ltd.)
ISB; Isosorbide (Rocket Fleure, trade name: POLYSORB)
PEG # 1000; polyethylene glycol having a number average molecular weight of 1000 (manufactured by Sanyo Chemical Co., Ltd.)
DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)
[Measurement of physical properties, etc.]
In the following examples, physical properties and the like were measured by the following method unless otherwise specified. The measurement of physical properties and the like is not limited to the following method and can be appropriately selected by those skilled in the art.

<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (made by SII Nano Technology, DSC220), about 10 mg of polycarbonate resin was heated and measured at a heating rate of 20 ° C./min, in accordance with JIS-K7121 (1987), Extrapolated glass transition start temperature, which is the temperature at the intersection of the straight line that extends the low-temperature base line to the high-temperature side and the tangent line drawn at the point where the slope of the step change portion of the glass transition is maximized Was determined as the glass transition temperature.

<Reduced viscosity>
The reduced viscosity of the polycarbonate resin was measured at a temperature of 20.0 ° C. ± 0.1 ° C. using an Ubbelohde type viscosity tube manufactured by Moriyu Rika Kogyo Co., using methylene chloride as a solvent. The concentration was precisely adjusted to 0.6 g / dL.
From the passage time t _{0 of the} solvent and the passage time t of the solution, the following formula:
η _rel = t / t ₀
More seek relative viscosity eta _rel, from the relative viscosity eta _rel, formula: was obtained _{η sp = (η-η 0} ) / η 0 = η specific viscosity eta _sp than _rel -1.

By dividing the specific viscosity η _sp by the concentration c (g / dL), the following formula:
η _red = η _sp / c
From this, the reduced viscosity (converted viscosity) η _red was determined.
The higher this number, the greater the molecular weight.

<Polycarbonate pellet YI value>
The hue of polycarbonate was evaluated by measuring the YI value (yellow index value) in the reflected light of the pellet in accordance with ASTM D1925. The apparatus used was a spectrocolorimeter CM-5 manufactured by Konica Minolta, and the measurement conditions were a measurement diameter of 30 mm and SCE (regular reflection light removal). A petri dish calibration glass CM-A212 was fitted into the measurement part, and zero calibration was performed by placing a zero calibration box CM-A124 thereon, followed by white calibration using a built-in white calibration plate.

<Quantification of moisture>
BHEPF was measured at 200 ° C. using a Karl Fischer moisture meter (CA-200 manufactured by Mitsubishi Chemical Corporation).

<Copolymerization composition>
Analysis of ¹ H NMR in the case of the copolymer polycarbonate of BHEPF, ISB and PEG # 1000 exemplified in the present invention is performed as follows. Calculate the integrated value of the next peak. (Α): 8.0-7.6 ppm: derived from all BHEPF structural units (proton number: 2, molecular weight: 464.51)
(Β): 5.6-4.8 ppm: derived from all ISB structural units (proton number: 3, molecular weight: 172.14)
(Γ): 3.7-3.5 ppm: derived from all PEG # 1000 structural units (proton number: 82.3, molecular weight: 1025.99)
(Δ): 2.8-1.0 ppm: derived from hydroxy end group (proton number: 1, molecular weight: 17.01)

[Raw material BHEPF]
<BHEPF (a)>
BHEPF was used for the production of polycarbonate without any treatment. The amount of water in the BHEPF was 11800 ppm.
<BHEPF (b)>
BHEPF was used for the production of polycarbonate without any treatment. The amount of water in the BHEPF was 4800 ppm.
<BHEPF (c)>
300 kg of the BHEPF (a) was dried at 110 ° C., 200 Pa for 10 hours in a conical dryer. The water content in the BHEPF was 6500 ppm.
<BHEPF (d)>
300 kg of the BHEPF (a) was dried at 140 ° C. and 200 Pa for 50 hours with a conical dryer. The amount of water in the BHEPF was 3200 ppm.
<BHEPF (e)>
300 kg of the BHEPF (b) and 1.0 kg of water were mixed with a rotary tumbler. The water content in the BHEPF was 10500 ppm.
<BHEPF (f)>
300 kg of the BHEPF (a) and 1.5 kg of water were mixed with a rotary tumbler. The amount of water in the BHEPF was 15400 ppm.

  Table 1 shows the water content in BHEPF (a) to (f) used for the production of polycarbonate.

[Example 1]
300 kg of BHEPF (a) was charged into a 1 m ³ silo from the flexible container bag, and the inside of the silo was evacuated and then replaced with nitrogen. Thereafter, a BHEPF and magnesium acetate 4 in the hopper were placed in a polymerization reactor (1) equipped with a stirring blade and a reflux condenser controlled at 130 ° C. and purged with nitrogen and dissolved in DPC, ISB, and PEG # 1000. Hydrate was added. The molar ratio of the polycarbonate raw material is BHEPF / ISB / PEG # 1000 / DPC / magnesium acetate tetrahydrate = 0.445 / 0.552 / 0.003 / 1.015 / 1.20 × 10 ^−5. Prepared.

  The inside of the polymerization reactor (1) was heated with a heat medium, and stirring was started when the internal temperature reached 100 ° C. 40 minutes after the start of temperature increase, the internal temperature is reached to 220 ° C., and control is performed so as to maintain this temperature. At the same time, pressure reduction is started, and after reaching 220 ° C., 13.3 kPa in 90 minutes (absolute pressure, the same applies hereinafter) Then, the pressure was maintained for another 30 minutes while maintaining the pressure. The phenol vapor produced as a by-product with the polymerization reaction is led to a reflux condenser at 100 ° C., and a monomer component contained in a small amount in the phenol vapor is returned to the polymerization reactor (1), and the phenol vapor not condensed is led to a condenser at 45 ° C. And recovered.

  After returning the polymerization reaction apparatus (1) to atmospheric pressure once, the polymerization reaction apparatus (2) equipped with a stirring blade and a reflux condenser controlled at 100 ° C. is transferred to the polymerization reaction apparatus (1). The oligomerized content of was transferred. Subsequently, the temperature increase and pressure reduction in the polymerization reaction apparatus (2) were started, and the internal temperature was 240 ° C. and the pressure was 200 Pa in 50 minutes. Thereafter, the pressure was reduced to 200 Pa or less over 20 minutes, the pressure was restored when the predetermined stirring power was reached, the contents were extracted in the form of strands, and pelletized with a rotary cutter. The reduced viscosity of the obtained polycarbonate resin was 0.353 dL / g, the glass transition temperature was 145 ° C., the pellet YI was 32, and the polycarbonate resin copolymer composition BHEPF / ISB / PEG # 1000 = 0.446 / 0.551 / 0. The appearance was good at 0.003.

[Example 2]
In Example 1, it carried out like Example 1 except having changed BHEPF (c) into BHEPF (a). The polycarbonate resin obtained had a reduced viscosity of 0.351 dL / g, a glass transition temperature of 145 ° C., a pellet YI of 43, and a copolymer composition BHEPF / ISB / PEG # 1000 = 0.444 / 0.553 / 0 of the polycarbonate resin. 0.003, a polycarbonate resin substantially equivalent to that of Example 1 was obtained.

[Example 3]
In Example 1, it carried out like Example 1 except having changed BHEPF (a) into BHEPF (e). The polycarbonate resin obtained had a reduced viscosity of 0.348 dL / g, a glass transition temperature of 145 ° C., a pellet YI of 37, and a copolymer composition BHEPF / ISB / PEG # 1000 = 0.445 / 0.552 / 0 of the polycarbonate resin. 0.003, a polycarbonate resin substantially equivalent to that of Example 1 was obtained.

[Comparative Example 1]
In Example 1, it carried out like Example 1 except having changed BHEPF (a) into BHEPF (b). When BHEPF (b) was introduced from the flexible container bag, a small amount of BHEPF fine powder was scattered. The reduced viscosity of the obtained polycarbonate resin is 0.339 dL / g, the glass transition temperature is 144 ° C., the pellet YI is 35, and the polycarbonate resin copolymer composition BHEPF / ISB / PEG # 1000 = 0.442 / 0.555 / 0. The copolymer composition varied as compared with Example 1, and YI increased.

[Comparative Example 2]
In Example 1, it carried out like Example 1 except having changed BHEPF (a) into BHEPF (d). When BHEPF (d) was introduced from the flexible container bag, a small amount of BHEPF fine powder was scattered. The polycarbonate resin obtained had a reduced viscosity of 0.341 dL / g, a glass transition temperature of 144 ° C., a pellet YI of 51, and a polycarbonate resin copolymer composition BHEPF / ISB / PEG # 1000 = 0.441 / 0.555 / 0. .004, the copolymer composition varied as compared with Example 1, and YI significantly increased.

[Comparative Example 3]
In Example 1, it carried out like Example 1 except having changed BHEPF (a) into BHEPF (d). When BHEPF (f) was charged from the flexible container bag, a large amount of BHEPF fine powder adhered to the charging hopper. The polycarbonate resin obtained had a reduced viscosity of 0.341 dL / g, a glass transition temperature of 144 ° C., a pellet YI of 51, and a polycarbonate resin copolymer composition BHEPF / ISB / PEG # 1000 = 0.439 / 0.557 / 0. The copolymer composition varied as compared with Example 1.
The results of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 2.

As shown in Table 2, in Examples 1 to 3 where the water content in BHEPF is 6000 mass ppm or more and 12000 mass ppm or less, the reduced viscosity of the obtained polycarbonate resin is high, and the polymer composition is determined from the amount of raw material used. There was little deviation from the required theoretical composition. In addition, a polycarbonate resin having a low YI and little coloring was obtained.
On the other hand, in the case of Comparative Example 1 and Comparative Example 2 containing less than 6000 ppm by weight of water in BHEPF, BHEPF is likely to be scattered, and the raw material molar ratio charged into the polymerization reactor (I) varies. The copolymer composition of the obtained polycarbonate resin greatly fluctuated, and as a result of a significant increase in YI and a decrease in the copolymerization reaction rate, the reduced viscosity of the obtained polycarbonate resin also decreased.

  Moreover, in the case of the comparative example 3 which made the water | moisture content in BHEPF more than 12000 mass ppm, since BHEPF becomes easy to adhere to a wall and the raw material molar ratio thrown into a polymerization reaction apparatus (I) fluctuates, the obtained polycarbonate As the copolymerization composition of the resin fluctuated greatly and the copolymerization reaction rate decreased, the reduced viscosity of the obtained polycarbonate resin also decreased.

Claims (5)

In a method for producing a polycarbonate resin by melt polycondensation of a dihydroxy compound containing at least a dihydroxy compound represented by the following formula (1) and a carbonic acid diester, the dihydroxy compound represented by the formula (1) has a water content of 6000. The manufacturing method of polycarbonate resin characterized by including mass ppm or more and 12000 mass ppm or less.

(In the above formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein X ¹ and X ² are each independently a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, substituted or unsubstituted carbon; A cycloalkylene group of 6 to 20 or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms, m and n each independently represents an integer of 0 to 5)   The dihydroxy compound represented by the formula (1) is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene or 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene. The method for producing a polycarbonate resin according to claim 1.   The method for producing a polycarbonate resin according to claim 1 or 2, wherein the dihydroxy compound represented by the formula (1) is preliminarily substituted with nitrogen and then subjected to a melt polycondensation reaction. The method for producing a polycarbonate resin according to claim 3, wherein the dihydroxy compound represented by the formula (1) is substituted with nitrogen in a silo having a capacity of 0.01 m ³ or more and 20 m ³ or less.   5. The method for producing a polycarbonate resin according to claim 3, wherein the dihydroxy compound represented by the formula (1) is charged to 25 kg or more and 10,000 kg or less of the silo and substituted with nitrogen.