TWI428366B - Polycarbonate resin, method of producing polycarbonate resin, and transparent film - Google Patents

Description

Polycarbonate resin, method for producing polycarbonate resin and transparent film

The present invention relates to a polycarbonate resin or the like, and more specifically relates to a polycarbonate resin containing at least a constituent unit derived from a dihydroxy compound having a specific bond structure.

In recent years, there has been reported a polycarbonate resin containing at least a constituent unit derived from a dihydroxy compound having a specific bond structure represented by the following structural formula (1). For example, Patent Document 1 describes a polycarbonate resin excellent in optical properties, which is used in a bisphenol compound having an anthracene ring in a side chain and 2,2-bis(4-hydroxydiphenyl)propane. Patent Document 2 describes a polycarbonate resin excellent in heat resistance and hue, which is used in a bisphenol compound having an anthracene ring in a side chain. Patent Document 3 describes a polycarbonate resin having a small photoelastic coefficient, which is used in a bisphenol compound having an anthracene ring in a side chain and pentacyclodecane dimethanol.

[Chemical 1]

(wherein, the formula (1) excludes a structure in which a hydrogen atom is bonded to an oxygen atom.)

Patent Document 1: Japanese Patent Laid-Open No. Hei 10-101786

Patent Document 2: Japanese Patent Laid-Open No. Hei 10-101787

Patent Document 3: Japanese Patent Laid-Open Publication No. 2004-067990

The polycarbonate resin is used in various optical materials because it exhibits excellent transparency and heat resistance. In particular, a polycarbonate resin containing at least a constituent unit derived from a dihydroxy compound having a bond structure represented by the above structural formula (1) is considered to be suitable for a retardation film or the like because of its small photoelastic coefficient.

However, according to the review by the inventors and the like, when the polycarbonate resin is used as an optical material, there is a problem that coloring is easy. Further, in order to obtain a polycarbonate resin having a high molecular weight, a large amount of catalyst must be used during polymerization, or a long-term polymerization reaction must be carried out.

An object of the present invention is to provide a polycarbonate resin containing at least a constituent unit derived from a dihydroxy compound having a bond structure represented by the above structural formula (1), a method for producing the same, and a transparent film.

According to the present invention, there is provided a polycarbonate resin which contains at least a constituent unit derived from a dihydroxy compound having a bond structure represented by the following structural formula (1) in a molecule, and a sulfur element content of 5 ppm. the following.

[Chemical 2]

(wherein, the formula (1) excludes a structure in which a hydrogen atom is bonded to an oxygen atom.)

Here, the dihydroxy compound having the bond structure represented by the above structural formula (1) is preferably a dihydroxy compound represented by the following general formula (2).

[Chemical 3]

(In the general formula (2), A ¹ and A ² each independently represent an arbitrary divalent hydrocarbon group, and X represents any one of a methylene group, a carbonyl group, and a direct bond.)

Further, in the above general formula (2), A ¹ and A ² preferably have a hydrocarbon group having 6 to 20 carbon atoms, and in the above general formula (2), A ¹ and A ² preferably have a carbon number of 6~. An aromatic hydrocarbon group having 12 carbon atoms.

Further, it is preferable to further have a constituent unit derived from at least one dihydroxy compound selected from the group consisting of a heterocyclic dihydroxy compound and an alicyclic dihydroxy compound, and the heterocyclic dihydroxy compound is preferably of the following formula ( 3) A dihydroxy compound represented.

[Chemical 4]

Moreover, according to the present invention, there is provided a method for producing a polycarbonate resin, which comprises a dihydroxy compound having a bond structure represented by the following structural formula (1) and having a sulfur element content of 9 ppm or less, and a carbonic acid compound The ester is polymerized in the presence of a polymerization catalyst.

[Chemical 5]

(wherein, the formula (1) excludes a structure in which a hydrogen atom is bonded to an oxygen atom.)

In addition, the dihydroxy compound having a bond structure represented by the above structural formula (1) is preferably a dihydroxy compound having a sulfur element content of 9 ppm or less represented by the following formula (2).

[Chemical 6]

(In the formula (2), A ¹ and A ² each independently represent an arbitrary divalent hydrocarbon group, and X represents any one of a methylene group, a carbonyl group, and a direct bond.)

Further, it is preferred to further carry out copolymerization by selecting at least one dihydroxy compound from the heterocyclic dihydroxy compound represented by the following formula (3) and the alicyclic dihydroxy compound.

[Chemistry 7]

Further, as the polymerization catalyst, at least one compound selected from the group consisting of an alkali metal compound and an alkaline earth metal compound is preferably used, and the amount of the polymerization catalyst used is 1 mol relative to the total dihydroxy compound used for the reaction. It is preferably 0.1 μm to 100 μm in terms of metal conversion. Further, the polymerization temperature is preferably from 210 ° C to 270 ° C.

Further, according to the present invention, a transparent film obtained by forming a polycarbonate resin obtained by the present invention can be provided. The transparent film is preferably used as an optical film, and more preferably a retardation film which is further extended to be aligned.

That is, the gist of the present invention is the following (1) to (15).

(1) A polycarbonate resin containing at least a constituent unit derived from a dihydroxy compound having a bond structure represented by the following structural formula (1) in a molecule, and having a sulfur element content of 5 ppm or less.

[化8]

(wherein, the formula (1) excludes a structure in which a hydrogen atom is bonded to an oxygen atom.)

(2) The polycarbonate resin of (1), preferably the dihydroxy compound having the bond structure represented by the above structural formula (1) is a dihydroxy compound represented by the following general formula (2).

[Chemistry 9]

(In the general formula (2), A ¹ and A ² each independently represent an arbitrary divalent hydrocarbon group, and X represents any one of a methylene group, a carbonyl group, and a direct bond.)

(3) The polycarbonate resin according to (2), preferably, in the above general formula (2), A ¹ and A ^{2 each} have a hydrocarbon group having 6 to 20 carbon atoms.

(4) The polycarbonate resin according to (2) or (3), preferably, in the above general formula (2), A ¹ and A ^{2 each} have an aromatic hydrocarbon group having 6 to 12 carbon atoms.

(5) The polycarbonate resin according to any one of (1) to (4), preferably further comprising at least one selected from the group consisting of a heterocyclic dihydroxy compound and an alicyclic dihydroxy compound. The constituent unit of a hydroxy compound.

(6) The polycarbonate resin according to (5), preferably, the heterocyclic dihydroxy compound is a dihydroxy compound represented by the following formula (3).

[化10]

(7) A method for producing a polycarbonate resin, which comprises a divalent compound having a bond structure represented by the following structural formula (1) and having a sulfur element content of 9 ppm or less, and a polymerization catalyst of a carbonic acid diester. The polymerization is carried out in the presence of it.

[11]

(wherein, the formula (1) excludes a structure in which a hydrogen atom is bonded to an oxygen atom.)

(8) The method for producing a polycarbonate resin according to (7), preferably a dihydroxy compound having a bond structure represented by the above structural formula (1), which is a sulfur element represented by the following formula (2) A dihydroxy compound having a content of 9 ppm or less.

[化12]

(In the formula (2), A ¹ and A ² each independently represent an arbitrary divalent hydrocarbon group, and X represents any one of a methylene group, a carbonyl group, and a direct bond.)

(9) The method for producing a polycarbonate resin according to (7) or (8), preferably, further comprising a heterocyclic dihydroxy compound and an alicyclic dihydroxy compound represented by the following formula (3) At least one dihydroxy compound is selected for copolymerization.

[Chemistry 13]

(10) The method for producing a polycarbonate resin according to any one of (7) to (9), wherein, as the polymerization catalyst, at least one selected from the group consisting of an alkali metal compound and an alkaline earth metal compound is used. Kind of compound.

(11) The method for producing a polycarbonate resin according to any one of (7) to (10), preferably, the amount of the polymerization catalyst used is 1 mol based on the total dihydroxy compound used in the reaction. The metal conversion gauge is 0.1 μm to 100 μm.

(12) The method for producing a polycarbonate resin according to any one of (7) to (11), wherein the polymerization temperature is preferably from 210 ° C to 270 ° C.

(13) A transparent film obtained by forming a polycarbonate resin according to any one of (1) to (6).

(14) A transparent film as in (13), preferably an optical film.

(15) The transparent film of (13), which is preferably a retardation film in which the optical film is extended and aligned.

According to the present invention, a polycarbonate having at least a constituent unit derived from a dihydroxy compound having a bond structure represented by the above structural formula (1) and having excellent transparency can be obtained.

Hereinafter, embodiments of the invention will be described in detail. The present invention is not limited to the following embodiments, and various changes can be made within the scope of the gist of the invention. Further, all of the ppm in the present invention means a ppm by weight. Moreover, the drawings used are for explaining the present embodiment and do not show the actual size.

[1] polycarbonate resin (Dihydroxy compound represented by the formula (1))

The polycarbonate resin of the present invention contains at least a constituent unit derived from a dihydroxy compound represented by the following structural formula (1) in the molecule.

[Chemistry 14]

(wherein, the formula (1) excludes a structure in which a hydrogen atom is bonded to an oxygen atom.)

Here, the dihydroxy compound having a bond structure represented by the structural formula (1) in the molecule has a structure having a hydroxyl group having two hydroxyl groups and having a linking group -CH ₂ —O— in the molecule, and the structure A dihydroxy compound having a structure in which a bond structure is excluded from a hydrogen atom bonded to an oxygen atom, and a compound which can react with a carbonic acid diester to form a polycarbonate in the presence of a polymerization catalyst, a compound of any structure It can be used or used in combination.

Further, the polycarbonate of the present invention preferably has a constituent unit derived from a heterocyclic dihydroxy compound and a lipid in addition to a constituent unit derived from a dihydroxy compound having a bond structure represented by the formula (1). A constituent unit of at least one dihydroxy compound is selected from the cyclic dihydroxy compounds. In this case, at least one dihydroxy compound selected from the heterocyclic dihydroxy compound and the alicyclic dihydroxy compound may have a bond structure represented by the structural formula (1) in its molecule. When at least one dihydroxy compound selected from the heterocyclic dihydroxy compound and the alicyclic dihydroxy compound is formed by a bond structure represented by the structural formula (1) in the molecule, the polycarbonate resin becomes There are two or more constituent units having a dihydroxy compound derived from a bond structure represented by the structural formula (1) in the molecule. Of course, the polycarbonate resin may have two or more constituent units derived from the following compounds: at least one dihydroxy compound selected from the heterocyclic dihydroxy compound and the alicyclic dihydroxy compound, and intramolecular therein A dihydroxy compound having a bond structure represented by the formula (1).

Further, the dihydroxy compound used in the polycarbonate resin of the present invention may be used in combination with a dihydroxy compound which does not have a bond structure represented by the structural formula (1).

Hereinafter, a dihydroxy compound having a bond structure represented by the structural formula (1) in its molecule may be simply referred to as a dihydroxy compound (I).

(dihydroxy compound (I))

The "linking group -CH ₂ -O-" in the dihydroxy compound (I) means a structure in which a molecule other than a hydrogen atom is bonded to each other to form a molecule. In the linking group, as an atom which can bond at least an oxygen atom or an atom which can bond a carbon atom and an oxygen atom at the same time, it is preferably a carbon atom, and the "linking group -CH ₂ -O in the dihydroxy compound (I) The number of -" is 1 or more, preferably 2 to 4.

More specifically, the dihydroxy compound (I) may, for example, be 9,9-bis(4-(2-hydroxyethoxy)phenyl)anthracene or 9,9-bis(4-(2-hydroxyethyloxy). 3-methylphenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)anthracene, 9,9-bis(4-(2- Hydroxyethoxy)-3-isobutylphenyl)indole, 9,9-bis(4-(2-hydroxyethoxy)-3-t-butylphenyl)anthracene, 9,9 double (4 -(2-hydroxyethoxy)-3-cyclohexylphenyl)anthracene, 9,9-bis(4(2-hydroxyethoxy)-3-phenylphenyl)anthracene, 9,9-bis ( 4-(2-hydroxyethoxy)-3,5-dimethylphenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy)3-tert-butyl-6-methyl Phenyl) ruthenium, 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)anthracene, etc., exemplified as having an aromatic group in the side chain, but in the main chain a compound having an ether group bonded to an aromatic group; an alkylene glycol exemplified by diethylene glycol, triethylene glycol, tetraethylene glycol or the like; bis[4-(2-hydroxyethoxyl) Phenyl]methane, bis[4-(2-hydroxyethoxy)phenyl]diphenylmethane, 1,1-bis[4-(2-hydroxyethoxy)phenyl]ethane, 1 , 1-bis[4-(2-hydroxyethoxy)phenyl]-1-phenylethane, 2,2-bis[4-(2-hydroxyethyl) Phenyl]propane, 2,2-bis[4-(2-hydroxyethoxy)-3-methylphenyl]propane, 2,2-bis[3,5-dimethyl-4-( 2-hydroxyethoxy)phenyl]propane, 1,1-bis[4-(2-hydroxyethoxy)phenyl]-3,3,5-trimethylcyclohexane, 1,1-double [4-(2-hydroxyethoxy)phenyl]cyclohexane, 1,4-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 1,3-bis[4-( 2-hydroxyethoxy)phenyl]cyclohexane, 2,2-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]propane, 2,2-bis[(2-hydroxyl) Ethoxy)-3-isopropylphenyl]propane, 2,2-bis[3-t-butyl-4-(2-hydroxyethoxy)phenyl]propane, 2,2-bis[4 -(2-hydroxyethoxy)phenyl]butane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]-4-methylpentane, 2,2-bis[4- (2-hydroxyethoxy)phenyl]octane, 1,1-bis[4-(2-hydroxyethoxy)phenyl]decane, 2,2-bis[3-bromo-4-( Bis(hydroxyalkoxyaryl) exemplified by 2-hydroxyethoxy)phenyl]propane, 2,2-bis[3-cyclohexyl-4-(2-hydroxyethoxy)phenyl]propane, etc. Alkanes; 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 1,1-bis[3-cyclohexyl-4-(2-hydroxyethoxy)phenyl] Cyclohexane, 1,1-bis[4-(2-hydroxyethoxy)benzene a bis(hydroxyalkoxyaryl)cycloalkane exemplified by cyclopentane or the like; 4,4'-bis(2-hydroxyethoxy)diphenyl ether, 4,4'-bis(2-hydroxyl) Dihydroxyalkoxy diaryl ethers exemplified by ethoxy)-3,3'-dimethyldiphenyl ether; 4,4'-bis(2-hydroxyethoxyphenyl) sulfide a bishydroxyalkoxy aryl sulfide exemplified by 4,4'-bis[4-(2-dihydroxyethoxy)-3-methylphenyl] sulfide or the like; 4,4'-double a bishydroxyalkoxy group exemplified by (2-hydroxyethoxyphenyl) anthracene, 4,4'-bis[4-(2-dihydroxyethoxy)-3-methylphenyl]anthracene or the like Aryl hydrazins; 4,4'-bis(2-hydroxyethoxyphenyl)anthracene, 4,4'-bis[4-(2-dihydroxyethoxy)-3-methylphenyl] a bishydroxyalkoxyaryl hydrazine exemplified by hydrazine, etc.; 1,4-bishydroxyethoxybenzene, 1,3-dihydroxyethoxybenzene, 1,2-bishydroxyethoxybenzene, 1, 3-bis[2-[4-(2-hydroxyethoxy)phenyl]propyl]benzene, 1,4-bis[2-[4-(2-hydroxyethoxy)phenyl]propyl] Benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, 1,3-bis[4-(2-hydroxyethoxy)phenyl]-5,7-dimethyladamantane, and the like. These dihydroxy compounds (I) may be used alone or in combination of two or more.

The dihydroxy compound having the bond structure represented by the above structural formula (1) is preferably a dihydroxy compound represented by the following general formula (2).

[化15]

(In the general formula (2), A ¹ and A ² each independently represent an arbitrary divalent hydrocarbon group, and X represents any one of a methylene group, a carbonyl group, and a direct bond.)

Here, as A ¹ and A ² , a hydrocarbon group having 6 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 12 carbon atoms are preferable.

Specific examples of the hydrocarbon group having 6 to 20 carbon atoms include a linear divalent alkylene group such as a methylene group, an exoethyl group, a n-propyl group, a n-butyl group, a n-pentyl group or a n-hexyl group. ; 1-methylethyl, 2-methylethyl, 1-ethylethyl, 2-ethylethyl, 1-methylpropyl, 2-methylpropyl, 3-methyl An alkyl group containing a branched chain such as a propyl group.

Further, a divalent alkylene group having an alicyclic structure represented by the following group {A] can be mentioned.

[Chemistry 16] [A]

(The substitution position of the two bonding bonds in each ring structure shown in the above [A] group, that is, the substitution position of the p-hydroxy group and the aromatic group is arbitrary.)

A ¹ and A ² are preferably each independently a methylene group, an ethyl group, a n-propyl group, a 1-methyl-ethyl group, a 2-methyl-ethyl group, from the viewpoint of good physical properties of the obtained resin. An alkylene group having a carbon number of 4 or less such as 1-ethylexylethyl or 2-ethylexylethyl, and a divalent group having an alicyclic structure represented by the following group [B].

[化17] [B]

(The substitution position of two bonding bonds in the ring structure shown in the above [B] group, that is, the substitution position of the p-hydroxy group and the aromatic group is arbitrary.)

Further, from the viewpoint of easy synthesis, it is preferred that A ¹ and A ² are each independently a methylene group, an ethyl group, a 1-methyl group ethyl group, a 2-methyl group ethyl group, and the following [C] group. A group of divalent groups having an alicyclic structure as shown.

[化18] [C]

(The substitution position of the two bonding bonds in the ring structure shown in the above [C] group, that is, the substitution position of the p-hydroxy group and the aromatic group is arbitrary.)

In the general formula (2), X is a methylene group, a carbonyl group or a direct bond, and from the viewpoint that the aromatic ring is fixed and the optical properties are good, a carbonyl group or a direct bond is preferred.

Specific examples of the compound include 9,9-bis(hydroxymethyl)anthracene, 9,9-bis(hydroxyethyl)anthracene, and 9,9-bis(1-methyl-2-hydroxyethyl)anthracene. 9,9-bis(2-methyl-2-hydroxyethyl)anthracene, 9,9-bis(4-hydroxycyclohexyl)anthracene or the like. These compounds may be used alone or in combination of two or more.

Next, specific examples of the aromatic hydrocarbon group having a carbon number of 6 to 12 carbon atoms include 9,9-bis(4-hydroxyphenyl)anthracene and 9,9-bis(4-hydroxy-3-methyl group. Phenyl) ruthenium, 9,9-bis{3-methyl-4-(2-hydroxyethoxy)phenyl]anthracene, 9,9-bis{4-(2-hydroxyethoxy)phenyl] Indole, 9,9-bis[4-(2-hydroxypropoxy)phenyl]anthracene, 9,9-bis{3-methyl-4-(2-hydroxypropoxy)phenyl]anthracene, 9 , 9-bis{3'-methyl-4'-(2-hydroxyethoxy)phenyl]anthracene, and the like.

(heterocyclic dihydroxy compound)

In addition to the constituent unit of the dihydroxy compound derived from the bond structure represented by the above structural formula (1), the polycarbonate resin of the present invention preferably contains a heterocyclic dihydroxy compound and an alicyclic ring. The constituent unit of at least one dihydroxy compound is selected from the dihydroxy compound. More specifically, the heterocyclic dihydroxy compound is a heterocyclic dihydroxy compound represented by a dihydroxy compound represented by the following formula (3), or 3,9-bis(2-hydroxy-1, 1-dimethylethyl)-2,4,8,10-four Spiro[5,5]undecane, 2-(5-ethyl-5-hydroxymethyl-1,3-di A spirohydrocarbon derivative such as alk-2-yl)-2-methylpropan-1-ol.

Among them, the heterocyclic dihydroxy compound is preferably a dihydroxy compound represented by the above formula (3).

Examples of the dihydroxy compound represented by the above formula (3) include isosorbide, isomannide, and Isoidide having a stereoisomer relationship. These may be used alone or in combination of two or more. Among these dihydroxy compounds, from the viewpoint of ease of manufacture, optical properties, and formability, it is preferable to dehydrate the sorbitol produced from various starches which are abundant in resources and easily available. The resulting isosorbide is polymerized.

In addition, isosorbide is easily oxidized by oxygen. Therefore, in order to prevent decomposition by oxygen at the time of storage or manufacturing, it is important to use a deoxidizing agent or a nitrogen atmosphere in such a manner that moisture is not mixed. If isosorbide is oxidized, decomposition products such as formic acid may occur. For example, when a polycarbonate resin is produced using isosorbide containing such a decomposition product, the obtained polycarbonate resin is colored, which causes a significant deterioration in physical properties. Further, it is also inferior to the polymerization reaction, and it is not preferable to obtain a polymer having a high molecular weight. Further, when a stabilizer for preventing the formation of formic acid is added, the obtained polycarbonate resin may be colored or the physical properties may be remarkably deteriorated depending on the type of the stabilizer. The stabilizer is a reducing agent or an ant. In addition, examples of the reducing agent include sodium borohydride and lithium borohydride, and examples of the acid generator include a base such as sodium hydroxide. In the addition of such an alkali metal salt, since the alkali metal also acts as a polymerization catalyst, if it is added in excess, the polymerization reaction cannot be suppressed, which is not preferable.

When the isosorbide containing no oxidative decomposition product is obtained, the isosorbide may be distilled as needed. Further, in order to prevent the oxidation or decomposition of isosorbide and to add a stabilizer, isosorbide may be distilled as needed. In this case, the distillation of isosorbide may be a single distillation or a continuous distillation, and is not particularly limited. The distillation is carried out under reduced pressure in an inert gas atmosphere such as argon or nitrogen. By carrying out the distillation of such isosorbide, a high-purity isosorbide having an formic acid content of 20 ppm or less, particularly 5 ppm or less can be used.

Further, the method for measuring the content of formic acid in isosorbide was carried out by ion chromatography (Ion Chromatography) according to the following method.

Approximately 0.5 g of isosorbide was weighed and placed in a 50 ml volumetric flask for constant volume with pure water. An aqueous sodium formate solution was used as a standard sample, and a peak in which the standard sample was consistent with the retention time was defined as formic acid, and the peak area was quantified by an absolute calibration line method.

The ion chromatography system uses the DX-500 model manufactured by Dionex, and the detector uses a conductivity detector. As the measuring column, the guard column was made of AG-15 manufactured by Dionex, and the separation column was AS-15 of Dionex. The measurement sample was injected into a sample loop of 100 μl, and 10 mM-NaOH was used as a solution, and the measurement was performed at a flow rate of 1.2 ml/min and a bath temperature of 35 °C. A suppressor was used as a thin film suppressor, and a reconstituted liquid was a 12.5 mM-H ₂ SO ₄ aqueous solution.

(alicyclic dihydroxy compound)

The polycarbonate resin of the present invention preferably has a constituent unit derived from an alicyclic dihydroxy compound, in addition to a constituent unit derived from a dihydroxy compound having a bond structure represented by the above structural formula (1).

The alicyclic dihydroxy compound is not particularly limited, and a compound having a 5-membered ring structure or a 6-membered ring structure is usually used. By making the alicyclic dihydroxy compound into a 5-membered ring structure and a 6-membered ring structure, the heat resistance of the obtained polycarbonate resin can be improved. The 6-member ring structure can also be fixed to a chair shape or a boat shape by using a covalent bond.

The number of carbon atoms contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, more preferably 30 or less. When the number of carbon atoms is too large, heat resistance is improved, but it is difficult to synthesize, it is difficult to refine, and the cost tends to be too high. The smaller the number of carbon atoms, the easier it is to purify and to be easily obtained.

Specific examples of the alicyclic dihydroxy compound having a 5-membered ring structure or a 6-membered ring structure include the alicyclic dihydroxy compound represented by the following general formula (II) or (III).

HOCH ₂ -R ¹ -CH ₂ OH (II)

HO-R ² -OH (III)

(In the formulae (II) and (III), R ¹ and R ^{2 each} represent a cycloalkyl group having 4 to 20 carbon atoms which may have a substituent.)

The cyclohexanedimethanol which is an alicyclic dihydroxy compound represented by the above general formula (II) is contained in the general formula (II), and R ^{1 is} represented by the following general formula (IIa) (wherein R ³ represents a carbon number) Various isomers represented by an alkyl group of 1 to 12). Specific examples of such a substance include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol.

[Chemistry 20]

Tricyclodecane dimethanol or pentacyclopentane dimethanol which is an alicyclic dihydroxy compound represented by the above general formula (II) is contained in the general formula (II) wherein R ^{1 is} represented by the following general formula (IIb) (wherein, n represents 0 or 1) represents various isomers.

[Chem. 21]

As the alicyclic dihydroxy compound represented by the above general formula (II), decalin dimethanol or tricyclotetraoxane dimethanol is contained in the general formula (II), and R ^{1 is} represented by the following general formula (IIc) ( In the formula, m represents various anisotropy represented by 0 or 1). Specific examples of such a substance include 2,6-decahydronaphthalene dimethanol, 1,5-decahydronaphthalene dimethanol, and 2,3-decahydronaphthalene dimethanol.

[化22]

Further, as a drop of the alicyclic dihydroxy compound represented by the above general formula (II) The alkane dimethanol is a various isomer represented by the following general formula (IId), wherein R ¹ is represented by the general formula (II). Specific examples of such a substance include 2,3-nor Alkanediethanol, 2,5-lower Alkane dimethanol and the like.

[化23]

As adamantane dimethanol which is an alicyclic dihydroxy compound represented by the general formula (II), R ¹ is contained in the general formula (II), and various isomers are represented by the following general formula (IIe). Specific examples of such a substance include 1,3-adamantane dimethanol.

[Chem. 24]

Further, the cyclohexanediol belonging to the alicyclic dihydroxy compound represented by the above general formula (III) is contained in the general formula (III) wherein R ^{2 is} represented by the following general formula (IIIa) (wherein R ³ represents carbon The various isomers represented by the alkyl group of 1 to 12). Specific examples of such a substance include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 1,3-cyclohexanediol. 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, and the like.

[化25]

Tricyclodecanediol or pentacyclopentadecanediol which is an alicyclic dihydroxy compound represented by the above general formula (III), which is contained in the general formula (III), R ^{2 is} represented by the following general formula (IIIb) (wherein, n represents 0 or 1) represents various isomers.

[Chem. 26]

As the decahydronaphthalenediol or tricyclotetradecanediol belonging to the alicyclic dihydroxy compound represented by the above general formula (III), R ² is contained in the general formula (III) in the following general formula (IIIc) ( In the formula, m represents 0 or 1) represents various isomers. Specific examples of such a substance include 2,6-decahydronaphthalenediol, 1,5-decahydronaphthalenediol, and 2,3-decahydronaphthalenediol.

[化27]

As a lowering of the alicyclic dihydroxy compound represented by the above general formula (III) Alkanediols, comprising based on (III), R ² represents the various isomers of the following general formula (IIId) of general formula. As such a substance, specifically, 2,3-nor can be used. Alkanediol, 2,5-lower Alkanediol and the like.

[化28]

As part of adamantane diol compound represented by the general formula (III) of the alicyclic dihydroxy, comprising based on (III), R ² represents the various isomers of the following general formula (llle) of general formula. As such a substance, specifically, 1,3-adamantanediol or the like can be used.

[化29]

In the specific examples of the alicyclic dihydroxy compound, in particular, cyclohexanedimethanol, tricyclodecane dimethanol, adamantane dimethanol, pentacyclopentadecanedimethanol, and the like are preferable. From the viewpoint of ease of handling and handling, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and tricyclodecane dimethanol are preferred. .

Further, the compound exemplified above is an example of the alicyclic dihydroxy compound which can be used in the present invention, and is not limited thereto. These alicyclic diol compounds may be used alone or in combination of two or more. Further, a heterocyclic dihydroxy compound and an alicyclic dihydroxy compound are preferably used in combination. In this case, either or both of the heterocyclic dihydroxy compound and the alicyclic dihydroxy compound may have the structure of the formula (1). .

(other dihydroxy compounds)

Further, in the polycarbonate resin of the present invention, in addition to the dihydroxy compound represented by the formula (3) and the alicyclic dihydroxy compound, a constituent unit derived from another dihydroxy compound may be contained.

Examples of such other dihydroxy compounds include aliphatic dihydroxy compounds, alkylene glycols, and bisphenols.

Examples of the aliphatic dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, and 1,2-butanediol. 1,5-heptanediol, 1,6-hexanediol, and the like.

Examples of the alkyloxyalkylene glycol include diethylene glycol, triethylene glycol, and tetraethylene glycol.

Examples of the bisphenol include 2,2-bis(4-hydroxyphenyl)propane [=bisphenol A] and 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-hydroxyl Phenyl)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 or the like.

Further, examples of the bisphenol include bis(4-hydroxyphenyl)fluorene, 2,4'-dihydroxydiphenylphosphonium, bis(4-hydroxyphenyl) sulfide, and 4,4'-dihydroxy group. Diphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-2,5-diethoxy diphenyl ether, 9,9- Bis(4-(2-hydroxyethoxy)phenyl)indole, 9,9-bis(4-(2-hydroxyethoxy-2-methyl)phenyl)anthracene, 9,9-bis (4 -Hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-2-methylphenyl)anthracene.

These other dihydroxy compounds may be used alone or in combination of two or more.

By using other dihydroxy compounds, effects such as improvement in flexibility, improvement in heat resistance, and improvement in formability can be obtained. However, if the content ratio of constituent units derived from other dihydroxy compounds is too large, the performance of the original optical characteristics is lowered.

Therefore, in the polycarbonate resin of the present invention, the total of the dihydroxy compound represented by the formula (1) and the heterocyclic dihydroxy compound and/or the alicyclic dihydroxy compound is relative to the total of the polycarbonate resin. The proportion of the hydroxy compound is preferably 90 mol% or more.

(physical properties of polycarbonate resin)

The polycarbonate resin of the present invention has a sulfur element content of 5 ppm or less, preferably 3 ppm or less, more preferably 2 ppm or less.

When the content of the sulfur element contained in the polycarbonate resin is too large, the polymerizability is lowered, and the polymerization time is prolonged, and the color tone of the obtained polymer may be deteriorated or the hydrolysis resistance may be lowered.

The method of adjusting the content of the sulfur element contained in the polycarbonate resin to a range of 5 ppm or less is not particularly limited, and examples thereof include adjusting the composition of the copolymerization, and purifying and using the raw material monomer to be used. The obtained polymer is temporarily prepared into a solution, refined, and the like.

The polycarbonate resin of the present invention has an intrinsic viscosity of usually 0.2 to 1.0 dl/g, preferably 0.3 to 0.8 dl/g. If the intrinsic viscosity is too small, the mechanical strength of the film obtained by melt molding tends to be lowered. Further, when the intrinsic viscosity is too large, the fluidity at the time of melting is lowered, and the formability tends to be poor.

Further, the glass transition temperature of the polycarbonate resin of the present invention is preferably 110 ° C or higher. If the glass transition temperature is less than 110 ° C, the heat resistance of the film which is used as a raw material tends to be poor. However, if the glass transition temperature is too high, stretching unevenness tends to occur when the film is stretched, and therefore the glass transition temperature is preferably 200 ° C or lower.

Further, the absolute value of the photoelastic coefficient of the polycarbonate resin of the present invention is preferably 25 × 10 ^-12 Pa ^-1 or less, more preferably 20 × 10 ^-12 Pa ^-1 or less. When the absolute value of the photoelastic coefficient exceeds 25 × 10 ^-12 Pa ^-1 , when the film is formed as a raw material, the variation in the phase difference in the plane of the film becomes large.

Further, the content of sulfur in the polycarbonate resin, the intrinsic viscosity of the polycarbonate resin, the glass transition temperature, and the photoelastic coefficient were measured by the methods described in the examples below.

[2] Method for producing polycarbonate resin

The polycarbonate resin of the present invention can be produced by a conventionally known polymerization method. The polymerization method may be any one of a melt polymerization method using a phosgene solution polymerization method or a reaction between a carbonic acid diester and a hydroxy compound.

Preferably, the dihydroxy compound having the bond structure of the formula (1), the heterocyclic dihydroxy compound and/or the alicyclic dihydroxy compound which may be used as required in the presence of a polymerization catalyst are preferably used. And other dihydroxy compounds, a melt polymerization method in which a reaction with a carbonic acid diester is carried out.

Here, the dihydroxy compound having the bond structure of the structural formula (1) used in the melt polymerization preferably has a sulfur element content of 9 ppm or less. Further, the content of the sulfur element is preferably 5 ppm or less, and more preferably 3 ppm or less.

When the content of the sulfur element contained in the dihydroxy compound having the bond structure of the structural formula (1) is too large, the polymerizability is lowered, the polymerization time is prolonged, and the resulting polymer is deteriorated in color tone or hydrolysis resistance. Reduce the situation.

The method of adjusting the content of the sulfur element contained in the dihydroxy compound having the bond structure of the structural formula (1) to a range of 9 ppm or less is not particularly limited, and examples thereof include the use of the structural formula (1). The raw material (for example, hydrazine) of the dihydroxy compound produced by the bond structure has a low sulfur element content, and the conditions for recrystallization purification are optimized.

(carbonic acid diester)

The carbonic acid diester used in the melt polymerization method is generally represented by the following general formula (4). These carbonic acid diesters may be used alone or in combination of two or more.

[化30]

(In the general formula (4), B ¹ and B ² may be an aliphatic group having a substituent of 1 to 18 carbon atoms or an aromatic group having a substituent, and B ¹ and B ² may be the same or different.)

Examples of the carbonic acid diester represented by the above general formula (4) include substituted diphenyl carbonates such as diphenyl carbonate and xylyl carbonate; dimethyl carbonate, diethyl carbonate and dith. Tributyl carbonate and the like.

Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable.

In the above melt polymerization method, the total dihydroxy compound of the diester represented by the general formula (4) with respect to the dihydroxy compound having the bond structure of the structural formula (1) used in the reaction is preferably 0.90 to 1.10. The molar ratio is used, preferably at a molar ratio of 0.96 to 1.04.

When the molar ratio of the carbonic acid diester used in the melt polymerization method is too small, the terminal OH group of the produced polycarbonate resin increases, the thermal stability of the polymer deteriorates, and there is a tendency that the desired high molecular weight body cannot be obtained. . On the other hand, if the molar ratio of the carbonic acid diester used is too large, the rate of the transesterification reaction is lowered under the same polymerization conditions, and there is a tendency that it is difficult to produce a polycarbonate resin having a desired molecular weight. In addition, the amount of the carbonic acid diester remaining in the polycarbonate resin to be produced tends to increase, and the residual carbonic acid diester tends to cause odor during molding or molding.

(polymerization catalyst)

As the polymerization catalyst (transesterification catalyst) in the melt polymerization, an alkali metal compound and/or an alkaline earth metal compound can be used. Further, an alkali compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound or an amine compound may be used in combination with an alkali metal compound and/or an alkaline earth metal compound, but it is particularly preferable to use only an alkali metal. a compound and/or an alkaline earth metal compound. In addition, in this specification, the terms "alkali metal" and "alkaline earth metal" are respectively used in "No. 1 group metal" and "Group 2 metal" in the Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005. Synonymous use.

Examples of the alkali metal compound used as the polymerization catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, lithium hydrogencarbonate, barium hydrogencarbonate, sodium carbonate, and carbonic acid. Potassium, lithium carbonate, barium carbonate, sodium acetate, potassium acetate, lithium acetate, barium acetate, sodium stearate, potassium stearate, lithium stearate, barium stearate, sodium borohydride, potassium borohydride, boron hydride Lithium, borohydride, sodium borohydride, potassium phenylate, lithium phenylate, borohydride phenyl, sodium benzoate, potassium benzoate, lithium benzoate, bismuth benzoate, disodium hydrogen phosphate, Dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dihydrogen phosphate, disodium phenyl phosphate, dipotassium phenyl phosphate, dilithium phenyl phosphate, diphenyl phenyl phosphate; alcohols of sodium, potassium, lithium, cesium ( Alcoholate), phenolate; disodium salt of bisphenol A, dipotassium salt, dilithium salt, diterpene salt, and the like.

Further, examples of the alkaline earth metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, barium hydroxide, calcium hydrogencarbonate, barium hydrogencarbonate, magnesium hydrogencarbonate, barium hydrogencarbonate, calcium carbonate, barium carbonate, and magnesium carbonate. , barium carbonate, calcium acetate, barium acetate, magnesium acetate, barium acetate, calcium stearate, barium stearate, magnesium stearate, barium stearate, and the like.

These alkali metal compounds and alkaline earth metal compounds may be used alone or in combination of two or more.

Further, specific examples of the basic boron compound which can be used in combination with an alkali metal compound and/or an alkaline earth metal compound include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, and trimethylamine. Ethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzylboron, tributyl Sodium, potassium, lithium, calcium, barium, magnesium, barium, etc. of phenyl boron, triphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, etc. Salt and so on.

Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salt. .

Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylethylammonium hydroxide. , trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide , tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylate hydroxide, methyltriphenylammonium hydroxide, Butyltriphenylammonium hydroxide and the like.

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

These basic compounds may be used alone or in combination of two or more.

When the amount of the above-mentioned polymerization catalyst is used, when an alkali metal compound and/or an alkaline earth metal compound is used, it is usually 0.1 μm to 100 μm in terms of metal, based on 1 mol of the total diol component. It is preferably used in the range of 0.5 μmol to 50 μmol, more preferably 1 μmol to 25 μmol. When the amount of the polymerization catalyst used is too small, there is a tendency that the polymerization activity necessary for producing a polycarbonate resin having a desired molecular weight is not obtained. On the other hand, when the amount of the polymerization catalyst used is too large, the hue of the obtained polycarbonate resin is deteriorated, and by-products are generated, and the fluidity is lowered or the occurrence of colloids is increased, and it is difficult to produce a polycarbonate resin of a desired quality.

(Polymerization)

The melt polymerization is usually carried out in a plurality of stages of two or more stages. Specifically, the first stage reaction is carried out at a temperature of 140 to 220 ° C (preferably 150 to 200 ° C) for 0.1 to 10 hours (preferably 0.5 to 3 hours). After the second stage, the pressure of the reaction system is gradually decreased from the pressure of the first stage, and the reaction temperature is raised upward, and the simultaneously occurring phenol is excluded from the reaction system, and finally the reaction system pressure is below 200 Pa and 210. A polycondensation reaction is carried out on the basis of a temperature range of ~280 °C.

In the polycondensation reaction, it is important to control the balance of temperature and pressure within the reaction system. In particular, when any one of temperature and pressure rapidly changes, the unreacted monomer is distilled off, and the molar ratio of the diol compound to the carbonic acid diester changes, and the degree of polymerization tends to decrease. The form of the reaction can be batch, continuous, or any combination of batch and continuous.

(phosphorus compound)

When the polycarbonate resin of the present invention is produced by a melt polymerization method, a phosphoric acid compound or a phosphorous acid compound may be added during polymerization in order to prevent coloration.

As the phosphoric acid compound, one type or two or more types of a trialkyl phosphate such as trimethyl phosphate or triethyl phosphate can be suitably used. The amount of the total diol component is preferably 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less. When the amount of the phosphorus compound added is too small, the effect of preventing coloring is low, and if it is too large, the haze value is increased, or the coloring is promoted or the heat resistance is lowered.

In the case of adding a phosphorous acid compound, the following thermal stabilizer can be optionally used. In particular, trimethyl phosphite, triethyl phosphite, decyl phenyl phosphite, trimethyl phosphate, ginseng (2,4-di-t-butylphenyl) phosphite, One or two or more kinds of bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite. The phosphorous acid compound is preferably added in an amount of 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less, based on the total diol component. When the amount of the phosphorous acid compound added is too small, the effect of preventing coloring is low, and if it is too large, the haze value is increased, or the coloring is promoted or the heat resistance is lowered.

It is preferably added in combination with a phosphoric acid compound and a phosphorous acid compound. The amount of addition in this case is preferably 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol%, based on the total amount of the phosphoric acid compound and the phosphorous acid compound, based on the total diol component described above. Ear% or more and 0.003 mol% or less. If the amount is too small, the effect of preventing coloring is low, and if it is too large, the fog value is increased, or the coloring is promoted or the heat resistance is lowered.

(additional ingredient)

In the polycarbonate resin of the present invention, various additives may be added to the extent that the object of the present invention is not impaired. The additive may, for example, be a thermal stabilizer or an antioxidant for preventing a decrease in molecular weight or a hue of a polycarbonate resin in molding or the like; and a release agent for further improving mold release property during melt molding; A light stabilizer or ultraviolet absorber for improving weather resistance; a yellowish bluing agent for offsetting a product derived from a resin or an ultraviolet absorber.

Examples of the thermal stabilizer include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid, and the like. Specific examples thereof include triphenyl phosphite, decyl (nonylphenyl) phosphite, ginseng (2,4-di-tert-butylphenyl) phosphite, and tridecyl phosphite. Trioctyl phosphite, tri-octadecyl phosphite, dinonyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl Diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol di Phosphate, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite, bis(nonylphenyl)pentanediol diphosphite, double (2 ,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate Salt, diphenyl mono-o-phenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4'-extended biphenyl diphosphonate (2,4- Di-t-butylphenyl), phenylphosphonic acid dimethyl salt, phenylphosphonic acid diethyl salt, phenylphosphonic acid dipropyl Wait.

Among these, it is preferred to use decyl phenyl phosphite, trimethyl phosphate, ginseng (2,4-di-t-butylphenyl) phosphite, bis (2,4-di) -T-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite and phenylphosphonic acid dimethyl salt.

These heat stabilizers may be used alone or in combination of two or more.

The heat stability may be further added in addition to the addition amount added during the melt polymerization. In other words, when a suitable amount of the phosphorous acid compound or the phosphoric acid compound is added to obtain a polycarbonate copolymer, if the phosphorous acid compound is further added by the addition method described later, the increase in the haze value during polymerization, coloring, and heat resistance can be avoided. The reduction can further add a large amount of thermal stability while preventing the deterioration of the hue.

The amount of the heat stabilizer to be added is preferably 0.0001 part by weight to 1 part by weight, more preferably 0.0005 part by weight to 0.5 part by weight, particularly preferably 0.001, when the polycarbonate resin is 100 parts by weight. ~0.2 parts by weight.

Examples of the antioxidant include pentaerythritol lanthanum (3-mercaptopropionate), pentaerythritol lanthanum (3-lauryl sulfonate), glycerin-3-stearyl sulfonate, and triethylene glycol-double. [3-(3-Terbutyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl) -4-hydroxyphenyl)propionate], pentaerythritol-indole [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-paran (3,5-di-t-butyl-4- Hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamate), 3,5-di-t-butyl-4- Hydroxy-benzylphosphonate-dimethyl ester, ginseng (3,5-di-t-butyl-4-hydroxybenzyl) trimer isocyanate, 4,4'-extended biphenyl diphosphonate ( 2,4-di-t-butylphenyl), 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylbenzene One or two or more kinds of propyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane.

The amount of the antioxidant added is preferably 0.0001 part by weight to 0.5 part by weight, based on 100 parts by weight of the polycarbonate resin.

Examples of the release agent include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin waxes, beeswax, olefin waxes, olefin-based waxes containing carboxyl groups and/or carbonic anhydride groups, and silicone oils. Organic polyoxyalkylene and the like.

The higher fatty acid ester is preferably a partial ester or a full ester of a saturated fatty acid having a carbon number of 1 to 20 or a polyhydric alcohol and a carbon number of 10 to 30. Examples of the partial ester or the full ester of such a monohydric or polyhydric alcohol and a saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, and stearic acid monosorbate. Stearic acid stearate, behenic acid monoglyceride, behenic acid behenate, pentaerythritol monostearyl ester, pentaerythritol tetrastearyl ester, pentaerythritol tetradecanoate, propylene glycol monostearyl ester, stearic acid Stearyl ester, palmity palmitate, butyl stearyl ester, methyl lauryl ester, isopropyl palmitate, biphenyl biphenyl ester, sorbitan monostearyl ester, 2-ethylhexyl stearyl ester Wait.

Among these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearyl ester, and behenic acid behenate are preferably used.

As the higher fatty acid, a saturated fatty acid having 10 to 30 carbon atoms is preferred. Examples of such a fatty acid include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid.

These release agents may be used alone or in combination of two or more. The amount of the releasing agent to be added is preferably 0.01 parts by weight to 5 parts by weight, based on 100 parts by weight of the polycarbonate resin.

Further, in the polycarbonate resin of the present invention, a light stabilizer or an ultraviolet absorber may be added to the extent that the object of the present invention is not impaired.

Examples of the photo-stabilizer or the ultraviolet absorber include 2-(2'-hydroxy-5'-th-octylphenyl)benzotriazole and 2-(3-tert-butyl-5-methyl group. -2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α ,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2'-methylenebis(4-isopropylphenyl-6-benzotriazolephenyl), 2,2 '-p-phenylene bis(1,3-benzoate) -4-ketone) and the like.

These light stabilizers or ultraviolet absorbers may be used alone or in combination of two or more. The amount of such a light stabilizer or the ultraviolet absorber to be added is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the polycarbonate resin.

As the bluing agent, any one that can be used for the polycarbonate resin can be used without limitation. In general, lanthanide dyes are readily available and are preferred.

Specific examples of the bluing agent include, for example, Solvent Violet 13 [CA. No (color index No. 60725)], general name Solvent Violet 31 [Ca. No 68210], and general name Solvent Violet 33 [CA. No. 60725], the general name Solvent Blue94 [CA. No 61500], the general name Solvent Violet36 [CA. No 68210], the general name Solvent Blue97 [Bayer company "Macrolex Violet RR"] and the general name Solvent Blue45 [CA. No61110 As a representative example. These bluing agents may be used alone or in combination of two or more.

These bluing agents are usually added in a ratio of 0.1 × 10 ^-4 to 2 × 10 ^-4 parts by weight in the case where the polycarbonate resin is 100 parts by weight.

The method for blending the polycarbonate resin and various additives of the invention is a roller, a V-type blender, a super mixer, a Nauta mixer, a class A method of mixing the above-mentioned components, a solution blending method in which the components are mixed in a state of a good solvent such as dichloromethane, and the like, and the like, and the like is not particularly limited. Any method can be used as long as it is a polymer blending method which can be generally used.

[3] Transparent film, optical film and retardation film

A transparent film can be produced by using the above polycarbonate resin as a raw material. Further, an optical film formed into a transparent film can be produced by stretching after film formation to produce a retardation film. The film forming method may be a conventionally known melt extrusion method, solution casting method, or the like.

Further, as the raw material of the optical film, in addition to the polycarbonate resin of the present invention, other polycarbonate resins such as bisphenol A or bisphenol Z may be used; and 9,9-bis(4-hydroxyphenyl) is used. Modified polycarbonate resin such as ruthenium, 9,9-bis(3-methyl-4-hydroxyphenyl)anthracene, 9,9-bis(3-ethyl-4-hydroxyphenyl)anthracene, and poly Ester resin; polyethylene terephthalate, polybutylene terephthalate, polynaphthalate, polycyclohexane dimethylene cyclohexane dicarboxylate, polycyclohexane di One or two or more kinds of other resins such as a polyester resin such as methyl terephthalate.

The thickness of the optical film is usually from 30 μm to 200 μm, preferably from 50 μm to 150 μm. Further, the phase difference of the film formed film is preferably 20 nm or less, more preferably 10 nm or less. When the phase difference of the film is too large, the film is stretched to form a retardation film, and the error of the phase difference in the film surface tends to be large.

As the method of extending the optical film, a known stretching method such as uniaxial stretching in either of the longitudinal and transverse directions and biaxial stretching extending in the longitudinal and lateral directions may be used. Further, a special biaxial stretching can be applied to suppress the three-dimensional refractive index of the film.

The stretching conditions for producing the retardation film are preferably carried out in the range of the glass transition temperature of the film raw material of from -20 ° C to +40 ° C. It is preferably in the range of -10 ° C to + 20 ° C of the glass transition temperature of the film material. If the extension temperature is much lower than the glass transition temperature of the polycarbonate resin, the phase difference of the stretched film becomes large, and in order to obtain the desired phase difference, the stretch ratio must be lowered, and the error of the phase difference in the film plane becomes large. The tendency. On the other hand, if the stretching temperature is much higher than the glass transition temperature, the phase difference of the obtained film becomes small, and in order to obtain a desired phase difference, it is necessary to increase the stretching ratio, and the range of appropriate stretching conditions tends to be narrow.

As the retardation film, a phase difference plate for various liquid crystal display devices can be used. When the retardation film is used for color compensation of an STN liquid crystal display device, the phase difference value is generally selected in the range of 400 nm to 2000 nm. Further, when the retardation film is used as a 1/2 wavelength plate, the phase difference is selected in the range of 200 nm to 400 nm. When the retardation film is used as a quarter-wavelength plate, the phase difference is selected in the range of 90 nm to 200 nm. A better phase difference as a quarter-wave plate is from 100 nm to 180 nm. The retardation film may be used singly or in combination of two or more, or may be used in combination with other films.

The retardation film can be laminated by a known iodine-based or dye-based polarizing plate and an adhesive. In the case of lamination, it is necessary to laminate the polarizing axis of the polarizing plate and the slow axis of the retardation film at a specific angle. Further, the retardation film can be used as a quarter-wave plate, laminated with a polarizing plate, and used as a circularly polarizing plate. In this case, in general, the polarization axis of the polarizing plate and the slow axis of the retardation film are substantially maintained at 45. The layers are stacked at opposite angles. Further, the retardation film may be laminated by using a polarizing protective film constituting the polarizing plate. Further, the retardation film may be used as a color compensation plate of an STN liquid crystal display device, and it may be used as an elliptically polarizing plate by laminating it with a polarizing plate.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples. However, the invention is not limited to the embodiments shown below.

In the following, the physical properties and characteristics of the polycarbonate resin and the polycarbonate resin composition were evaluated by the following methods.

(1) Content of sulfur element in polycarbonate resin

The sample was collected in a platinum plate and heated in a quartz tube tubular furnace (AQF-100 type manufactured by Mitsubishi Chemical Corporation) to absorb sulfur and chlorine in the combustion gas with a 0.03% aqueous hydrogen peroxide solution. The SO ₄ ^2- , Cl ^- in the absorption liquid was measured by an ion chromatography analyzer (ICS-1000 model manufactured by Dionex Co., Ltd.).

(2) The content of sulfur element in the dihydroxy compound

The measurement is carried out based on the method for measuring the sulfur element in the above polycarbonate resin.

(3) Determination of glass transition temperature Tg of polycarbonate resin

The glass transition temperature Tg of the polycarbonate resin was measured by using a differential scanning calorimeter (DSC220, manufactured by SII Nanotechnology Co., Ltd.) in accordance with JIS K7121. About 10 mg of the polyester resin was placed in an aluminum pan made of the same company and sealed, and the temperature was raised to 300 ° C at a temperature increase rate of 20 ° C / min. From the resulting DSC data, the heterodyne glass was used to transfer the onset temperature.

(4) Determination of ultimate viscosity of polycarbonate resin

Ubbelohde type viscometer (centralized DT-504 automatic viscometer) was used, and a 1:1 mixed solvent of phenol and 1,1,2,2-tetrachloroethane was used as a solvent at a temperature of 30.0 °C ± 0.1 °C. The measurement was carried out. The concentration was precisely adjusted to 1.00 g/dl.

The sample was stirred and dissolved at 120 ° C for 30 minutes, and used for measurement after cooling.

From the passage time t _{0 of the} solvent and the passage time t of the solution, the relative viscosity η _{rel is} obtained from the following formula.

η _rel =t/t ₀

The specific viscosity η _{sp is} obtained from the relative viscosity η _rel by the following formula.

η _sp =(η-η ₀ )/η ₀ =η _rel -1

The specific viscosity (converted viscosity) η _{red was} obtained by dividing the specific viscosity η _sp by the concentration c (g/dl) by the following formula.

η _red =η _sp /c

Next, the number of rare solutions of the reduced concentration c was adjusted, and the respective reducing viscosities were measured. Finally, the reduction viscosity is plotted against the concentration c, and on the obtained curve, the ultimate viscosity [η] is obtained from the point of extrapolation to infinite dilution (c = 0).

(5) Color tone of polycarbonate resin (b value)

According to JIS K7373, a sampled particle is filled in a cylindrical quartz tube having a diameter of 30 mm and a height of 12 mm, using an electrochromic color meter (ZE-2000, manufactured by Nippon Denshoku Industries Co., Ltd.), generally rotating at about 90 degrees and 4 times at the same time. The tristimulus values X, Y, and Z were measured on the average, and the b value was obtained by the following formula.

b value = 70 (Y-100Z/Zn) / L

(where L = 10Y ^1/2 , Z _n represents the Z value of the standard light of the fully diffused reflection surface.)

(6) Hydrolysis resistance of polycarbonate resin

The sample pellets were placed in a pressure cooker (manufactured by Hirayama Seisakusho Co., Ltd., model: PC-242), and treated at 120 ° C and a water vapor pressure of 0.11 MPa for 24 hours. The hydrolysis resistance is expressed by the retention (%) of the ultimate viscosity after treatment with respect to the ultimate viscosity before treatment.

(Synthesis Example 1) (9,9-[4-(2-hydroxyethoxy)phenyl]anthracene)

In a reaction vessel equipped with a stirrer and a cooling tube, 350 parts by mass of 99.5% by weight of anthrone and 1070 parts by mass of phenoxyethanol (manufactured by Yokkaichi Synthetic Co., Ltd., trade name: PHE-G) were charged and added. 2.3 parts by mass of β-propionic acid, 570 parts by weight of 95% sulfuric acid was dropped over 60 minutes. Thereafter, the reaction temperature was maintained at 50 ° C for 5 hours.

After completion of the reaction, 920 parts by mass of a 48% by mass aqueous sodium hydroxide solution was added dropwise to the reaction liquid to adjust the liquid temperature to 80 °C. The pH after the end of the dropping was about 8. Thereafter, 2500 parts by mass of methanol was added, and the mixture was cooled to 10 ° C to precipitate a solid matter.

Next, the solid matter was filtered, and 3,500 parts by mass of toluene and 1000 parts by mass of pure water were heated to 85 °C. After removing the aqueous phase, the organic phase was further washed twice with water at 85 ° C, the organic phase was cooled to 10 ° C, and toluene was distilled off to obtain a solid component.

Thereafter, the mixture was dissolved in 15,000 parts by mass of ethyl acetate, and 35 parts by mass of activated carbon (manufactured by Nippon Norit Co., Ltd., trade name: SX+) was charged, and the mixture was heated and stirred at 60 ° C for 2 hours. Next, the activated carbon was filtered, and ethyl acetate was distilled off and dried. The sulfur content of the obtained 9,9-[4-(2-hydroxyethoxy)phenyl]anthracene was 4.2 ppm (referred to as "BHEPF-1"). Further, the structural formula of 9,9-[4-(2-hydroxyethoxy)phenyl]anthracene is as follows.

[化31]

9,9-[4-(2-hydroxyethoxy)phenyl]anthracene (BHEPF)

(Synthesis Example 2) (9,9-[4-(2-hydroxyethoxy)phenyl]anthracene)

In the synthesis example 1, the same operation as in the synthesis example 1 was carried out except that the water washing was performed only once. The sulfur content of the obtained 9,9-[4-(2-hydroxyethoxy)phenyl]anthracene was 8.3 ppm (referred to as "BHEPF-2").

(Synthesis Example 3) (9,9-[4-(2-hydroxyethoxy)phenyl]anthracene)

45 parts by mass of decyl ketone having a purity of 99.5% by weight and 138 parts by mass of phenoxyethanol (manufactured by Yokkaichi Synthetic Co., Ltd., trade name: PHE-G) were placed in a reaction vessel equipped with a stirrer and a cooling tube. 0.2 ml of β-propionic acid was added to 40 ml of 95% sulfuric acid for 30 minutes. Thereafter, the reaction temperature was maintained at 50 ° C for 5 hours.

After completion of the reaction, 100 ml of methanol was added to the reaction mixture, and the mixture was further stirred for 1 hour. Then, 150 ml of pure water was added to precipitate a reaction product, which was cooled to room temperature, and then filtered and/or separated. To the obtained solid fraction, 800 ml of methanol was used, and the mixture was heated, dissolved while stirring, and the solid was precipitated while cooling to room temperature to carry out recrystallization purification. The precipitate was filtered and then dried.

The sulfur content of the obtained 9,9-[4-(2-hydroxyethoxy)phenyl]anthracene was 15 ppm (referred to as "BHEPF-3").

(Synthesis Example 4) (Reference Example 1) Synthesis of 9H-indole-9,9-diacetic acid and 9,9-di-t-butyl ester

Nitrogen was passed through a reaction vessel equipped with a stirrer and a cooling tube, and 68.9 parts by mass of potassium-tert-butoxide and 178 parts by mass of tetrahydrofuran (hereinafter abbreviated as "THF") were charged to prepare a suspension and stirred. The internal temperature was cooled to 3 °C. 30 parts by mass of the dissolved mass part was dropped into the crucible for 45 minutes while adjusting the dropping speed so that the internal temperature did not exceed 6 °C. 44.5 parts by mass of THF was added to the obtained slurry mixture, and the mixture was cooled and stirred until the internal temperature was lowered to 3 °C. To the slurry, a solution of 119.7 parts by mass of tert-butyl bromide dissolved in 89 parts by mass of THF was dropped over 90 minutes. During this time, the dripping speed is adjusted so that the internal temperature does not exceed 10 °C.

After the completion of the dropwise addition, the mixture was further stirred for 30 minutes, and then the content liquid was returned to room temperature. Then, the reaction liquid was poured into 300 parts by mass of pure water, and extracted with 448.5 parts by mass of ethyl acetate. The organic layer was washed once with 304.6 parts by mass of 1N hydrochloric acid, washed three times with 300 parts by mass of pure water, and once with 358.5 parts by mass of saturated brine, and dried with sodium sulfate. The sodium sulfate was filtered, and then the solvent was distilled off to obtain the target di-t-butyl ester as a brown oil.

(Reference Example 2) Synthesis of 9H-茀-9,9-diacetic acid

Next, nitrogen was passed through a reaction vessel equipped with a stirrer and a cooling tube, and the total amount of the di-tert-butyl ester obtained in Reference Example 1, 376.1 parts by mass of dichloroethane, and 92.7 parts by mass of trifluoroacetic acid were charged and heated to the inside. The temperature became 60 ° C and the reaction was 6.5 hours. After cooling, the resulting precipitate was filtered and the solvent was distilled off. Further, vacuum drying was carried out to obtain a mixture of the dicarboxylic acid and the monocarboxylic acid of the target in the form of a brown oil. A part of the sample was taken and determined by 1 H-NMR, and it was found that the oil was a mixture of a dicarboxylic acid and a monocarboxylic acid of 4.2/1. This mixture was used without purification and used directly in the following reduction reaction.

(Reference Example 3) Synthesis of 9H-茀-9,9-diethanol

Next, nitrogen was passed through a reaction vessel equipped with a stirrer and a cooling tube, and 101.5 parts by mass of Red-A1, 44.5 parts by mass of THF, and 86.7 parts by mass of toluene in a 65% strength (toluene solution) were charged, and the mixture was sufficiently stirred and dissolved. In this solution, 78.7 parts by mass of a mixed solvent of 72.5 mmol of the dicarboxylic acid synthesized in Reference Example 2 and a monocarboxylic acid dissolved in THF/toluene (1/2 volume ratio) was added dropwise over 20 minutes. Solution. During this period, the temperature of the internal solution was observed to rise from 28 ° C to 35 ° C. After stirring at room temperature for 1.5 hours, the internal temperature was further raised to 53 ° C and stirred for 5 hours to complete the reaction. Thereafter, the mixture was cooled to an internal temperature of 8 ° C, and 421.6 parts by mass of 3N diluted hydrochloric acid was carefully added to quench the reaction mixture. The quenching liquid system is divided into two layers, so the organic layer is separated, and the aqueous layer is extracted with 89.7 parts by mass of ethyl acetate after adding 105.4 parts by mass of 3N diluted hydrochloric acid, and the previous organic layer is mixed with the ethyl acetate layer. The organic layer was washed twice with 200 parts by mass of pure water and 239 parts by mass of saturated brine, and dried over sodium sulfate. After filtration, the solvent was distilled off, and then recrystallized from an ethyl acetate-hexane mixed solvent to obtain 9.94 parts by mass of the target 9H-indole-9,9-diethanol in the form of white needle crystals.

9000 parts by mass of ethyl acetate was added to 9.94 parts by mass of the obtained 9H-fluorene-9,9-diethanol, and dissolved, and 0.5 parts by mass of activated carbon (manufactured by Nippon Norit Co., Ltd., trade name: SX+) was added. The mixture was heated and stirred at 60 ° C for 2 hours. Thereafter, the activated carbon was filtered, and ethyl acetate was distilled off and dried. The obtained cerium-9,9-diethanol had a sulfur content of 4.8 ppm (referred to as "DEF-1"). In addition, the structural formula of -9,9-diethanol is as follows.

[化32]

茀-9,9-diethanol (DEF)

(Synthesis Example 5)

In Synthesis Example 4, the same operation was carried out except that the activated carbon treatment was not carried out to synthesize -9,9-diethanol. The obtained cerium-9,9-diethanol had a sulfur content of 12 ppm (referred to as "DEF-2").

(Synthesis Example 6)

9,9-bis(4-hydroxy-3-methylphenyl)anthracene (trade name: BCF) was purchased from Osaka Gas Chemical Co., Ltd. The sulfur content of this compound was measured and found to be 13 ppm (hereinafter referred to as "BCF-1").

Further, the structural formula of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene is as follows.

[化33]

9,9-bis(4-hydroxy-3-methylphenyl)indole (BCF)

(Synthesis Example 7)

700 parts by mass of BCF-1 of Synthesis Example 6 was dissolved in 15,000 parts by mass of ethyl acetate, and 35 parts by mass of activated carbon (manufactured by Nippon Norit Co., Ltd., trade name: SX+) was placed, and the mixture was heated and stirred at 60 ° C for 2 hours. Next, the activated carbon was filtered, and ethyl acetate was distilled off and dried. The sulfur content of the obtained 9,9-bis(4-hydroxy-3-methyl)indole was 4.1 ppm (indicated as "BCF-2").

The results are shown in Table 1.

(Example 1)

9,9-[4-(2-hydroxyethoxy)phenyl]anthracene (BHEPF-1) 62.22 prepared in Synthesis Example 1 was prepared with respect to 27.65 parts by mass of isosorbide (hereinafter abbreviated as "ISB"). Parts by mass, tricyclodecane dimethanol (hereinafter abbreviated as "TCDDM") 27.85 parts by mass and diphenyl carbonate (hereinafter abbreviated as "DPC") 101.33 parts by mass, and a 2% by weight aqueous solution of cerium carbonate as a catalyst 0.39 ×10 ^-1 parts by mass (10 μmol in terms of metal relative to the total dihydroxy compound 1 mol) was placed in a reactor, and the temperature of the heating bath was heated to 170 ° C under a nitrogen atmosphere, and stirred as necessary. The raw material was dissolved over 60 minutes.

Thereafter, the temperature was raised to 220 ° C over 70 minutes and held for 90 minutes. On the other hand, after the raw material was dissolved, the pressure was raised from normal pressure to 13.3 kPa over a period of 40 minutes, and held for 120 minutes. The temperature was further raised to 240 ° C over 20 minutes. The pressure was reduced to 0.13 kPa over a period of 30 minutes and maintained until the end of the reaction.

After the raw material was dissolved, the time from the start of the pressure reduction until the stirring was stopped was determined as the polymerization time, and the polymerization time was 217 minutes, and the ultimate viscosity of the obtained polycarbonate resin was 0.733 dl/g.

(Example 2)

In the same manner as in Example 1, except that BHEPF-1 obtained in Synthesis Example 1 was used instead of BHEPF-1 obtained in Synthesis Example 1, the same operation as in Example 1 was carried out. The polymerization time was 268 minutes. The polycarbonate resin obtained had an ultimate viscosity of 0.691 dl/g.

(Example 3)

34.1 parts by mass of 9H-fluorene-9,9-diethanol (DEF-1) and 146 parts by mass of DPC prepared in Synthesis Example 4, and 2% by weight aqueous solution of cerium carbonate as a catalyst were added to 0.85 parts by mass of ISOB. ×10 ^{- 2} parts by mass (16 μmol in terms of metal relative to the total dihydroxy compound 1 mol) was placed in a reactor, and the temperature of the heating bath was heated to 180 ° C in a nitrogen atmosphere, and stirred as needed. The raw material was dissolved over 45 minutes.

Thereafter, the temperature was raised to 200 ° C over 20 minutes, and after 20 minutes, the temperature was raised from 200 ° C to 225 ° C over 20 minutes, and held for 30 minutes. The temperature was further raised from 225 ° C to 240 ° C over 15 minutes, and was maintained until the end of the reaction. On the other hand, after the raw material was dissolved, the pressure was raised from normal pressure to 20 kPa over 20 minutes, and held for 50 minutes. The pressure was further reduced to 0.13 kPa over 60 minutes, and was maintained until the end of the reaction.

The polymerization time was 215 minutes, and the resulting polycarbonate resin had an ultimate viscosity of 0.643 dl/g.

(Comparative Example 1)

In the same manner as in Example 1, except that BHEPF-1 obtained in Synthesis Example 1 was used instead of BHEPF-3 obtained in Synthesis Example 3, the same operation as in Example 1 was carried out. The polymerization time was 447 minutes. The polycarbonate resin obtained had an ultimate viscosity of 0.4471 dl/g.

(Example 4)

The same operation as in Example 3 was carried out, except that DEF-2 produced in Synthesis Example 5 was used instead of DEF-1 produced in Synthesis Example 4. The polymerization time was 250 minutes. The polycarbonate resin obtained had an ultimate viscosity of 0.556 dl/g.

(Example 5)

In Example 2, after the raw material was dissolved, the temperature was raised to 220 ° C over 70 minutes and held for 90 minutes. On the other hand, after the raw material was dissolved, the pressure was raised from normal pressure to 13.3 kPa over a period of 40 minutes for 120 minutes. The temperature was further raised to 280 ° C over 20 minutes. The same operation as in Example 2 was carried out except that the pressure was reduced to 0.13 kPa over 30 minutes and kept until the end of the reaction. The polymerization time was 250 minutes. The polycarbonate resin obtained had an ultimate viscosity of 0.523 dl/g.

(Comparative Example 2)

In Comparative Example 1, the same operation as in Comparative Example 1 was carried out except that the amount of the catalyst was changed to three times. The polymerization time was 263 minutes. The polycarbonate resin obtained had an ultimate viscosity of 0.702 dl/g.

(Example 6)

61.1 parts by mass of 9,9-bis(4-hydroxy-3-methylphenyl)indole (BCF-2) of Synthesis Example 7 and 117.6 parts by mass of DPC with respect to 55.1 parts by mass of ISB, and carbonic acid as a catalyst 0.88 parts by mass of 铯2% by weight aqueous solution (10 μmol in terms of metal relative to total dihydroxy compound 1 mol) was placed in a reactor, heated to 170 ° C in a nitrogen atmosphere, and stirred while stirring, for 60 minutes. Dissolve the material in minutes.

Then, in the same manner as in Example 1, the temperature was raised and reduced, and the reaction was continued until the reaction was completed.

The polymerization time was 240 minutes. The polycarbonate resin obtained had an ultimate viscosity of 0.593 dl/g.

(Comparative Example 3)

The same operation as in Example 5 was carried out except that BCF-1 of Synthesis Example 6 was used as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene.

The polymerization time was 300 minutes. The polycarbonate resin obtained had an ultimate viscosity of 0.458 dl/g.

The results are shown in Table 2.

As a result of the results shown in Table 2, it was found that when the content of the sulfur element in the polycarbonate resin is more than 5 ppm, the polymerization rate is lowered, the polymerization time is prolonged, and the color tone is deteriorated.

Further, in Comparative Examples 1 and 2 and Comparative Example 2, it is understood that when the amount of sulfur element in the monomer is large and the amount of sulfur element in the polymer is increased, the polymerization rate can be increased by increasing the amount of the catalyst. Increased, but in this case, the color tone of the polymer deteriorates. Comparing Example 5 with Comparative Example 1 or Comparative Example 2, the polycarbonate resin of Example 5 was inferior to the two comparative examples in terms of color tone even when the sulfur content in the polymer was 5 ppm or less. However, it is a polycarbonate resin which is better than Comparative Example 1 or Comparative Example 2 in terms of polymerization rate, polymerization time, ultimate viscosity, and hydrolysis resistance. In summary, the polycarbonate resin of Example 5 contains sulfur. A polycarbonate resin having an amount of more than 5 ppm is preferred.

The present invention has been described with reference to the specific embodiments thereof, and it is understood that various changes and modifications may be made without departing from the spirit and scope of the invention.

The present application is filed in accordance with Japanese Patent Application No. 2008-305688, filed on Nov. 28, 2008, and Japanese Patent Application No. 2009-094458, filed on The content is written here.

(industrial availability)

According to the present invention, a polycarbonate resin containing at least a constituent unit derived from a dihydroxy compound having a bond structure represented by the above structural formula (1) can be obtained, and the transparency is excellent. Therefore, the industrial value of the present invention is remarkable.

Claims (7)

A polycarbonate resin comprising a constituent unit derived from 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and a dihydroxy compound selected from the following formula (3), 3, 9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-four Spiro[5,5]undecane, 2-(5-ethyl-5-hydroxymethyl-1,3-di a constituent unit of at least one dihydroxy compound of the alkyl-2-yl)-2-methylpropan-1-ol or an alicyclic dihydroxy compound having a carbon number of 70 or less; the content of the sulfur element is 5 ppm or less; A method for producing a polycarbonate resin, characterized in that a 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and a carbonic acid diester are contained in a polymerization catalyst having a sulfur element content of 9 ppm or less. The polymerization is carried out in the presence of it. The method for producing a polycarbonate resin according to the second aspect of the invention, wherein at least one dihydroxy group selected from the heterocyclic dihydroxy compound and the alicyclic dihydroxy compound represented by the following formula (3) The compound is copolymerized; The method for producing a polycarbonate resin according to the second aspect of the invention, wherein at least one compound selected from the group consisting of an alkali metal compound and an alkaline earth metal compound is used as the polymerization catalyst. The method for producing a polycarbonate resin according to the second aspect of the invention, wherein the amount of the polymerization catalyst used is 0.1 μm in terms of metal in terms of the total amount of the dihydroxy compound 1 mol used for the reaction. 100μm ear. The method for producing a polycarbonate resin according to claim 2, wherein the polymerization temperature is from 210 ° C to 270 ° C. The polycarbonate resin of the first aspect of the patent application is obtained by forming a transparent film from the above polycarbonate resin.