JP2004107677A - High molecular weight polycarbonate and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for easily producing high molecular weight polycarbonate, using a polymerization method safe for human body and causing no harmful effect on environment. <P>SOLUTION: The high molecular weight polycarbonate is produced by transesterification comprising heating a diol and a carbonate diester in the presence of a basic oxide catalyst, wherein the catalyst amount is preferably 20-100 ppm per produced polycarbonate, the high molecular weight polycarbonate is collected from a solvent solution after cooling the produced polycarbonate and the obtained polycarbonate preferably has ≥50,000 weight-average molecular weight. The electrophotographic photoreceptor containing the high molecular weight polycarbonate as a binding resin can rapidly obtain, for a long term, an image having high stability and high quality. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a high-molecular-weight polycarbonate by a transesterification method and a method for producing the same, and more particularly, to a high-molecular-weight polycarbonate by a transesterification reaction using a raw material containing no halogen atom and a method for producing the same.

JP-A-05-202180.

Polycarbonate is a resin having various characteristics such as transparency, high heat resistance, excellent mechanical strength, and good moldability due to its amorphous property, and its demand is rapidly expanding. Its applications cover a very wide range of fields such as, for example, building materials, optical disk substrates, automobile parts, optical lenses, and various functional films. Further, in recent years, demand for glass substitutes and metal material substitutes has been rapidly increasing from the viewpoint of safety and weight reduction, and many polycarbonates suitable for them have been developed. .

Under these circumstances, special fields such as automotive engine-related parts, eyeglass lenses, and electrophotographic photoreceptor parts require a high degree of mechanical strength. There is a need for polycarbonates with significantly higher molecular weights.

On the other hand, electrophotographic apparatuses are often used in fields such as copiers and laser beam printers in recent years because high-quality images can be obtained at high speed. Conventionally, inorganic photoconductive materials such as selenium, selenium-tellurium alloy, selenium-arsenic alloy, and cadmium sulfide have been used for electrophotographic photoreceptors used in these electrophotographic apparatuses. Electrophotographic photoreceptors using organic photoconductive materials that can be manufactured and disposable have become the mainstream. Among them, a charge generation layer and a charge generation layer that generate charges by exposure using these organic photoconductive materials Functionally-separated laminated organic photoreceptors formed by laminating a charge transport layer that transports a variety of electrophotographic characteristics such as electrical sensitivity, chargeability and their repetition stability have been proposed. Has already been put to practical use.

By the way, organic photoreceptors generally have lower mechanical strength than inorganic photoreceptors, and are scratched and worn by mechanical external force such as a cleaning blade, a developing brush, and paper. There is a problem that the life is short due to deterioration. Further, in a system using a contact charging system which has been used in recent years from the viewpoint of ecology, abrasion of the photoreceptor is greatly increased as compared with a charging system using a corotron, and the above-mentioned problem becomes more serious. As the abrasion progresses, the sensitivity of the photoreceptor decreases, causing fogging of the copy, and the charging potential decreases to lower the copy density. Therefore, development of a surface layer material such as a binder resin and a charge transporting material that can form a photosensitive layer having sufficient durability is desired.

In addition, since a flexible electrophotographic photosensitive member in which a coating film of a photosensitive layer is formed on a film of polyethylene terephthalate or the like on which a conductive layer is formed by a method such as vapor deposition, the electrophotographic apparatus can be processed repeatedly into a belt shape, so that the electrophotographic apparatus can be used repeatedly. Although it has the advantage that the degree of freedom of the shape of the electrophotographic apparatus can be expanded, there is a demand that the photoconductor must sufficiently follow flexible movement. For example, a photoconductor using various polycarbonate resins as a binder resin for a surface layer has been proposed.

However, when a coating film of a photosensitive layer is formed by a coating process using a conventionally proposed binder resin, a belt-shaped electrophotographic photosensitive member having relatively good durability can be obtained, but its mechanical strength is not necessarily sufficient. However, if the belt is repeatedly rotated for a long period of time in a belt driving device in a copying machine, cracks occur in the photosensitive layer, and the problem that cracks appear on the copied image remains. I was In order to solve the above-mentioned problems, a binder resin having excellent mechanical properties and flexibility is strongly required. From such a viewpoint, polycarbonate is currently most widely used. Polycarbonate used as a binder resin in the photosensitive layer has a higher molecular weight than those used for other purposes, and specifically requires a polystyrene equivalent weight average molecular weight of 50,000 or more. At present, such a high-molecular-weight polycarbonate has been limited to a method of producing a phosgene method using phosgene as a raw material.

By the way, since phosgene is a chemical substance that is extremely harmful to the human body, a method for producing polycarbonate using triphosgene or chloroformate as a raw material has been studied as an alternative. However, these raw materials are harmful to the human body, and the method is a method using halogen which has an adverse effect on the environment, and cannot be said to be a completely safe production method.

On the other hand, a transesterification method using diphenyl carbonate as a raw material is known as a typical method for producing a polycarbonate without using a halogen. In this method, since the polycarbonate is thermally decomposed by heating and the melt viscosity is extremely high, the obtained polycarbonate has an upper limit of its weight average molecular weight of about 30,000. It is not possible to produce a polycarbonate having an average molecular weight of 50,000 or more.
As described above, the development of an electrophotographic photoreceptor that produces a high-molecular-weight polycarbonate without using a halogen and uses the obtained high-molecular-weight polycarbonate as a binder resin can reduce adverse effects on the human body and the environment. Has been eager to.

The present invention has been made in view of the above-described circumstances in the related art. That is, an object of the present invention is to provide a method for easily producing a high-molecular-weight polycarbonate by a method that is safe for the human body and has no adverse effect on the environment.

The present inventors have conducted intensive studies on the production of a high-molecular-weight polycarbonate polymer that does not adversely affect the human body and the environment.As a result, a specific catalyst is used in a transesterification method for producing a polycarbonate using diol and carbonate diester as raw materials. Thus, the present inventors have found that a high-molecular-weight polycarbonate can be easily produced, and have completed the present invention.

That is, in the method for producing a high molecular weight polycarbonate of the present invention, a diol and a carbonate diester are polymerized by a transesterification reaction in which the diol and the carbonate diester are heated in the presence of a basic oxide catalyst. Characterized in that it is obtained from a solution dissolved in
The high molecular weight polycarbonate obtained by the present invention preferably has a residual amount of the catalyst of 10 to 100 ppm and a weight average molecular weight of 50,000 or more (in terms of polystyrene). The amount of the basic oxide catalyst used in the production method is preferably in the range of 20 to 100 ppm based on the produced high molecular weight polycarbonate.

In the production of the high molecular weight polycarbonate in the present invention, the diol is selected from the group consisting of bisphenols, hydrogenated bisphenols, biphenols, hydrogenated biphenols, aryl diols, cycloalkane diols and aliphatic diols. It is preferable to use one kind or a mixture of two or more kinds. Further, as the carbonate diester, it is preferable to use one or a mixture of two or more selected from the group consisting of diaryl carbonates and dialkyl carbonates.

Hereinafter, the method for producing the high molecular weight polycarbonate of the present invention will be described in detail. In the present invention, the diols and carbonate diesters used as starting materials do not contain a halogen atom which is harmful to the human body and adversely affects the environment in their chemical structures.

Conventionally, a production method of obtaining a polycarbonate by using such a diol and a carbonate diester as starting materials, adding a catalyst thereto, heating the mixture under reduced pressure, and allowing the transesterification reaction to proceed is already known. However, in the conventional transesterification method, thermal decomposition of the produced polycarbonate is promoted in the latter half of the reaction, resulting in a polycarbonate having a weight average molecular weight of about 30,000 or less, and producing a high molecular weight polycarbonate having a weight average molecular weight of 50,000 or more. I can't. Further, polycarbonate has a unique property that the melt viscosity is extremely high, and extrusion molding is particularly difficult with high molecular weight ones.

For these reasons, in the conventional transesterification method, a relatively low-molecular-weight polycarbonate having an upper limit of the weight-average molecular weight of about 30,000 is produced, and as described above, an engine for an automobile that requires a high mechanical strength is required. It was not possible to obtain a high molecular weight polycarbonate having a weight average molecular weight of 50,000 or more, particularly a high molecular weight polycarbonate of 80,000 or more, which is used in a special field such as a related part, an eyeglass lens or an electrophotographic photosensitive member part.

However, the present invention solves the above problem by the following method, and provides a method for easily producing a high molecular weight polycarbonate having a weight average molecular weight of 50,000 or more in terms of polystyrene, preferably a high molecular weight polycarbonate of 80,000 or more. It was found.
A first feature of the present invention resides in the use of a basic oxide as a catalyst. When a basic oxide catalyst is used in the transesterification reaction between a diol and a carbonate diester, a polycarbonate formation reaction under specific reaction conditions is performed. This is advantageous in that the decomposition reaction of polycarbonate is suppressed while being effective in improving the polycarbonate.

A second feature of the present invention is to limit the amount of the basic oxide used as the catalyst to a relatively small amount, thereby accelerating the reaction in the direction of producing a high molecular weight polycarbonate having a large weight average molecular weight. be able to. The amount of the basic oxide catalyst used is in the range of 20 to 100 ppm, preferably in the range of 50 to 80 ppm, based on the theoretical yield of the high molecular weight polycarbonate to be produced. It is a suitable amount that can be used. If the amount used is less than 20 ppm, the production reaction of the polycarbonate cannot proceed sufficiently, and it will be saturated at a low molecular weight, and a high molecular weight polycarbonate having a weight average molecular weight of 50,000 or more cannot be obtained. On the other hand, when the amount exceeds 100 ppm, the production reaction of the polycarbonate proceeds, but at the same time, the decomposition reaction becomes active, so that the molecular weight also does not rise sufficiently and the high molecular weight polycarbonate having a weight average molecular weight of 50,000 or more is used. I can't get it.

第 A third feature of the present invention resides in that the produced molten polycarbonate is cooled, then dissolved in a solvent and collected. Generally, polycarbonate has a very high melt viscosity when its weight average molecular weight is 50,000 or more, depending on its chemical structure. For example, polycarbonate A having a weight average molecular weight of 50,000 obtained by polymerization of bisphenol A and diphenyl carbonate has a melt viscosity of 100,000 poise even at a high temperature of 300 ° C., and usually has a melt viscosity of 10 Since the upper limit is about 000 poise, it is difficult to collect by extrusion.

Therefore, in the present invention, without extruding the produced polycarbonate in a molten state, once cooled to room temperature, in the state of a solution dissolved by adding a solvent to this, or by flowing the solution into a poor solvent of polycarbonate By collecting in a recrystallized state produced by the above method, a high molecular weight polycarbonate having a weight average molecular weight of 50,000 or more polymerized by a transesterification method can be easily collected.

The basic oxide catalyst used in the method for producing a high molecular weight polycarbonate of the present invention is selected from transition metal or heavy metal oxides, and specifically, zinc oxide, antimony oxide, lead oxide, and iron oxide. Iron oxide, iron oxide, iron oxide, germanium oxide, cobalt oxide, etc., but the present invention is not limited thereto. Among these, zinc oxide is effective and preferable for controlling the reaction because it promotes the normal transesterification reaction and suppresses the reverse reaction.

出 発 The starting materials used to produce the high molecular weight polycarbonate of the present invention are diols and carbonate diesters. As the raw material diol in the present invention, any material can be used, and specific examples include the following.

Examples of bisphenols include 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxyphenyl) ) Propane, 1,1-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) hexane, 2,2-bis (4- (Hydroxyphenyl) hexane, 3,3-bis (4-hydroxyphenyl) hexane, 1,1-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) heptane, 3,3-bis (4-hydroxyphenyl) heptane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) heptane Nyl) octane, 2,2-bis (4-hydroxyphenyl) octane, 3,3-bis (4-hydroxyphenyl) octane, 4,4-bis (4-hydroxyphenyl) octane, 2,2-bis (4 -Hydroxyphenyl) -4-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,4-trimethylcyclohexane, 1,1-bis (4 -Hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 4,4 '-[1,4-phenylenebis (1-methyl-ethylidene) )] Bis (2,6-dimethylphenol), 4,4 '-[1,4-phenylenebis (1-methyl-ethylidene) Bisphenol, 4,4 '- [1,3-phenylene bis (1-methyl - ethylidene)] bisphenol,

2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxy-3-methylphenyl) methane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 1,1 -Bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) butane, 2,2-bis (4-hydroxy-3-methylphenyl) butane, 1, 1-bis (4-hydroxy-3-methylphenyl) hexane, 2,2-bis (4-hydroxy-3-methylphenyl) hexane, 3,3-bis (4-hydroxy-3-methylphenyl) hexane, 1 1,1-bis (4-hydroxy-3-methylphenyl) heptane, 2,2-bis (4-hydroxy-3-methylphenyl) heptane, 3,3-bis (4-hydr (Xy-3-methylphenyl) heptane, 4,4-bis (4-hydroxy-3-methylphenyl) heptane, 1,1-bis (4-hydroxy-3-methylphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) octane, 3,3-bis (4-hydroxy-3-methylphenyl) octane, 4,4-bis (4-hydroxy-3-methylphenyl) octane, 2,2- Bis (4-hydroxy-3-methylphenyl) -4-methylbutane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -3 , 3,4-Trimethylcyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, bis (4-hydroxy-3-methyl Phenyl) diphenylmethane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene,

2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ) Ethane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) butane, 2,2-bis (4-hydroxy -3,5-dimethylphenyl) butane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) hexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) hexane, 3-bis (4-hydroxy-3,5-dimethylphenyl) hexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) heptane, 2,2-bis (4-hydrido) To xy-3,5-dimethylphenyl) heptane, 3,3-bis (4-hydroxy-3,5-dimethylphenyl) heptane and 4,4-bis (4-hydroxy-3,5-dimethylphenyl) Butane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) octane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) octane, 3,3-bis (4-hydroxy- 3,5-dimethylphenyl) octane, 4,4-bis (4-hydroxy-3,5-dimethylphenyl) octane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) -4-methylbutane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,4-trimethyl Cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) -1-phenylethane, bis (4-hydroxy-3,5-dimethylphenyl) diphenylmethane, 9,9-bis (4-hydroxy- 3,5-dimethylphenyl) fluorene,

2,2-bis [4-hydroxy-3- (1,1-dimethylethyl) phenyl] propane, bis [4-hydroxy-3- (1,1-dimethylethyl) phenyl] methane, 1,1-bis [ 4-hydroxy-3- (1,1-dimethylethyl) phenyl] ethane, 1,1-bis [4-hydroxy-3- (1,1-dimethylethyl) phenyl] propane, 1,1-bis [4- Hydroxy-3- (1,1-dimethylethyl) phenyl] butane, 2,2-bis [4-hydroxy-3- (1,1-dimethylethyl) phenyl] butane, 1,1-bis [4-hydroxy- 3- (1,1-dimethylethyl) phenyl] hexane, 2,2-bis [4-hydroxy-3- (1,1-dimethylethyl) phenyl] hexane, 3,3-bis [4-hydroxy-3- (1,1 Dimethylethyl) phenyl] hexane, 1,1-bis [4-hydroxy-3- (1,1-dimethylethyl) phenyl] heptane, 2,2-bis [4-hydroxy-3- (1,1-dimethylethyl) ) Phenyl] heptane, 3,3-bis [4-hydroxy-3- (1,1-dimethylethyl) phenyl] heptane, 4,4-bis [4-hydroxy-3- (1,1-dimethylethyl) ) Phenyl] heptane, 1,1-bis [4-hydroxy-3- (1,1-dimethylethyl) phenyl] octane, 2,2-bis [4-hydroxy-3- (1,1-dimethylethyl) Phenyl] octane, 3,3-bis [4-hydroxy-3- (1,1-dimethylethyl) phenyl] octane, 4,4-bis [4-hydroxy-3- (1,1-dimethylethyl) phenyl Octane, 2,2-bis [4-hydroxy-3- (1,1-dimethylethyl) phenyl] -4-methylbutane, 1,1-bis [4-hydroxy-3- (1,1-dimethylethyl) phenyl ] Cyclohexane, 1,1-bis [4-hydroxy-3- (1,1-dimethylethyl) phenyl] -3,3,4-trimethylcyclohexane, 1,1-bis [4-hydroxy-3- (1, 1-dimethylethyl) phenyl] -1-phenylethane, bis [4-hydroxy-3- (1,1-dimethylethyl) phenyl] diphenylmethane, 9,9-bis [4-hydroxy-3- (1,1- Dimethylethyl) phenyl] fluorene,

2,2-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) phenyl] propane, bis [4-hydroxy-3,5-di (1,1-dimethylethyl) phenyl] methane, 1,1-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) phenyl] ethane, 1,1-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) Phenyl] propane, 1,1-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) phenyl] butane, 2,2-bis [4-hydroxy-3,5-di (1,1 -Dimethylethyl) phenyl] butane, 1,1-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) phenyl] hexane, 2,2-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) phenyl] hex 3,3-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) phenyl] hexane, 1,1-bis [4-hydroxy-3,5-di (1,1-dimethyl) Ethyl) phenyl] heptane, 2,2-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) phenyl] heptane, 3,3-bis [4-hydroxy-3,5-di ( 1,1-dimethylethyl) phenyl] heptane, 4,4-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) phenyl] heptane, 1,1-bis [4-hydroxy- 3,5-di (1,1-dimethylethyl) phenyl] octane, 2,2-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) phenyl] octane, 3,3-bis [ 4-hydroxy-3,5-di (1,1-dimethyl Tyl) phenyl] octane, 4,4-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) phenyl] octane, 2,2-bis [4-hydroxy-3,5-di (1 , 1-Dimethylethyl) phenyl] -4-methylbutane, 1,1-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) phenyl] cyclohexane, 1,1-bis [4-hydroxy- 3,5-di (1,1-dimethylethyl) phenyl] -3,3,4-trimethylcyclohexane, 1,1-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) phenyl] -1-phenylethane, bis [4-hydroxy-3,5-di (1,1-dimethylethyl) phenyl] diphenylmethane, 9,9-bis [4-hydroxy-3,5-di (1,1-dimethyl) ethyl) Phenyl] fluorene,

2,2-bis [4-hydroxy-3-phenylphenyl] propane, bis [4-hydroxy-3-phenylphenyl] methane, 1,1-bis [4-hydroxy-3-phenylphenyl] ethane, 1,1 -Bis [4-hydroxy-3-phenylphenyl] propane, 1,1-bis [4-hydroxy-3-phenylphenyl] butane, 2,2-bis [4-hydroxy-3-phenylphenyl] butane, 1-bis [4-hydroxy-3-phenylphenyl] hexane, 2,2-bis [4-hydroxy-3-phenylphenyl] hexane, 3,3-bis [4-hydroxy-3-phenylphenyl] hexane, 1 1,1-bis [4-hydroxy-3-phenylphenyl] heptane, 2,2-bis [4-hydroxy-3-phenylphenyl] heptane, , 3-Bis [4-hydroxy-3-phenylphenyl] heptane, 4,4-bis [4-hydroxy-3-phenylphenyl] heptane, 1,1-bis [4-hydroxy-3-phenylphenyl] Octane, 2,2-bis [4-hydroxy-3-phenylphenyl] octane, 3,3-bis [4-hydroxy-3-phenylphenyl] octane, 4,4-bis [4-hydroxy-3-phenylphenyl] ] Octane, 2,2-bis [4-hydroxy-3-phenylphenyl] -4-methylbutane, 1,1-bis [4-hydroxy-3-phenylphenyl] cyclohexane, 1,1-bis [4-hydroxy- 3-phenylphenyl] -3,3,4-trimethylcyclohexane, 1,1-bis [4-hydroxy-3-phenylphenyl] -1-fe Ruetan, bis [4-hydroxy-3-phenyl-phenyl] methane, 9,9-bis [4-hydroxy-3-phenylphenyl] fluorene,

2,2-bis [4-hydroxy-3,5-diphenylphenyl] propane, bis [4-hydroxy-3,5-diphenylphenyl] methane, 1,1-bis [4-hydroxy-3,5-diphenylphenyl ] Ethane, 1,1-bis [4-hydroxy-3,5-diphenylphenyl] propane, 1,1-bis [4-hydroxy-3,5-diphenylphenyl] butane, 2,2-bis [4-hydroxy -3,5-diphenylphenyl] butane, 1,1-bis [4-hydroxy-3,5-diphenylphenyl] hexane, 2,2-bis [4-hydroxy-3,5-diphenylphenyl] hexane, 3-bis [4-hydroxy-3,5-diphenylphenyl] hexane, 1,1-bis [4-hydroxy-3,5-diphenylphenyl] heptane, 2 2-bis [4-hydroxy-3,5-diphenylphenyl] heptane, 3,3-bis [4-hydroxy-3,5-diphenylphenyl] heptane, 4,4-bis [4-hydroxy-3, 5-diphenylphenyl] heptane, 1,1-bis [4-hydroxy-3,5-diphenylphenyl] octane, 2,2-bis [4-hydroxy-3,5-diphenylphenyl] octane, 3,3- Bis [4-hydroxy-3,5-diphenylphenyl] octane, 4,4-bis [4-hydroxy-3,5-diphenylphenyl] octane, 2,2-bis [4-hydroxy-3,5-diphenylphenyl ] -4-methylbutane, 1,1-bis [4-hydroxy-3,5-diphenylphenyl] cyclohexane, 1,1-bis [4-hydroxy-3,5-di Phenylphenyl] -3,3,4-trimethylcyclohexane, 1,1-bis [4-hydroxy-3,5-diphenylphenyl] -1-phenylethane, bis [4-hydroxy-3,5-diphenylphenyl] diphenylmethane 9,9-bis [4-hydroxy-3,5-diphenylphenyl] fluorene,

2,2-bis [4-hydroxy-3-cyclohexylphenyl] propane, bis [4-hydroxy-3-cyclohexylphenyl] methane, 1,1-bis [4-hydroxy-3-cyclohexylphenyl] ethane, 1,1 -Bis [4-hydroxy-3-cyclohexylphenyl] propane, 1,1-bis [4-hydroxy-3-cyclohexylphenyl] butane, 2,2-bis [4-hydroxy-3-cyclohexylphenyl] butane, 1-bis [4-hydroxy-3-cyclohexylphenyl] hexane, 2,2-bis [4-hydroxy-3-cyclohexylphenyl] hexane, 3,3-bis [4-hydroxy-3-cyclohexylphenyl] hexane, , 1-bis [4-hydroxy-3-cyclohexylphenyl] heptane, 2 2-bis [4-hydroxy-3-cyclohexylphenyl] heptane, 3,3-bis [4-hydroxy-3-cyclohexylphenyl] heptane, 4,4-bis [4-hydroxy-3-cyclohexylphenylphenyl] Heptane, 1,1-bis [4-hydroxy-3-cyclohexylphenyl] octane, 2,2-bis [4-hydroxy-3-cyclohexylphenyl] octane, 3,3-bis [4-hydroxy-3-cyclohexyl] Phenyl] octane, 4,4-bis [4-hydroxy-3-cyclohexylphenyl] octane, 2,2-bis [4-hydroxy-3-cyclohexylphenyl] -4-methylbutane, 1,1-bis [4-hydroxy -3-cyclohexylphenyl] cyclohexane, 1,1-bis [4-hydroxy-3 Cyclohexylphenyl] -3,3,4-trimethylcyclohexane, 1,1-bis [4-hydroxy-3-cyclohexylphenyl] -1-phenylethane, bis [4-hydroxy-3-cyclohexylphenyl] diphenylmethane, 9,9 -Bis [4-hydroxy-3-cyclohexylphenyl] fluorene,

2,2-bis [4-hydroxy-3,5-dicyclohexylphenyl] propane, bis [4-hydroxy-3,5-dicyclohexylphenyl] methane, 1,1-bis [4-hydroxy-3,5-dicyclohexylphenyl] ] Ethane, 1,1-bis [4-hydroxy-3,5-dicyclohexylphenyl] propane, 1,1-bis [4-hydroxy-3,5-dicyclohexylphenyl] butane, 2,2-bis [4-hydroxy -3,5-dicyclohexylphenyl] butane, 1,1-bis [4-hydroxy-3,5-dicyclohexylphenyl] hexane, 2,2-bis [4-hydroxy-3,5-dicyclohexylphenyl] hexane, 3, 3-bis [4-hydroxy-3,5-dicyclohexylphenyl] hexane, 1,1-bis [4 Hydroxy-3,5-dicyclohexylphenyl] heptane, 2,2-bis [4-hydroxy-3,5-dicyclohexylphenyl] heptane, 3,3-bis [4-hydroxy-3,5-dicyclohexylphenyl] heptane 4,4-bis [4-hydroxy-3,5-dicyclohexylphenylphenyl] heptane, 1,1-bis [4-hydroxy-3,5-dicyclohexylphenyl] octane, 2,2-bis [4-hydroxy -3-dicyclohexylphenyl] octane, 3,3-bis [4-hydroxy-3,5-dicyclohexylphenyl] octane, 4,4-bis [4-hydroxy-3,5-dicyclohexylphenyl] octane, 2,2- Bis [4-hydroxy-3,5-dicyclohexylphenyl] -4-methylbutane, 1 1-bis [4-hydroxy-3,5-dicyclohexylphenyl] cyclohexane, 1,1-bis [4-hydroxy-3,5-dicyclohexylphenyl] -3,3,4-trimethylcyclohexane, 1,1-bis [ 4-hydroxy-3,5-dicyclohexylphenyl] -1-phenylethane, bis [4-hydroxy-3,5-dicyclohexylphenyl] diphenylmethane, 9,9-bis [4-hydroxy-3,5-dicyclohexylphenyl] fluorene And the like.

Next, biphenols include (1,1'-biphenyl) -4,4'-diol, (1,1'-biphenyl) -2,4'-diol, and (1,1'-biphenyl) -3. , 4'-diol, (1,1'-biphenyl) -2,2'-diol, (1,1'-biphenyl) -2,3'-diol, (1,1'-biphenyl) -3,3 '-Diol, 3,3'-dimethyl-[(1,1'-biphenyl) -4,4'-diol], 2,2'-dimethyl-[(1,1'-biphenyl) -4,4' -Diol], 3,5,3 ', 5'-tetramethyl-[(1,1'-biphenyl) -4,4'-diol], 3,5,2', 3'-tetramethyl-[( 1,1,1′-biphenyl) -4,4′-diol], 2,3,2 ′, 3′-tetramethyl-[(1,1′-biphenyl) Enyl) -4,4'-diol], 3,3'-dimethyl-[(1,1'-biphenyl) -2,4'-diol], 4,3'-dimethyl-[(1,1'-diol) Biphenyl) -2,4'-diol], 4,2'-dimethyl-[(1,1'-biphenyl) -2,4'-diol], 2,2'-dimethyl-[(1,1'-diol) Biphenyl) -3,4'-diol], 2,5'-dimethyl-[(1,1'-biphenyl) -3,4'-diol], 4,2'-dimethyl-[(1,1'- Biphenyl) -3,4'-diol], 4,5'-dimethyl-[(1,1'-biphenyl) -3,4'-diol], 4,4'-dimethyl [(1,1'-biphenyl) ) -2,2'-diol], 4,3'-dimethyl [(1,1'-biphenyl) -2,2'-diol], 3,3 - dimethyl [(1,1'-biphenyl) -2,2'-diol],

3,3'-diphenyl-[(1,1'-biphenyl) -4,4'-diol], 2,2'-diphenyl-[(1,1'-biphenyl) -4,4'-diol], 3,5,3 ', 5'-tetraphenyl-[(1,1'-biphenyl) -4,4'-diol], 3,5,2', 3'-tetraphenyl-[(1,1 ' -Biphenyl) -4,4'-diol], 2,3,2 ', 3'-tetraphenyl-[(1,1'-biphenyl) -4,4'-diol], 3,3'-diphenyl- [(1,1'-biphenyl) -2,4'-diol], 4,3'-diphenyl-[(1,1'-biphenyl) -2,4'-diol], 4,2'-diphenyl- [(1,1'-biphenyl) -2,4'-diol], 2,2'-diphenyl-[(1,1'-biphenyl) 3,4'-diol], 2,5'-diphenyl-[(1,1'-biphenyl) -3,4'-diol], 4,2'-diphenyl-[(1,1'-biphenyl)- 3,4'-diol], 4,5'-diphenyl-[(1,1'-biphenyl) -3,4'-diol], 4,4'-diphenyl-[(1,1'-biphenyl)- 2,2'-diol], 4,3'-diphenyl-[(1,1'-biphenyl) -2,2'-diol], 3,3'-diphenyl-[(1,1'-biphenyl)- 2,2'-diol],

3,3'-dicyclohexyl-[(1,1'-biphenyl) -4,4'-diol], 2,2'-dicyclohexyl-[(1,1'-biphenyl) -4,4'-diol], 3,5,3 ', 5'-tetracyclohexyl-[(1,1'-biphenyl) -4,4'-diol], 3,5,2', 3'-tetracyclohexyl-[(1,1 ' -Biphenyl) -4,4'-diol], 2,3,2 ', 3'-tetracyclohexyl-[(1,1'-biphenyl) -4,4'-diol], 3,3'-dicyclohexyl- [(1,1'-biphenyl) -2,4'-diol], 4,3'-dicyclohexyl-[(1,1'-biphenyl) -2,4'-diol], 4,2'-dicyclohexyl- [(1,1'-biphenyl) -2,4'-diol], , 2'-Dicyclohexyl-[(1,1'-biphenyl) -3,4'-diol], 2,5'-dicyclohexyl-[(1,1'-biphenyl) -3,4'-diol], 4 , 2'-Dicyclohexyl-[(1,1'-biphenyl) -3,4'-diol], 4,5'-dicyclohexyl-[(1,1'-biphenyl) -3,4'-diol], 4 , 4'-Dicyclohexyl [(1,1'-biphenyl) -2,2'-diol], 4,3'-cyclohexyl [(1,1'-biphenyl) -2,2'-diol], 3,3 '-Dicyclohexyl [(1,1'-biphenyl) -2,2'-diol] and the like.

Examples of hydrogenated bisphenols include 2,2-bis (4-hydroxycyclohexyl) propane, bis (4-hydroxycyclohexyl) methane, 1,1-bis (4-hydroxycyclohexyl) ethane, and 1,1-bis (4- (Hydroxycyclohexyl) propane, 1,1-bis (4-hydroxycyclohexyl) butane, 2,2-bis (4-hydroxycyclohexyl) butane, 1,1-bis (4-hydroxycyclohexyl) hexane, 2,2-bis ( 4-hydroxycyclohexyl) hexane, 3,3-bis (4-hydroxycyclohexyl) hexane, 1,1-bis (4-hydroxycyclohexyl) heptane, 2,2-bis (4-hydroxycyclohexyl) heptane, 3,3 -Bis (4-hydroxycyclohexyl) heptane, 4 4-bis (4-hydroxycyclohexyl) heptane, 1,1-bis (4-hydroxycyclohexyl) octane, 2,2-bis (4-hydroxycyclohexyl) octane, 3,3-bis (4-hydroxycyclohexyl) octane 4,4-bis (4-hydroxycyclohexyl) octane, 2,2-bis (4-hydroxycyclohexyl) -4-methylbutane, 1,1-bis (4-hydroxycyclohexyl) cyclohexane, 1,1-bis (4 -Hydroxycyclohexyl) -3,3,4-trimethylcyclohexane, 1,1-bis (4-hydroxycyclohexyl) -1-phenylethane, bis (4-hydroxycyclohexyl) diphenylmethane, 9,9-bis (4-hydroxycyclohexyl) ) Fluorene, 4,4 '-[1 4-cyclohexenebis (1-methyl-ethylidene)] bis (2,6-dimethylcyclohexanol), 4,4 '-[1,4-cyclohexenebis (1-methyl-ethylidene)] biscyclohexanol, 4,4 '-[1,3-cyclohexenebis (1-methyl-ethylidene)] cyclohexanol,

2,2-bis (4-hydroxy-3-methylcyclohexyl) propane, bis (4-hydroxy-3-methylcyclohexyl) methane, 1,1-bis (4-hydroxy-3-methylcyclohexyl) ethane, 1,1 -Bis (4-hydroxy-3-methylcyclohexyl) propane, 1,1-bis (4-hydroxy-3-methylcyclohexyl) butane, 2,2-bis (4-hydroxy-3-methylcyclohexyl) butane, 1-bis (4-hydroxy-3-methylcyclohexyl) hexane, 2,2-bis (4-hydroxy-3-methylcyclohexyl) hexane, 3,3-bis (4-hydroxy-3-methylcyclohexyl) hexane, 1 1,1-bis (4-hydroxy-3-methylcyclohexyl) heptane, 2,2-bis (4-hydrido) (Xy-3-methylcyclohexyl) heptane, 3,3-bis (4-hydroxy-3-methylcyclohexyl) heptane, 4,4-bis (4-hydroxy-3-methylcyclohexyl) heptane, 1,1- Bis (4-hydroxy-3-methylcyclohexyl) octane, 2,2-bis (4-hydroxy-3-methylcyclohexyl) octane, 3,3-bis (4-hydroxy-3-methylcyclohexyl) octane, 4,4 -Bis (4-hydroxy-3-methylcyclohexyl) octane, 2,2-bis (4-hydroxy-3-methylcyclohexyl) -4-methylbutane, 1,1-bis (4-hydroxy-3-methylcyclohexyl) cyclohexane , 1,1-bis (4-hydroxy-3-methylcyclohexyl) -3,3,4-trimethyl Cyclohexane, 1,1-bis (4-hydroxy-3-methylcyclohexyl) -1-phenylethane, bis (4-hydroxy-3-methylcyclohexyl) diphenylmethane, 9,9-bis (4-hydroxy-3-methylcyclohexyl) ) Fluorene,

2,2-bis (4-hydroxy-3,5-dimethylcyclohexyl) propane, bis (4-hydroxy-3,5-dimethylcyclohexyl) methane, 1,1-bis (4-hydroxy-3,5-dimethylcyclohexyl) ) Ethane, 1,1-bis (4-hydroxy-3,5-dimethylcyclohexyl) propane, 1,1-bis (4-hydroxy-3,5-dimethylcyclohexyl) butane, 2,2-bis (4-hydroxy -3,5-dimethylcyclohexyl) butane, 1,1-bis (4-hydroxy-3,5-dimethylcyclohexyl) hexane, 2,2-bis (4-hydroxy-3,5-dimethylcyclohexyl) hexane, 3-bis (4-hydroxy-3,5-dimethylcyclohexyl) hexane, 1,1-bis (4-hydroxy-3, -Dimethylcyclohexyl) heptane, 2,2-bis (4-hydroxy-3,5-dimethylcyclohexyl) heptane, 3,3-bis (4-hydroxy-3,5-dimethylcyclohexyl) heptane, 4,4- Bis (4-hydroxy-3,5-dimethylcyclohexyl) heptane, 1,1-bis (4-hydroxy-3,5-dimethylcyclohexyl) octane, 2,2-bis (4-hydroxy-3,5-dimethyl) Cyclohexyl) octane, 3,3-bis (4-hydroxy-3,5-dimethylcyclohexyl) octane, 4,4-bis (4-hydroxy-3,5-dimethylcyclohexyl) octane, 2,2-bis (4- Hydroxy-3,5-dimethylcyclohexyl) -4-methylbutane, 1,1-bis (4-hydroxy-3,5-dimethyl) L-cyclohexyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylcyclohexyl) -3,3,4-trimethylcyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylcyclohexyl)- 1-phenylethane, bis (4-hydroxy-3,5-dimethylcyclohexyl) diphenylmethane, 9,9-bis (4-hydroxy-3,5-dimethylcyclohexyl) fluorene,

2,2-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] propane, bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] methane, 1,1-bis [ 4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] ethane, 1,1-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] propane, 1,1-bis [4- Hydroxy-3- (1,1-dimethylethyl) cyclohexyl] butane, 2,2-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] butane, 1,1-bis [4-hydroxy- 3- (1,1-dimethylethyl) cyclohexyl] hexane, 2,2-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] hex 3,3-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] hexane, 1,1-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] heptane, 2,2-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] heptane, 3,3-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] heptane, 4,4-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] heptane, 1,1-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] octane, 2,2-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] octane, 3,3-bis [4-hydroxy-3- (1,1-dimethylethyl) Cyclohexyl] octane, 4,4-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] octane, 2,2-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] -4-methylbutane, 1,1-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] cyclohexane, 1,1-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl ] -3,3,4-trimethylcyclohexane, 1,1-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclohexyl] -1-phenylethane, bis [4-hydroxy-3- (1, 1-dimethylethyl) cyclohexyl] diphenylmethane, 9,9-bis [4-hydroxy-3- (1,1-dimethylethyl) cyclo Hexyl] fluorene,

2,2-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) cyclohexyl] propane, bis [4-hydroxy-3,5-di (1,1-dimethylethyl) cyclohexyl] methane, 1,1-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) cyclohexyl] ethane, 1,1-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) Cyclohexyl] propane, 1,1-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) cyclohexyl] butane, 2,2-bis [4-hydroxy-3,5-di (1,1 -Dimethylethyl) cyclohexyl] butane, 1,1-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) cyclohexyl] hexane, 2,2-bis [4-hydroxy-3,5- (1,1-dimethylethyl) cyclohexyl] hexane, 3,3-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) cyclohexyl] hexane, 1,1-bis [4-hydroxy-3 , 5-Di (1,1-dimethylethyl) cyclohexyl] heptane, 2,2-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) cyclohexyl] heptane, 3,3-bis [ 4-hydroxy-3,5-di (1,1-dimethylethyl) cyclohexyl] heptane, 4,4-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) cyclohexyl] heptane, 1,1-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) cyclohexyl] octane, 2,2-bis [4-hydroxy-3,5-di (1,1-dimethyle L) cyclohexyl] octane, 3,3-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) cyclohexyl] octane, 4,4-bis [4-hydroxy-3,5-di (1 , 1-Dimethylethyl) cyclohexyl] octane, 2,2-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) cyclohexyl] -4-methylbutane, 1,1-bis [4-hydroxy- 3,5-di (1,1-dimethylethyl) cyclohexyl] cyclohexane, 1,1-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) cyclohexyl] -3,3,4-trimethyl Cyclohexane, 1,1-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) cyclohexyl] -1-phenylethane, bis [4-hydroxy-3, 5-di (1,1-dimethylethyl) cyclohexyl] diphenylmethane, 9,9-bis [4-hydroxy-3,5-di (1,1-dimethylethyl) cyclohexyl] fluorene,

2,2-bis [4-hydroxy-3-phenylcyclohexyl] propane, bis [4-hydroxy-3-phenylcyclohexyl] methane, 1,1-bis [4-hydroxy-3-phenylcyclohexyl] ethane, 1,1 -Bis [4-hydroxy-3-phenylcyclohexyl] propane, 1,1-bis [4-hydroxy-3-phenylcyclohexyl] butane, 2,2-bis [4-hydroxy-3-phenylcyclohexyl] butane, 1-bis [4-hydroxy-3-phenylcyclohexyl] hexane, 2,2-bis [4-hydroxy-3-phenylcyclohexyl] hexane, 3,3-bis [4-hydroxy-3-phenylcyclohexyl] hexane, 1 , 1-bis [4-hydroxy-3-phenylcyclohexyl] heptane, 2 2-bis [4-hydroxy-3-phenylcyclohexyl] heptane, 3,3-bis [4-hydroxy-3-phenylcyclohexyl] heptane, 4,4-bis [4-hydroxy-3-phenylcyclohexyl] Butane, 1,1-bis [4-hydroxy-3-phenylcyclohexyl] octane, 2,2-bis [4-hydroxy-3-phenylcyclohexyl] octane, 3,3-bis [4-hydroxy-3-phenylcyclohexyl] ] Octane, 4,4-bis [4-hydroxy-3-phenylcyclohexyl] octane, 2,2-bis [4-hydroxy-3-phenylcyclohexyl] -4-methylbutane, 1,1-bis [4-hydroxy- 3-phenylcyclohexyl] cyclohexane, 1,1-bis [4-hydroxy-3-phenyl Cyclohexyl] -3,3,4-trimethylcyclohexane, 1,1-bis [4-hydroxy-3-phenylcyclohexyl] -1-phenylethane, bis [4-hydroxy-3-phenylcyclohexyl] diphenylmethane, 9,9- Bis [4-hydroxy-3-phenylcyclohexyl] fluorene,

2,2-bis [4-hydroxy-3,5-diphenylcyclohexyl] propane, bis [4-hydroxy-3,5-diphenylcyclohexyl] methane, 1,1-bis [4-hydroxy-3,5-diphenylcyclohexyl] ] Ethane, 1,1-bis [4-hydroxy-3,5-diphenylcyclohexyl] propane, 1,1-bis [4-hydroxy-3,5-diphenylcyclohexyl] butane, 2,2-bis [4-hydroxy -3,5-diphenylcyclohexyl] butane, 1,1-bis [4-hydroxy-3,5-diphenylcyclohexyl] hexane, 2,2-bis [4-hydroxy-3,5-diphenylcyclohexyl] hexane, 3, 3-bis [4-hydroxy-3,5-diphenylcyclohexyl] hexane, 1,1-bis [4 Hydroxy-3,5-diphenylcyclohexyl] heptane, 2,2-bis [4-hydroxy-3,5-diphenylcyclohexyl] heptane, 3,3-bis [4-hydroxy-3,5-diphenylcyclohexyl] heptane 4,4-bis [4-hydroxy-3,5-diphenylcyclohexyl] heptane, 1,1-bis [4-hydroxy-3,5-diphenylcyclohexyl] octane, 2,2-bis [4-hydroxy- 3,5-diphenylcyclohexyl] octane, 3,3-bis [4-hydroxy-3,5-diphenylcyclohexyl] octane, 4,4-bis [4-hydroxy-3,5-diphenylcyclohexyl] octane, 2,2 -Bis [4-hydroxy-3,5-diphenylcyclohexyl] -4-methylbutane, 1,1 Bis [4-hydroxy-3,5-diphenylcyclohexyl] cyclohexane, 1,1-bis [4-hydroxy-3,5-diphenylcyclohexyl] -3,3,4-trimethylcyclohexane, 1,1-bis [4- Hydroxy-3,5-diphenylcyclohexyl] -1-phenylethane, bis [4-hydroxy-3,5-diphenylcyclohexyl] diphenylmethane, 9,9-bis [4-hydroxy-3,5-diphenylcyclohexyl] fluorene,

2,2-bis [4-hydroxy-3-cyclohexylcyclohexyl] propane, bis [4-hydroxy-3-cyclohexylcyclohexyl] methane, 1,1-bis [4-hydroxy-3-cyclohexylcyclohexyl] ethane, 1,1 -Bis [4-hydroxy-3-cyclohexylcyclohexyl] propane, 1,1-bis [4-hydroxy-3-cyclohexylcyclohexyl] butane, 2,2-bis [4-hydroxy-3-cyclohexylcyclohexyl] butane, 1-bis [4-hydroxy-3-cyclohexylcyclohexyl] hexane, 2,2-bis [4-hydroxy-3-cyclohexylcyclohexyl] hexane, 3,3-bis [4-hydroxy-3-cyclohexylcyclohexyl] hexane, 1 , 1-bis [4 Hydroxy-3-cyclohexylcyclohexyl] heptane, 2,2-bis [4-hydroxy-3-cyclohexylcyclohexyl] heptane, 3,3-bis [4-hydroxy-3-cyclohexylcyclohexyl] heptane, 4,4-bis [4-hydroxy-3-cyclohexylphenylcyclohexyl] heptane, 1,1-bis [4-hydroxy-3-cyclohexylcyclohexyl] octane, 2,2-bis [4-hydroxy-3-cyclohexylcyclohexyl] octane, 3, 3-bis [4-hydroxy-3-cyclohexylcyclohexyl] octane, 4,4-bis [4-hydroxy-3-cyclohexylcyclohexyl] octane, 2,2-bis [4-hydroxy-3-cyclohexylcyclohexyl] -4- Methylbutane 1,1-bis [4-hydroxy-3-cyclohexylcyclohexyl] cyclohexane, 1,1-bis [4-hydroxy-3-cyclohexylcyclohexyl] -3,3,4-trimethylcyclohexane, 1,1-bis [4- Hydroxy-3-cyclohexylcyclohexyl] -1-phenylethane, bis [4-hydroxy-3-cyclohexylcyclohexyl] diphenylmethane, 9,9-bis [4-hydroxy-3-cyclohexylcyclohexyl] fluorene,

2,2-bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] propane, bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] methane, 1,1-bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] ] Ethane, 1,1-bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] propane, 1,1-bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] butane, 2,2-bis [4-hydroxy -3,5-dicyclohexylcyclohexyl] butane, 1,1-bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] hexane, 2,2-bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] hexane, 3, 3-bis [4-hydroxy-3,5-disi Lohexylcyclohexyl] hexane, 1,1-bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] heptane, 2,2-bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] heptane, 3,3-bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] heptane, 4,4-bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] heptane, 1,1-bis [4-hydroxy-3,5-dicyclohexyl] Cyclohexyl] octane, 2,2-bis [4-hydroxy-3-dicyclohexylcyclohexyl] octane, 3,3-bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] octane, 4,4-bis [4-hydroxy- 3,5-dicyclohexylcyclohexyl] o Tan, 2,2-bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] -4-methylbutane, 1,1-bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] cyclohexane, 1,1-bis [4 -Hydroxy-3,5-dicyclohexylcyclohexyl] -3,3,4-trimethylcyclohexane, 1,1-bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] -1-phenylethane, bis [4-hydroxy-3 , 5-dicyclohexylcyclohexyl] diphenylmethane, 9,9-bis [4-hydroxy-3,5-dicyclohexylcyclohexyl] fluorene, and the like.

Next, hydrogenated biphenols include (1,1'-bicyclohexyl) -4,4'-diol, (1,1'-bicyclohexyl) -2,4'-diol, and (1,1'-diol). (Bicyclohexyl) -3,4'-diol, (1,1'-bicyclohexyl) -2,2'-diol, (1,1'-bicyclohexyl) -2,3'-diol, (1,1 ' -Bicyclohexyl) -3,3'-diol, 3,3'-dimethyl-[(1,1'-bicyclohexyl) -4,4'-diol], 2,2'-dimethyl-[(1,1 '-Bicyclohexyl) -4,4'-diol], 3,5,3', 5'-tetramethyl-[(1,1'-bicyclohexyl) -4,4'-diol], 3,5 2 ', 3'-tetramethyl-[(1,1'-bicyclohexyl) -4,4' Diol], 2,3,2 ', 3'-tetramethyl-[(1,1'-bicyclohexyl) -4,4'-diol], 3,3'-dimethyl-[(1,1'-bi Cyclohexyl) -2,4'-diol], 4,3'-dimethyl-[(1,1'-bicyclohexyl) -2,4'-diol], 4,2'-dimethyl-[(1,1 ' -Bicyclohexyl) -2,4'-diol], 2,2'-dimethyl-[(1,1'-bicyclohexyl) -3,4'-diol], 2,5'-dimethyl-[(1, 1'-bicyclohexyl) -3,4'-diol], 4,2'-dimethyl-[(1,1'-bicyclohexyl) -3,4'-diol], 4,5'-dimethyl-[( 1,1'-bicyclohexyl) -3,4'-diol], 4,4'-dimethyl [(1,1 ' Bicyclohexyl) -2,2'-diol], 4,3'-dimethyl [(1,1'-bicyclohexyl) -2,2'-diol], 3,3'-dimethyl [(1,1'-diol) Bicyclohexyl) -2,2'-diol],

3,3'-diphenyl-[(1,1'-bicyclohexyl) -4,4'-diol], 2,2'-diphenyl-[(1,1'-bicyclohexyl) -4,4'-diol ], 3,5,3 ', 5'-tetraphenyl-[(1,1'-bicyclohexyl) -4,4'-diol], 3,5,2', 3'-tetraphenyl-[(1 , 1'-bicyclohexyl) -4,4'-diol], 2,3,2 ', 3'-tetraphenyl-[(1,1'-bicyclohexyl) -4,4'-diol], 3, 3'-diphenyl-[(1,1'-bicyclohexyl) -2,4'-diol], 4,3'-diphenyl-[(1,1'-bicyclohexyl) -2,4'-diol], 4,2'-diphenyl-[(1,1'-bicyclohexyl) -2,4'-diol], , 2'-Diphenyl-[(1,1'-bicyclohexyl) -3,4'-diol], 2,5'-diphenyl-[(1,1'-bicyclohexyl) -3,4'-diol] , 4,2'-diphenyl-[(1,1'-bicyclohexyl) -3,4'-diol], 4,5'-diphenyl-[(1,1'-bicyclohexyl) -3,4'- Diol], 4,4'-diphenyl-[(1,1'-bicyclohexyl) -2,2'-diol], 4,3'-diphenyl- フ ェ ニ ル [(1,1'-bicyclohexyl) -2,2 '-Diol], 3,3'-diphenyl-[(1,1'-bicyclohexyl) -2,2'-diol],

3,3'-dicyclohexyl-[(1,1'-bicyclohexyl) -4,4'-diol], 2,2'-dicyclohexyl-[(1,1'-bicyclohexyl) -4,4'-diol ], 3,5,3 ', 5'-tetracyclohexyl-[(1,1'-bicyclohexyl) -4,4'-diol], 3,5,2', 3'-tetracyclohexyl-[(1 , 1'-bicyclohexyl) -4,4'-diol], 2,3,2 ', 3'-tetracyclohexyl-[(1,1'-bicyclohexyl) -4,4'-diol], 3, 3'-dicyclohexyl-[(1,1'-bicyclohexyl) -2,4'-diol], 4,3'-dicyclohexyl-[(1,1'-bicyclohexyl) -2,4'-diol], 4,2'-dicyclohexyl-[(1, '-Bicyclohexyl) -2,4'-diol], 2,2'-dicyclohexyl-[(1,1'-bicyclohexyl) -3,4'-diol], 2,5'-dicyclohexyl-[(1 , 1'-bicyclohexyl) -3,4'-diol], 4,2'-dicyclohexyl-[(1,1'-bicyclohexyl) -3,4'-diol], 4,5'-dicyclohexyl- [ (1,1'-bicyclohexyl) -3,4'-diol], 4,4'-dicyclohexyl [(1,1'-bicyclohexyl) -2,2'-diol], 4,3'-cyclohexyl [ (1,1'-bicyclohexyl) -2,2'-diol] and 3,3'-dicyclohexyl [(1,1'-bicyclohexyl) -2,2'-diol].

Next, examples of the aryl diols include 2,6-naphthalene diol, 2,7-naphthalene diol, 2,3-naphthalene diol, 2,5-naphthalene diol, 1,2-naphthalene diol, and 1,3-naphthalene diol. 1,4-naphthalene diol, 1,5-naphthalene diol, 1,7-naphthalene diol, 1,8-naphthalene diol, 1,4-benzenediol, 1,2-benzenediol, 1,3-benzenediol, etc. Is mentioned.

Next, as cycloalkanediols, 1,4-cyclohexanediol, 1,1-cyclohexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexane dimethylol, 1,1-cyclohexanediol To cyclohexane dimethylol, 1,2-cyclohexane dimethylol, 1,3-cyclohexane dimethylol, 1,4-cyclopentanediol, 1,1-cyclopentanediol, 1,3-cyclopentanediol, 1,5-cyclohexane Butanediol, 1,1-cycloheptanediol, 1,2-cycloheptanediol, 1,3-cycloheptanediol, 1,4-cyclopentanediol, 1,5-cyclohoctanediol, 1,1 -Cyclooctanediol, 1,2-cyclooctanediol 1,3 cyclo-octanediol, 1,4-octane diol, include tricyclodecanedimethylol roll or the like.

Further, as aliphatic diols, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,2 -Pentanediol, 1,3-pentanediol and the like. In the present invention, any of the above diols is effective for producing a high molecular weight polycarbonate, but any two or more of these diols may be used in combination.

Further, as the raw material carbonate diester in the present invention, any one can be used. Specifically, diaryl carbonates such as diphenyl carbonate and dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, di (1- Examples thereof include dialkyl carbonates such as (methylethyl) carbonate, dibutyl carbonate, di (1-methylpropyl) carbonate, and di (1,1-dimethylethyl) carbonate. For producing the high molecular weight polycarbonate of the present invention, any of the above carbonate diesters is effective, and any two or more of these carbonate diesters may be used in combination.

In the present invention, as the solvent used for dissolving the produced polycarbonate, any arbitrary solvent can be used as long as the solvent can dissolve the predetermined polycarbonate.Specifically, tetrahydrofuran, cyclic ether such as dioxane, dichloromethane, dichloromethane, Chlorinated aliphatic hydrocarbons such as chloroform, chlorinated aromatic hydrocarbons such as monochlorobenzene, aromatic hydrocarbons such as toluene and xylene, esters such as methyl acetate, ethyl acetate, propyl acetate, and isopropyl acetate; Aliphatic hydrocarbons such as cyclohexane and cyclohexanone; and ketones such as methyl ethyl ketone and methyl isopropyl ketone. Among these, tetrahydrofuran which has high solubility of polycarbonate and does not contain halogen is more preferable.

In the present invention, as the poor solvent for precipitating the polycarbonate in a molten state, any solvent can be used as long as it does not dissolve the predetermined polycarbonate at all. Specifically, water, methanol, ethanol, isopropyl alcohol , N-butanol, aliphatic alcohols such as isopentyl alcohol, and aliphatic hydrocarbons such as cyclohexanone. Among these, water that is harmless to the human body and the environment is more preferable.

The production method of the present invention uses a weight-average molecular weight strongly required in special fields such as automobile engine-related parts, eyeglass lenses, and electrophotographic photoreceptor parts without using any halogen harmful to the human body and the environment. Can easily produce a high-molecular-weight polycarbonate having a molecular weight of 50,000 or more, and can obtain a carbonate resin having a higher molecular weight than the conventional one by a safe production method having excellent industrial productivity.

Next, regarding the method for producing a high molecular weight polycarbonate of the present invention, production conditions using a zinc oxide catalyst will be specifically described.
First, a diol and a carbonate diester as starting materials and a predetermined amount of a zinc oxide catalyst are charged into a reactor at room temperature. Immediately after the introduction, the inside of the reactor is sufficiently replaced with nitrogen, and then the pressure is reduced to about 10 mmHg. Then, the temperature of the reactor is raised to 160 to 220 ° C., and varies depending on the type and chemical structure of the raw material compound used. And reduce the pressure to 1 Torr or less.

Next, the temperature is raised to 220 to 260 ° C. at a rate of about 20 ° C./hour, and further to 280 to 350 ° C. at a rate of about 10 ° C./hour. The stirring torque of the reactor was monitored while maintaining this temperature and a reduced pressure of 1 Torr or less. When the torque reached a predetermined value corresponding to the weight average molecular weight of the desired high molecular weight polycarbonate, the stirring was stopped. To terminate the polymerization.
Thereafter, the reactor is left to cool to room temperature, a predetermined amount of a solvent for dissolving the produced polycarbonate is added when the temperature reaches room temperature, and the reactor is stirred again. By monitoring the stirring torque and returning to a torque corresponding to a state in which the produced polycarbonate is completely dissolved, this dissolved solution is poured into a poor solvent to precipitate out, and this is filtered to obtain a desired high molecular weight polycarbonate. Is obtained.

に お い て In the production method of the present invention, the reaction temperature is appropriately selected according to the structure of the target polycarbonate. For example, in a polycarbonate having a high glass transition temperature containing bisphenols and biphenyls as a main component, it is preferable to set a high reaction temperature in each step, and a comparative reaction containing hydrogenated bisphenols and hydrogenated biphenyls as a main component. In the case of a polycarbonate having a low glass transition temperature, the reaction temperature in each step is preferably set low. In addition, it is important to set a high reaction temperature for polycarbonate containing naphthalene diol as a main component, especially since its melt viscosity is high.

Hereinafter, the present invention will be described specifically with reference to Examples and the like, but the present invention is not limited to these Examples.

0.80 mol of 1,1-bis (4-hydroxyphenyl) cyclohexane, 0.88 mol of diphenyl carbonate and 7.1 mg of zinc oxide were charged into a 1 liter (L) polymerization apparatus. Immediately after the inside of the polymerization apparatus was sufficiently replaced with nitrogen, the pressure was reduced to about 30 mmHg. While maintaining the reduced pressure, the content temperature was heated to 180 ° C., and stirring of the content was started at 150 rpm. At this point, the top temperature of the rectification column rose to 140 ° C., and phenol distillation began. Further, the content temperature was maintained at 180 ° C., and the reaction was carried out for 1 hour. When the amount of phenol distilled out exceeded 80% of the theoretical amount, the pressure in the polymerization apparatus was gradually increased to 0.7 Torr over 1 hour. The pressure was reduced. At this point, the amount of distillate phenol was over 90% of theory. Thereafter, the temperature of the contents was increased to 260 ° C. at a rate of 20 ° C./hour, and further increased to 300 ° C. at a rate of 10 ° C./hour. The reaction was carried out for 7 hours while maintaining this temperature and a degree of vacuum of 1 Torr or less, and the polymerization was terminated when a rise in the stirring torque in the polymerization apparatus was confirmed. Further, in this state, it was left for about 14 hours.

Next, it was confirmed that the temperature of the content had dropped to room temperature, and 1.50 kg of tetrahydrofuran was charged into the polymerization apparatus. As a result, it was confirmed that the polycarbonate produced by the polymerization had begun to dissolve, and stirring was started at 30 rpm. Next, the completely dissolved solution was gradually dropped into 7.50 L of distilled water over 20 hours. The precipitate was separated by filtration and dried at 100 ° C. under a reduced pressure of 70 mmHg or more for 40 hours to obtain 231 g of polycarbonate.

The IR spectrum (measured by SYSTEM-2000 manufactured by PerkinElmer) of the obtained polycarbonate (carbonate polymer) is shown in FIG. 10, and its H ¹ -NMR (UNITY-300 / 300 MHz manufactured by Varian) is shown. ) The spectrum is shown in FIG.
In Figure 10, seen carbonyl peaks characteristic of 1773cm ^-1, The peak of the cyclohexane ring was observed 1000~1600cm ^-1. In addition, in FIG. 11, peaks indicating the presence of hydrogen directly connected to phenylene near 7 ppm, and peaks indicating the presence of hydrogen directly connected to cyclohexane near 1.5 ppm and 2.3 ppm are seen. Was 7 ppm / 2.3 ppm / 1.5 ppm = 8/4/6. From these spectrum diagrams, it was found that the desired polycarbonate was obtained.

Moreover, as a result of measuring the molecular weight using gel permission chromatography (manufactured by Tosoh Corporation, HLC8020 / solvent tetrahydrofuran / polystyrene conversion), the obtained polycarbonate was a high molecular weight polycarbonate having a weight average molecular weight of 100,000. Further, when the amount of residual zinc oxide in the obtained high molecular weight polycarbonate was measured using fluorescent X-ray, it was 24 ppm.

２３０230 g of polycarbonate was obtained in the same manner as in Example 1, except that the amount of zinc oxide was changed to 22.3 mg. When the weight average molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, it was 80,000 as a high molecular weight polycarbonate.

ポ リ カ ー ボ ネ ー ト 231 g of polycarbonate was obtained in the same manner as in Example 1, except that the amount of zinc oxide was changed to 15.2 mg. When the weight average molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, it was 150,000 high molecular weight polycarbonate.

0.80 mol of 2,2-bis (4-hydroxyphenyl) propane, 0.88 mol of diphenyl carbonate and 10.2 mg of zinc oxide were charged into a 1 L polymerization apparatus. Immediately thereafter, the inside of the polymerization apparatus was sufficiently replaced with nitrogen, and the pressure was reduced to about 30 mmHg. While maintaining the reduced pressure, the content temperature was heated to 180 ° C., and stirring of the content was started at 150 rpm. At this point, the top temperature of the rectification column rose to 140 ° C., and phenol distillation began. Further, the content was kept at 180 ° C. and reacted for 1 hour. When the amount of phenol distilled out exceeded 80% of the theoretical amount, the pressure of the polymerization apparatus was gradually reduced to 0.7 Torr over 1 hour. . The amount of phenol distilled to date has exceeded 90% of the theoretical amount.
Thereafter, the content temperature was increased to 220 ° C. at a rate of 20 ° C./hour, and further increased to 280 ° C. at a rate of 10 ° C./hour. This temperature was maintained at a degree of vacuum of 1 Torr or less, and the reaction was carried out for 10 hours. When a rise in the stirring torque in the polymerization apparatus was confirmed, the polymerization was terminated. Further, in this state, it was left for about 12 hours.

Next, after confirming that the temperature of the content had dropped to room temperature, 1.50 kg of tetrahydrofuran was charged into the polymerization apparatus. As a result, it was confirmed that the polycarbonate produced by the polymerization had begun to dissolve, and stirring was started at 30 rpm. Next, the completely dissolved solution was gradually dropped into 7.50 L of distilled water over 20 hours. The precipitate was separated by filtration and dried at 100 ° C. under a reduced pressure of 70 mmHg or more for 40 hours to obtain a polycarbonate.
When the molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, it was a high molecular weight polycarbonate having a weight average molecular weight of 120,000.

0.81 mol of (1,1'-biphenyl) -4,4'-diol, 0.88 mol of diphenyl carbonate and 8.5 mg of zinc oxide were charged into a 1 L polymerization apparatus. Immediately thereafter, the inside of the polymerization apparatus was sufficiently replaced with nitrogen, and the pressure was reduced to about 30 mmHg. While maintaining the reduced pressure, the content temperature was heated to 200 ° C., and stirring of the content was started at 150 rpm. At this point, the top temperature of the rectification column rose to 140 ° C., and phenol distillation began. Further, the content temperature was maintained at 200 ° C. and the reaction was carried out for 1 hour. When the amount of phenol distilled out exceeded 80% of the theoretical amount, the pressure of the polymerization apparatus was gradually reduced to 0.5 Torr over 1 hour. . At this point, the amount of phenol distilled was more than 90% of the theoretical amount.
Thereafter, the temperature of the contents was increased to 260 ° C. at a rate of 20 ° C./hour, and further increased to 320 ° C. at a rate of 10 ° C./hour. The reaction was carried out for 6 hours while maintaining this temperature and a degree of vacuum of 1 Torr or less, and the polymerization was terminated when a rise in the stirring torque in the polymerization apparatus was confirmed. Further, in this state, it was left for about 18 hours.

Next, after confirming that the temperature of the content had dropped to room temperature, 1.50 kg of tetrahydrofuran was charged into the polymerization apparatus. As a result, it was confirmed that the polycarbonate produced by the polymerization had begun to dissolve, and stirring was started at 30 rpm. Next, the completely dissolved solution was gradually dropped into 7.50 L of distilled water over 20 hours. The precipitate was separated by filtration and dried at 100 ° C. under a reduced pressure of 70 mmHg or more for 40 hours to obtain a polycarbonate.
When the molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, it was a high molecular weight polycarbonate having a weight average molecular weight of 150,000.

0.80 mol of 2,2-bis (4-hydroxycyclohexyl) propane, 0.88 mol of diphenyl carbonate and 10.6 mg of zinc oxide were charged into a 1 L polymerization apparatus. Immediately thereafter, the inside of the polymerization apparatus was sufficiently replaced with nitrogen, and the pressure was reduced to about 30 mmHg. While maintaining the reduced pressure, the content temperature was heated to 160 ° C., and stirring of the content was started at 150 rpm. At this point, the top temperature of the rectification column rose to 140 ° C., and phenol distillation began. Further, the temperature of the contents was maintained at 160 ° C., and the reaction was carried out for 3 hours. When the phenol distillation amount exceeded 80% of the theoretical amount, the pressure of the polymerization apparatus was gradually reduced to 0.7 Torr over 3 hours. . At this point, the amount of phenol distilled was more than 90% of the theoretical amount.
Thereafter, the content temperature was increased to 220 ° C. at a rate of 20 ° C./hour, and further increased to 280 ° C. at a rate of 10 ° C./hour. This temperature was maintained at a degree of vacuum of 1 Torr or less, and the reaction was carried out for 10 hours. When a rise in the stirring torque in the polymerization apparatus was confirmed, the polymerization was terminated. Further, in this state, it was left for about 12 hours.

Next, after confirming that the temperature of the content had dropped to room temperature, 1.50 kg of tetrahydrofuran was charged into the polymerization apparatus. As a result, it was confirmed that the polycarbonate produced by the polymerization had begun to dissolve, and stirring was started at 30 rpm. Next, the completely dissolved solution was gradually dropped into 7.50 L of distilled water over 20 hours. The precipitate was separated by filtration and dried at 80 ° C. under a reduced pressure of 70 mmHg or more for 40 hours to obtain a polycarbonate.
When the molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, it was a high molecular weight polycarbonate having a weight average molecular weight of 100,000.

0.80 mol of (1,1'-bicyclohexyl) -4,4'-diol, 0.88 mol of diphenyl carbonate and 10.6 mg of zinc oxide were charged into a 1 L polymerization apparatus. Immediately thereafter, the inside of the polymerization apparatus was sufficiently replaced with nitrogen, and the pressure was reduced to about 30 mmHg. While maintaining the reduced pressure, the content temperature was heated to 160 ° C., and stirring of the content was started at 150 rpm. At this point, the top temperature of the rectification column rose to 140 ° C., and phenol distillation began. Further, the temperature of the contents was maintained at 160 ° C., and the reaction was carried out for 3 hours. When the phenol distillation amount exceeded 80% of the theoretical amount, the pressure of the polymerization apparatus was gradually reduced to 0.7 Torr over 3 hours. . At this point, the amount of phenol distilled was more than 90% of the theoretical amount.
Thereafter, the content temperature was increased to 220 ° C. at a rate of 20 ° C./hour, and further increased to 280 ° C. at a rate of 10 ° C./hour. This temperature was maintained at a degree of vacuum of 1 Torr or less, and the reaction was carried out for 10 hours. When a rise in the stirring torque in the polymerization apparatus was confirmed, the polymerization was terminated. Further, in this state, it was left for about 12 hours.

Next, after confirming that the temperature of the content had dropped to room temperature, 1.50 kg of tetrahydrofuran was charged into the polymerization apparatus. As a result, it was confirmed that the polycarbonate produced by the polymerization had begun to dissolve, and stirring was started at 30 rpm. Next, the completely dissolved solution was gradually dropped into 7.50 L of distilled water over 20 hours. The precipitate was separated by filtration and dried at 80 ° C. under a reduced pressure of 70 mmHg or more for 40 hours to obtain a polycarbonate.
When the molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, it was a high molecular weight polycarbonate having a weight average molecular weight of 100,000.

0.80 mol of 1,4-cyclohexanediol, 0.88 mol of diphenyl carbonate and 5.68 mg of zinc oxide were charged into a 1 L polymerization apparatus. Immediately thereafter, the inside of the polymerization apparatus was sufficiently replaced with nitrogen, and the pressure was reduced to about 30 mmHg. While maintaining the reduced pressure, the content temperature was heated to 160 ° C., and stirring of the content was started at 150 rpm. At this point, the top temperature of the rectification column rose to 140 ° C., and phenol distillation began. Further, the temperature of the contents was maintained at 160 ° C., and the reaction was carried out for 3 hours. When the phenol distillation amount exceeded 80% of the theoretical amount, the pressure of the polymerization apparatus was gradually reduced to 0.7 Torr over 3 hours. . At this point, the amount of phenol distilled was more than 90% of the theoretical amount.
Thereafter, the content temperature was increased to 220 ° C. at a rate of 20 ° C./hour, and further increased to 260 ° C. at a rate of 10 ° C./hour. The reaction was carried out for 18 hours while maintaining this temperature and a degree of vacuum of 1 Torr or less, and the polymerization was terminated when a rise in the stirring torque in the polymerization apparatus was confirmed. Further, in this state, it was left for about 12 hours.

Next, after confirming that the temperature of the content had dropped to room temperature, 1.50 kg of tetrahydrofuran was charged into the polymerization apparatus. As a result, it was confirmed that the polycarbonate produced by the polymerization had begun to dissolve, and stirring was started at 30 rpm. Then, after complete dissolution, the solution was added dropwise to 7.50 L of distilled water over 20 hours. The precipitate was separated by filtration and dried at 80 ° C. under a reduced pressure of 70 mmHg or more for 40 hours to obtain a polycarbonate.
When the molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, it was a high molecular weight polycarbonate having a weight average molecular weight of 150,000.

0.80 mol of ethylene glycol, 0.88 mol of diphenyl carbonate and 3.52 mg of zinc oxide were charged into a 1 L polymerization apparatus. Immediately thereafter, the inside of the polymerization apparatus was sufficiently replaced with nitrogen, and the pressure was reduced to about 30 mmHg. While maintaining the reduced pressure, the content temperature was heated to 180 ° C., and stirring of the content was started at 150 rpm. At this point, the top temperature of the rectification column rose to 140 ° C., and phenol distillation began. Further, the temperature of the content was maintained at 180 ° C., and the reaction was carried out for 3 hours. When the phenol distillation amount exceeded 80% of the theoretical amount, the pressure of the polymerization apparatus was gradually reduced to 0.7 Torr over 3 hours. . At this point, the amount of phenol distilled was more than 90% of the theoretical amount.
Thereafter, the content temperature was increased to 240 ° C. at a rate of 20 ° C./hour, and further increased to 280 ° C. at a rate of 10 ° C./hour. The reaction was carried out for 18 hours while maintaining this temperature and a degree of vacuum of 1 Torr or less, and the polymerization was terminated when a rise in the stirring torque in the polymerization apparatus was confirmed. Further, in this state, it was left for about 12 hours.

Next, after confirming that the temperature of the content had dropped to room temperature, 1.50 kg of tetrahydrofuran was charged into the polymerization apparatus. As a result, it was confirmed that the polycarbonate produced by the polymerization had begun to dissolve, and stirring was started at 30 rpm. Then, the completely dissolved solution was dropped into 7.50 L of distilled water over 20 hours. The precipitate was separated by filtration and dried at 80 ° C. under a reduced pressure of 70 mmHg or more for 40 hours to obtain a polycarbonate.
When the molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, it was a high molecular weight polycarbonate having a weight average molecular weight of 200,000.

0.40 mol of 1,1-bis (4-hydroxyphenyl) cyclohexane, 0.40 mol of 2,6-naphthalenediol, 0.88 mol of diphenyl carbonate and 9.08 mg of zinc oxide were charged into a 1 L polymerization apparatus. Immediately after that, the inside of the polymerization apparatus was sufficiently replaced with nitrogen, and the pressure was reduced to about 30 mmHg. While maintaining the reduced pressure, the content temperature was heated to 180 ° C., and stirring of the content was started at 150 rpm. At this point, the top temperature of the rectification column rose to 140 ° C., and phenol distillation began. Further, when the content temperature was maintained at 180 ° C. and the reaction was carried out for 1 hour, the distillation of phenol was stopped, so that the content temperature was increased to 220 ° C. at a rate of 10 ° C./hour. Further, the content was kept at 180 ° C. and reacted for 1 hour. When the amount of phenol distilled out exceeded 80% of the theoretical amount, the pressure of the polymerization apparatus was gradually reduced to 0.7 Torr over 1 hour. . At this point, the amount of phenol distilled was more than 90% of the theoretical amount.
Thereafter, the content temperature was increased to 280 ° C. at a rate of 20 ° C./hour, and further increased to 320 ° C. at a rate of 10 ° C./hour. The reaction was carried out for 7 hours while maintaining this temperature and a degree of vacuum of 1 Torr or less, and the polymerization was terminated when a rise in the stirring torque in the polymerization apparatus was confirmed. Further, in this state, it was left for about 14 hours.

Next, after confirming that the temperature of the content had dropped to room temperature, 1.50 kg of tetrahydrofuran was charged into the polymerization apparatus. As a result, it was confirmed that the polycarbonate produced by the polymerization had begun to dissolve, and stirring was started at 30 rpm. Next, the completely dissolved solution was gradually dropped into 7.50 L of distilled water over 20 hours. The precipitate was separated by filtration and dried at 100 ° C. under a reduced pressure of 70 mmHg or more for 40 hours to obtain a polycarbonate.
When the molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, it was a high molecular weight polycarbonate having a weight average molecular weight of 100,000.

0.80 mol of 1,1-bis (4-hydroxyphenyl) cyclohexane, 0.88 mol of dimethyl carbonate and 9.8 mg of zinc oxide were charged into a 1 L polymerization apparatus. Immediately thereafter, the inside of the polymerization apparatus was sufficiently replaced with nitrogen, and the pressure was reduced to about 30 mmHg. While maintaining the reduced pressure, the content temperature was heated to 180 ° C., and stirring of the content was started at 150 rpm. At this point, the top temperature of the rectification column rose to 60 ° C., and methanol distillation began. Further, the temperature of the content was maintained at 180 ° C., and the reaction was carried out for 1 hour. When the amount of distilled methanol exceeded 80% of the theoretical amount, the pressure of the polymerization apparatus was gradually reduced to 0.7 Torr over 1 hour. . At this point, the amount of methanol distilled exceeded 90% of the theoretical amount.
Thereafter, the content temperature was increased to 260 ° C. at a rate of 20 ° C./hour, and further increased to 300 ° C. at a rate of 10 ° C./hour. The reaction was carried out for 7 hours while maintaining this temperature and a degree of vacuum of 1 Torr or less, and the polymerization was terminated when a rise in the stirring torque in the polymerization apparatus was confirmed. Further, in this state, it was left for about 14 hours.

Next, after confirming that the temperature of the content had dropped to room temperature, 1.50 kg of tetrahydrofuran was charged into the polymerization apparatus. As a result, it was confirmed that the polycarbonate produced by the polymerization had begun to dissolve, and stirring was started at 30 rpm. Next, the completely dissolved solution was gradually dropped into 7.50 L of distilled water over 20 hours. The precipitate was separated by filtration and dried at 100 ° C. under a reduced pressure of 70 mmHg or more for 40 hours to obtain a polycarbonate.
When the molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, it was a high molecular weight polycarbonate having a weight average molecular weight of 90,000.

0.80 mol of 1,1-bis (4-hydroxyphenyl) cyclohexane, 0.44 mol of diphenyl carbonate, 0.44 mol of dimethyl carbonate and 8.5 mg of zinc oxide were charged into a 1 L polymerization apparatus. Immediately thereafter, the inside of the polymerization apparatus was sufficiently replaced with nitrogen, and the pressure was reduced to about 30 mmHg. While maintaining the reduced pressure, the content temperature was heated to 180 ° C., and stirring of the content was started at 150 rpm. At this point, the top temperature of the rectification column rose to 60 ° C., and methanol distillation began. Thereafter, about 10 minutes later, the top temperature of the rectification column rose to 100 ° C., and distillation of the azeotrope of methanol and phenol started. Further, the content temperature was maintained at 180 ° C. and the reaction was carried out for 1 hour. When the amount of methanol and phenol distilled out exceeded 80% of the theoretical amount, the polymerization apparatus was gradually raised to 0.7 Torr over 1 hour. The pressure was reduced. At this point, the amount of methanol and phenol distilled off exceeded 90% of the theoretical amount. Thereafter, the temperature of the contents was increased to 260 ° C. at a rate of 20 ° C./hour, and further increased to 300 ° C. at a rate of 10 ° C./hour. The reaction was carried out for 7 hours while maintaining this temperature and a degree of vacuum of 1 Torr or less, and the polymerization was terminated when a rise in the stirring torque in the polymerization apparatus was confirmed. Further, in this state, it was left for about 14 hours.

Next, after confirming that the temperature of the content had dropped to room temperature, 1.50 kg of tetrahydrofuran was charged into the polymerization apparatus. As a result, it was confirmed that the polycarbonate produced by the polymerization had begun to dissolve, and stirring was started at 30 rpm. Next, the completely dissolved solution was gradually dropped into 7.50 L of distilled water over 20 hours. The precipitate was separated by filtration and dried at 100 ° C. under a reduced pressure of 70 mmHg or more for 40 hours to obtain a polycarbonate.
When the molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, it was a high molecular weight polycarbonate having a weight average molecular weight of 100,000.

A polycarbonate was obtained in the same manner as in Example 1, except that 7.1 mg of zinc oxide used as a catalyst in Example 1 was replaced with 7.1 mg of antimony trioxide.
When the molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, it was a high molecular weight polycarbonate having a weight average molecular weight of 70,000.

A polycarbonate was obtained in the same manner as in Example 1, except that 7.1 mg of zinc oxide used as a catalyst in Example 1 was replaced with 7.1 mg of lead oxide.
When the molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, it was a high molecular weight polycarbonate having a weight average molecular weight of 70,000.

Comparative Example 1
A polycarbonate was obtained in the same manner as in Example 1, except that 7.1 mg of zinc oxide used as a catalyst in Example 1 was replaced with 7.1 mg of tetrabutoxytitanium. When the molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, the weight average molecular weight was 20,000.

Comparative Example 2
A polycarbonate was obtained in the same manner as in Example 1, except that 7.1 mg of zinc oxide used as a catalyst in Example 1 was replaced with 7.1 mg of calcium acetate.
When the molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, the weight average molecular weight was 20,000.

Comparative Example 3
A polycarbonate was obtained in the same manner as in Example 1, except that 7.1 mg of zinc oxide used as a catalyst in Example 1 was replaced with 7.1 mg of metallic sodium.
When the molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, the weight average molecular weight was 15,000.

Comparative Example 4
0.5 mol of 1,1-bis (hydroxyphenyl) cyclohexane, 1.5 mol of sodium hydroxide and 0.005 mol of benzyltriethylammonium chloride are charged into a 5 L flask, which is dissolved in 2 L of deionized water and stirred. Then, 2 L of methylene chloride was added thereto. Then, while maintaining the inside of the flask at 10 ° C., 0.55 mol of phosgene was gradually added to the methylene chloride layer over 1 hour with stirring, and after all the phosgene was added dropwise, stirring was continued for 1 hour. 2.5 ml of butylamine was added and stirring was continued vigorously for another 20 hours. The generated methylene chloride layer was washed with 2 L of distilled water, an acid and an alkali in this order, and precipitated in 7 L of methanol. The obtained polycarbonate was separated by filtration and dried under vacuum at 80 ° C. for 8 hours to obtain 110 g of polycarbonate.
When the molecular weight of the obtained polycarbonate was measured in the same manner as in Example 1, it was a high molecular weight polycarbonate having a weight average molecular weight of 70,000.

Table 1 shows the results obtained in Examples 1 to 14 and Comparative Examples 1 to 4.

As can be seen from the above results, the present invention provides a high-molecular weight polycarbonate polymer having a weight-average molecular weight of 50,000 or more, particularly when polymerized using a basic oxide catalyst in the transesterification reaction, As shown in the comparative examples, the polymerization reaction by the transesterification does not proceed sufficiently with other catalysts, so that a high molecular weight polycarbonate polymer cannot be obtained. In addition, in the present invention, when the amount of the basic oxide catalyst used is in the range of 20 to 100 ppm, a polycarbonate having a higher molecular weight can be obtained.

Usage example 1
Using the polycarbonate obtained in Example 1 as a binder resin, an electrophotographic photosensitive member was produced by the following method.
First, a mixture of 30 parts by weight of an organic zirconium compound (acetylacetone zirconium butyrate) and 170 parts by weight of n-butyl alcohol in which 4 parts by weight of a polyvinyl butyral resin (Eslec BM-S, manufactured by Sekisui Chemical Co., Ltd.) is dissolved is used. 3 parts by weight of (γ-aminopropyltrimethoxysilane) were mixed and stirred to obtain an undercoat layer coating solution. Next, the above-mentioned undercoat layer was coated on a 30 mmφ ED tube aluminum substrate roughened to a center line average roughness Ra = 0.18 μm by a liquid honing treatment using alumina spherical fine powder (D50 = 30 μm). The solution was applied by dip coating and cured at 150 ° C. for 1 hour to form a 1.2 μm-thick undercoat layer.

Next, 3 parts by weight of chlorogallium phthalocyanine having clear X-ray diffraction peaks at 7.4 °, 16.6 °, 25.5 ° and 28.3 ° as a charge generating material, and vinyl chloride-vinyl acetate were used. A mixture consisting of 2 parts by weight of a polymer (VMCH, manufactured by Nippon Unicar Co., Ltd.) and 180 parts by weight of butyl acetate was subjected to dispersion treatment in a sand mill for 4 hours and dip-coated on the undercoat layer using a coating solution obtained. After drying, a charge generation layer having a thickness of 0.2 μm was formed.
Next, 6 parts by weight of the polycarbonate obtained in Example 1, N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine 4 parts by weight and 0.2 parts by weight of 2,6-di-t-butyl-4-methylphenol were added to 80 parts by weight of tetrahydrofuran and dissolved and applied by dip coating on the charge generation layer. This was dried at 120 ° C. for 40 minutes to form a charge transport layer having a thickness of 25 μm, thereby producing an electrophotographic photosensitive member having three layers.

The obtained electrophotographic photosensitive member was mounted on a printer having a contact charging system (PC-PR1000 / 4R, manufactured by NEC Corporation), and a print test of 50,000 sheets was performed to measure and evaluate electrophotographic characteristics. went. At that time, the charged potential of the photoreceptor, the residual potential, the image quality of the printed image formed, and the abrasion amount of the photosensitive layer after the 50,000 sheet test were examined. Table 2 shows the obtained results.

Usage examples 2 to 14
In Use Example 1, all of Use Example 1 was repeated except that the polycarbonates obtained in Examples 2 to 14 were used in place of the polycarbonate obtained in Example 1 used as a binder resin of the charge transport layer. An electrophotographic photoreceptor was prepared in the same manner as described above. Using the obtained electrophotographic photosensitive member, measurement and evaluation of electrophotographic characteristics were performed in the same manner as in Use Example 1. Table 2 shows the obtained results.

Reference Comparative Examples 1-4
In Use Example 1, except that the polycarbonates obtained in Comparative Examples 1 to 4 were used in place of the polycarbonate obtained in Example 1 used as the binder resin of the charge transport layer, respectively, An electrophotographic photoreceptor was prepared in the same manner as described above. Using the obtained electrophotographic photosensitive member, measurement and evaluation of electrophotographic characteristics were performed in the same manner as in Use Example 1. Table 2 shows the obtained results.

The photoconductors of Use Examples 1 to 14 using the polycarbonate obtained in Examples 1 to 14 as a binder resin for the surface layer, when a print test was performed using a printer having a contact charging device, the Stable electrical characteristics were obtained with little abrasion and no reduction in chargeability of the photoreceptor or increase in residual potential. Further, no image quality abnormality caused by leak discharge of the photoconductor was observed.
On the other hand, the photoreceptors of Reference Comparative Examples 1 to 3 using the polycarbonates obtained in Comparative Examples 1 to 3 suffered large abrasion due to the low molecular weight of the polycarbonate, increased the dark decay, and increased the chargeability. , And fog was observed in the image in the low density portion. In addition, there was a current leak from the contact charging device in a portion where the film thickness was reduced due to abrasion, and the leaked portion had to be repaired with an insulating substance and run. This part became an image quality defect. In the photoconductor of Reference Comparative Example 4, although the photoconductor was hardly worn, there was a current leak from the contact charging device due to the corrosion of the photoconductor by chlorine remaining in the polycarbonate. It had to be repaired with toxic substances and run. This part became an image quality defect.

Usage examples 15 to 28
16 parts by weight of a polyvinyl butyral resin (Eslec BM-S, manufactured by Sekisui Chemical Co., Ltd.) is stirred and mixed with 550 parts by weight of cyclohexanone, and then 8 parts by weight of a resole type phenol resin (Phenolite J-325, manufactured by Dainippon Ink and Chemicals, Inc.) Was added and stirred. Further, 60 parts by weight of a titanium oxide pigment was added to this liquid, and the mixture was subjected to a dispersion treatment with a sand grind mill for 5 hours to obtain an undercoat layer coating liquid. Using this coating solution, a ring honing device was used to apply a coating on a 84 mmφ aluminum substrate roughened to a center line average roughness Ra = 0.18 μm by liquid honing, and this was applied at 170 ° C. for 1 hour. By curing treatment, an undercoat layer having a thickness of 4 μm was formed.

Next, as a charge generation material, 15 parts by weight of titanyl phthalocyanine having clear X-ray diffraction peaks at 9.5 °, 11.7 °, 15.0 °, 24.1 ° and 27.3 °, polyvinyl butyral A coating solution obtained by dispersing a mixture of 10 parts by weight of a resin (S-LEC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 300 parts by weight of n-butyl alcohol in a sand grind mill for 4 hours is coated on the undercoat layer. And dried to form a charge generation layer having a thickness of 0.2 μm.
Next, 4 parts by weight of a charge transporting material: N, N-bis (3,4-dimethylphenyl) biphenyl-4-amine and 6 parts by weight of the polycarbonate obtained in each of Examples 1 to 14 were mixed with chlorobenzene 80 A charge transporting layer having a thickness of 27 μm was formed by applying a coating solution which was dissolved in addition to parts by weight and dried to prepare an electrophotographic photosensitive member having three layers. The obtained electrophotographic photosensitive member was mounted on a color copying machine (Acolor-635, manufactured by Fuji Xerox Co., Ltd.) having an intermediate transfer drum system, and a light amount was adjusted to perform a printing operation. Table 3 shows the results obtained with respect to the image quality of the photoconductor at that time.

Reference Comparative Examples 5 to 8
In Use Example 15 except that the polycarbonates obtained in Comparative Examples 1 to 4 were used in place of the polycarbonate obtained in Example 1 used as the binder resin of the charge transport layer, respectively, An electrophotographic photoreceptor was prepared in the same manner as described above. Using the obtained electrophotographic photosensitive member, evaluation was performed using a color copying machine having an intermediate transfer drum system in the same manner as in Use Example 15. Table 3 shows the obtained results.

Table 3 shows the results obtained in Use Examples 15 to 28 and Reference Comparative Examples 5 to 8.

The photoreceptors of Use Examples 15 to 28 using the polycarbonate obtained in Examples 1 to 14 as a binder resin for the surface layer did not cause image fogging and had little black spots, and had good image quality. was gotten.
On the other hand, in the photoconductors of Reference Comparative Examples 5 to 7 using the polycarbonates obtained in Comparative Examples 1 to 3, image fogging occurs due to abrasion of the surface layer due to the low molecular weight of the polycarbonate, and further, black spots There were many occurrences, and abnormal image quality was observed. Further, in the photoreceptor of Reference Comparative Example 8, image fogging was caused due to corrosion of the photoreceptor due to residual chlorine in the binder resin.

Usage examples 29 to 42
A coating solution composed of 10 parts by weight of a polyamide resin, 150 parts by weight of methyl alcohol, and 40 parts by weight of water is applied onto a conductive support (Metal Me, manufactured by Toray Industries, Ltd.) having a vapor-deposited aluminum film provided on the surface of a polyethylene terephthalate film. This was dried to form an undercoat layer having a thickness of 1 μm. Next, 9 parts by weight of hydroxygallium phthalocyanine having diffraction peaks at 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.1 °. , A mixture of 2 parts by weight of polyvinyl butyral resin (Eslec BM-1, manufactured by Sekisui Chemical Co., Ltd.) and 30 parts by weight of n-butyl alcohol was placed in a ball mill pot, and a SUS stainless steel ball (1/8 inch Φ) was used as a mill member. After use and milling for 60 hours, a solution obtained by adding and diluting 30 parts by weight of n-butyl alcohol and diluting and stirring was applied on the undercoat layer, and dried to obtain a charge having a thickness of 0.3 μm. A generating layer was formed.

Next, 4 parts by weight of N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine and Examples 1 to 14, respectively. 6 parts by weight of the obtained polycarbonate was added to and dissolved in 55 parts by weight of methylene chloride, and this was applied and dried to form a charge transport layer having a thickness of 25 μm, thereby producing an electrophotographic photoreceptor having three layers. .
About the obtained electrophotographic photoreceptor, the coating film of the photosensitive layer was peeled off from the conductive substrate, and a bending repetition test was performed up to 5000 times using a bending strength tester. Further, the electrophotographic photosensitive member was processed into a belt shape, and mounted on a copying machine (Vision 800, manufactured by Fuji Xerox Co., Ltd.) having a belt rotation driving device, and a copy running test was performed up to 100,000 cycles. Table 4 shows the obtained results.

Reference Comparative Examples 9 to 12
An electrophotographic photosensitive member was produced in the same manner as in Use Example 29 except that the polycarbonates obtained in Comparative Examples 1 to 4 were used as the binder resin of the charge transport layer, and the same evaluation was performed. Table 4 shows the obtained results.

Since the photoreceptors of Use Examples 29 to 42 use the high molecular weight polycarbonate obtained in Examples 1 to 14 for the surface layer, they do not break even after the bending test, and also have good after copying test. Image quality was obtained. On the other hand, the photoreceptors of Reference Comparative Examples 9 to 11 were all low in molecular weight of the polycarbonate used for the surface layer, and the photoreceptor of Reference Comparative Example 12 was corroded by the residual chlorine. It broke during the bending test, and many white spot failures caused by cracks occurred after the copy running test.

FIG. 3 is an IR spectrum of the high molecular weight polycarbonate obtained in Example 1. FIG. 2 is an NMR spectrum of the high molecular weight polycarbonate obtained in Example 1.

Claims (8)

The diol and the carbonate diester are polymerized by a transesterification reaction heated in the presence of a basic oxide catalyst, and the polycarbonate produced by the transesterification reaction is cooled and then obtained from a solution dissolved in a solvent. A method for producing a molecular weight polycarbonate. The method for producing a high molecular weight polycarbonate according to claim 1, wherein the amount of the basic oxide catalyst used is in the range of 20 to 100 ppm based on the theoretical yield of the high molecular weight polycarbonate to be produced. 3. The method according to claim 1, wherein the high molecular weight polycarbonate has a weight average molecular weight of 50,000 or more. The method for producing a high molecular weight polycarbonate according to any one of claims 1 to 3, wherein the basic oxide catalyst is zinc oxide. The diol is one selected from the group consisting of bisphenols, hydrogenated bisphenols, biphenols, hydrogenated biphenols, aryl diols, cycloalkane diols and aliphatic diols, or a mixture of two or more thereof. The method for producing a high-molecular-weight polycarbonate according to any one of claims 1 to 4, characterized in that: The high molecular weight polycarbonate according to any one of claims 1 to 5, wherein the carbonate diester is one selected from the group consisting of diaryl carbonates and dialkyl carbonates, or a mixture of two or more thereof. Manufacturing method. A high-molecular-weight polycarbonate obtained by the method according to claim 1. A high molecular weight polycarbonate obtained by the method according to claim 7, wherein a residual amount of the catalyst is 10 to 100 ppm.

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