Polycarbonate resin, method for producing the same, and optical lens

Abstract

To provide a polycarbonate resin having a high refractive index, a low Abbe number, and high moist heat resistance.SOLUTION: The polycarbonate resin includes structural units represented by the general formula (1) in the figure. (In the general formula (1), X represents a C1-4 alkylene group, and a and b each independently represent an integer from 1 to 10.)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polycarbonate resin and a method for producing the same. The present invention also relates to an optical lens containing a polycarbonate resin.

Background Art

[0002] As a material for optical lenses used in the optical systems of various cameras such as cameras, film-integrated cameras, and video cameras, optical glass or optical resin is used. Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., but has problems such as high material cost, poor moldability, and low productivity. On the other hand, an optical lens made of an optical resin has the advantage that it can be mass-produced by injection molding. For example, in a camera lens, a polycarbonate resin or the like is used. However, in recent years, due to the trend of products becoming thinner, lighter, shorter, and smaller, the development of resins with a high refractive index has been demanded. Generally, when the refractive index of an optical material is high, a lens element having the same refractive index can be realized with a surface having a smaller curvature, so that the amount of aberration generated on this surface can be reduced.

[0003] As a result, it becomes possible to reduce the number of lenses, reduce the eccentricity sensitivity of the lenses, and reduce the lens thickness to make the lens lighter.

[0004] Also, generally in the optical system of a camera, aberration correction is performed by combining a plurality of concave lenses and convex lenses. That is, for the chromatic aberration generated by a convex lens, a concave lens having chromatic aberration of the opposite sign to that of the convex lens is combined to synthetically cancel out the chromatic aberration. At this time, the concave lens is required to have high dispersion (that is, a low Abbe number).

[0005] Therefore, the development of resins for optical lenses with a high refractive index and a low Abbe number has been carried out. For example, a copolymer of a bisphenol A type polycarbonate structural unit and a structural unit represented by the following formula (E) has been disclosed in Patent Document 1 to have an improved refractive index. Patent Document 1 The examples of Patent Document 1 describe that a refractive index of 1.62 to 1.64 and an Abbe number of 23 to 26 were achieved. It is considered that the improvement of the refractive index is due to the structural unit represented by the formula (E).

Chemical formula

[0006] In addition, a copolymer of a polycarbonate resin containing a structural unit having a fluorene structure and bisphenol A has been disclosed in Patent Document 2. The examples of this document describe that a refractive index of 1.616 to 1.636 was achieved. Note that the structural unit disclosed in this document is different from the formula (E).

[0007] As described above, polycarbonate resins and optical lenses having a high refractive index and a low Abbe number have not yet been provided.

[0008] Furthermore, in recent years, water resistance and heat resistance have been required for various electronic devices. As an environmental test for evaluating the water resistance and heat resistance of such electronic devices, the "PCT test" (Pressure Cooker Test) is carried out. This test is a damp heat resistance test, and the ingress of moisture into the sample is accelerated in terms of time for evaluation. Therefore, optical lenses made of optical resins used in electronic devices not only have a high refractive index and a low Abbe number, but also maintain their optical physical properties after the PCT test. ​​​​​​​​​​​It is required to be maintained. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Publication No. 2007 / 142149 [Patent Document 2] Japanese Patent Application Publication No. 6-25398 Summary of the Invention [Problem to be solved by the invention]

[0010] The problem to be solved by the present invention is to provide a polymer having a high refractive index, a low Abbe number, and high resistance to moisture and heat. The present invention provides a carbonate resin. It is also an object of the present invention to provide an optical lens. [Means for solving the problem]

[0011] As a result of intensive research conducted by the present inventors to solve the above problems, the following polycarbonate resin It was found that the above problems could be solved by using a resin and an optical lens, and the present invention was arrived at. Reached. The present invention is, for example, as follows. [1] A polycarbonate resin comprising a structural unit represented by the following general formula (1): [ka] In the general formula (1), X represents an alkylene group having 1 to 4 carbon atoms, and a and b each independently represent Represents an integer between 1 and 10.) [2] Further comprising a constitutional unit represented by the following general formula (2) and / or the following general formula (3): [1] The polycarbonate resin according to the present invention. [ka] (In General Formula (2), Y represents an alkylene group having 1 to 4 carbon atoms, and c and d each independently represent an integer from 1 to 10.) [Chemical Formula] (In General Formula (3), Z represents an alkylene group having 1 to 4 carbon atoms, R 1 ~R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, and e and f each independently represent an integer from 0 to 5.) [3] A polycarbonate resin containing structural units represented by General Formulas (1) to (3), wherein the proportion of the structural unit represented by General Formula (1) is 10 to 80 mol%, the proportion of the structural unit represented by General Formula (2) is 10 to 60 mol%, and the proportion of the structural unit represented by General Formula (3) is 5 to 80 mol%, the poly carbonate resin according to [2]. [4] A polycarbonate resin containing structural units represented by General Formulas (1) to (3), wherein the proportion of the structural unit represented by General Formula (1) is 20 to 80 mol%, the proportion of the structural unit represented by General Formula (2) is 10 to 60 mol%, and the proportion of the structural unit represented by General Formula (3) is 5 to 70 mol%, the poly carbonate resin according to [2]. [5] A polycarbonate resin containing structural units represented by General Formulas (1) and (2), wherein the proportion of the structural unit represented by General Formula (1) is 10 to 80 mol%, The polycarbonate resin according to [2], wherein the proportion of the structural unit represented by the general formula (2) is 20 to 90 mol%. Polycarbonate resin. [6] A polycarbonate resin containing structural units represented by general formulas (1) and (2), , wherein the proportion of the structural unit represented by the general formula (1) is 30 to 60 mol%, and the proportion of the structural unit represented by the general formula (2) is 40 to 70 mol%, the polycarbonate resin according to [2]. Polycarbonate resin. [7] An optical lens containing the polycarbonate resin according to any one of [1] to [6]. [8] A method for producing the polycarbonate resin according to any one of [1] to [6], comprising a step of melt polycondensing a dihydroxy compound containing a dihydroxy compound represented by the following general formula (4) and a carbonic acid diester. Method. [Chemical formula] (In the general formula (4), X represents an alkylene group having 1 to 4 carbon atoms, and a and b each independently represent an integer of 1 to 10.) [Advantages of the Invention]

[0012] The polycarbonate resin of the present invention exhibits a high refractive index, a low Abbe number, and high heat and humidity resistance. Further, by using the resin, an excellent optical lens can be obtained. [Brief Description of the Drawings]

[0013]

Figure 1

Figure 2

Figure 3

[0014] Hereinafter, the present invention will be described in detail. (1) Polycarbonate resin The polycarbonate resin of the present invention is a polycarbonate resin having a structural unit represented by the general formula (1) (hereinafter, also referred to as "structural unit (1)").

Chemical formula

[0015] In addition to the structural unit (1), the polycarbonate resin of the present invention may contain one or more other structural units. As the other structural units, a fluorene derivative unit, a binaphthol derivative unit, etc. are preferable.

[0016] Specifically, the polycarbonate resin of the present invention preferably further contains a binaphthol derivative unit represented by the following general formula (2) and / or a fluorene derivative unit represented by the following general formula (3).

Chemical formula

Chemical formula

[0017] The polycarbonate resin of the present invention preferably contains structural units represented by general formulas (1) to (3), and more preferably consists essentially of structural units represented by general formulas (1) to (3). As used herein, "consisting essentially of" means that the polycarbonate resin of the present invention may contain other structural units as long as the effects of the invention are not impaired. For example, among the structural units of the polycarbonate resin of the present invention, preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more are composed of structural units represented by general formulas (1) to (3). When the polycarbonate resin of the present invention contains structural units represented by general formulas (1) to (3), the proportion of the structural unit represented by general formula (1) is 10 to 80 mol%, the proportion of the structural unit represented by general formula (2) is 10 to 60 mol%, and the proportion of the structural unit represented by general formula (3) is preferably 5 to 80 mol%. Also, since a higher refractive index can be obtained, the proportion of the structural unit represented by general formula (1) is 20 to 80 mol%, the proportion of the structural unit represented by general formula (2) is 10 to 60 mol%, and the proportion of the structural unit represented by general formula (3) is more preferably 5 to 70 mol%. The polycarbonate resin of the present invention having a more preferable composition ratio has a very high refractive index of 1.670 or more, which has not been achieved so far.

[0018] The polycarbonate resin of the present invention preferably contains structural units represented by general formulas (1) and (2).​​​​​​​​​​​ It contains units, and more preferably consists essentially of the structural units represented by general formulas (1) and (2). For example, among the structural units of the polycarbonate resin of the present invention, preferably 90% or more, more preferably 95% or more, still more preferably 98% or more, are composed of the structural units represented by general formulas (1) and (2). When the polycarbonate resin of the present invention contains the structural units represented by general formulas (1) and (2), the proportion of the structural unit represented by general formula (1) is 10 to 80 mol%, and the proportion of the structural unit represented by general formula (2) is preferably 20 to 90 mol%. By setting such proportions, a polycarbonate resin having a very high refractive index of 1.670 or more, which has not been achieved heretofore, can be obtained. Further, since better moldability can be obtained, the proportion of the structural unit represented by general formula (1) is 30 to 60 mol%, and the proportion of the structural unit represented by general formula (2) is more preferably 40 to 70 mol%. When the polycarbonate resin of the present invention contains the structural units represented by general formulas (1) to (3), or when it contains the structural units represented by general formulas (1) and (2), how these structural units are contained in the resin is not particularly limited. In one aspect of the present invention, the polycarbonate resin may contain a copolymer containing the structural units represented by general formulas (1) to (3) or the structural units represented by general formulas (1) and (2), and may be a ternary resin or a binary resin containing homopolymers composed of the respective structural units. Alternatively, it may be a blend of a copolymer containing the structural units represented by general formulas (1) and (2) and a homopolymer containing the structural units represented by general formula (3), or a copolymer containing the structural units represented by general formulas (1) and (2).

[0019] When the polycarbonate resin of the present invention contains the structural units represented by general formulas (1) to (3), or when it contains the structural units represented by general formulas (1) and (2), or when it contains the structural units represented by general formulas (1) and (2), how these structural units are contained in the resin is not particularly limited. In one aspect of the present invention, the polycarbonate resin may contain a copolymer containing the structural units represented by general formulas (1) to (3) or the structural units represented by general formulas (1) and (2), and may be a ternary resin or a binary resin containing homopolymers composed of the respective structural units. Alternatively, it may be a blend of a copolymer containing the structural units represented by general formulas (1) and (2) and a homopolymer containing the structural units represented by general formula (3), or a copolymer containing the structural units represented by general formulas (1) and (2). In one aspect of the present invention, the polycarbonate resin may contain a copolymer containing the structural units represented by general formulas (1) to (3) or the structural units represented by general formulas (1) and (2), and may be a ternary resin or a binary resin containing homopolymers composed of the respective structural units. Alternatively, it may be a blend of a copolymer containing the structural units represented by general formulas (1) and (2) and a homopolymer containing the structural units represented by general formula (3), or a copolymer containing the structural units represented by general formulas (1) and (2). In one aspect of the present invention, the polycarbonate resin may contain a copolymer containing the structural units represented by general formulas (1) to (3) or the structural units represented by general formulas (1) and (2), and may be a ternary resin or a binary resin containing homopolymers composed of the respective structural units. Alternatively, it may be a blend of a copolymer containing the structural units represented by general formulas (1) and (2) and a homopolymer containing the structural units represented by general formula (3), or a copolymer containing the structural units represented by general formulas (1) and (2). In one aspect of the present invention, the polycarbonate resin may contain a copolymer containing the structural units represented by general formulas (1) to (3) or the structural units represented by general formulas (1) and (2), and may be a ternary resin or a binary resin containing homopolymers composed of the respective structural units. Alternatively, it may be a blend of a copolymer containing the structural units represented by general formulas (1) and (2) and a homopolymer containing the structural units represented by general formula (3), or a copolymer containing the structural units represented by general formulas (1) and (2). In one aspect of the present invention, the polycarbonate resin may contain a copolymer containing the structural units represented by general formulas (1) to (3) or the structural units represented by general formulas (1) and (2), and may be a ternary resin or a binary resin containing homopolymers composed of the respective structural units. Alternatively, it may be a blend of a copolymer containing the structural units represented by general formulas (1) and (2) and a homopolymer containing the structural units represented by general formula (3), or a copolymer containing the structural units represented by general formulas (1) and (2). In one aspect of the present invention, the polycarbonate resin may contain a copolymer containing the structural units represented by general formulas (1) to (3) or the structural units represented by general formulas (1) and (2), and may be a ternary resin or a binary resin containing homopolymers composed of the respective structural units. Alternatively, it may be a blend of a copolymer containing the structural units represented by general formulas (1) and (2) and a homopolymer containing the structural units represented by general formula (3), or a copolymer containing the structural units represented by general formulas (1) and (2). In one aspect of the present invention, the polycarbonate resin may contain a copolymer containing the structural units represented by general formulas (1) to (3) or the structural units represented by general formulas (1) and (2), and may be a ternary resin or a binary resin containing homopolymers composed of the respective structural units. Alternatively, it may be a blend of a copolymer containing the structural units represented by general formulas (1) and (2) and a homopolymer containing the structural units represented by general formula (3), or a copolymer containing the structural units represented by general formulas (1) and (2).​​​​​ It may be a blend of a copolymer containing a unit and a copolymer containing structural units represented by general formulas (1) and (3). It may be a blend of a copolymer containing a unit and a copolymer containing structural units represented by general formulas (1) and (3).

[0020] The polycarbonate resin of the present invention may contain any of random, block, and alternating copolymer structures. It may contain any of random, block, and alternating copolymer structures.

[0021] The preferred polystyrene-reduced weight average molecular weight (Mw) of the polycarbonate resin of the present invention is 20,000 to 200,000.

[0022] More preferably, the polystyrene-reduced weight average molecular weight (Mw) is 25,000 to 120 ,000, still more preferably 28,000 to 55,000, and particularly preferably 30,000 to 45,000.

[0023] If Mw is less than 20,000, the molded article becomes brittle, which is not preferable. If Mw is greater than 200 ,000, the melt viscosity increases, making it difficult to take out the resin after production, Furthermore, the fluidity deteriorates, making it difficult to perform injection molding in the molten state, which is not preferable.

[0024] The refractive index (nD) of the polycarbonate resin of the present invention at 23°C and a wavelength of 589 nm is preferably 1.635 to 1.695, more preferably 1.640 to 1.690, still more preferably 1.645 to 1.685, and particularly preferably 1.670 to 1.685. The polycarbonate resin of the present invention has a high refractive index (nD) and is suitable as an optical lens material. The refractive index can be measured for a 0.1 mm thick film using an Abbe refractometer according to the method of JIS-K- 7142.

[0025] The Abbe number (ν) of the polycarbonate resin of the present invention is preferably 24 or less, more preferably 22 or less, still more preferably 20 or less. The Abbe number can be calculated using the following formula from the refractive indices at wavelengths of 486 nm, 589 nm, and 656 nm at 23°C. ν=(nD-1) / (nF-nC) nD: Refractive index at a wavelength of 589 nm nC: Refractive index at a wavelength of 656 nm nF: Refractive index at a wavelength of 486 nm

[0026] Other resins can be blended with the polycarbonate resin of the present invention for use in the production of molded articles. Examples of other resins include polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, etc.

[0027] Furthermore, antioxidants, release agents, ultraviolet absorbers, flowability modifiers, crystal nucleating agents, reinforcing agents, dyes, antistatic agents, antibacterial agents, etc. can be added to the polycarbonate resin of the present invention.

[0028] Examples of molding methods include, but are not limited to, injection molding, compression molding, casting, roll processing, extrusion molding, stretching, etc.

[0029] When the polycarbonate resin of the present invention is used in injection molding, the preferred glass transition temperature ( Tg) is 90 to 180°C, more preferably 95 to 175°C, still more preferably 100 to 170°C, even more preferably 130 to 170°C, and particularly preferably 135 to 150°C. If Tg is lower than 90°C, the usable temperature range becomes narrow, which is not preferable. ​​​​Also, when the temperature exceeds 180°C, the melting temperature of the resin becomes high, and resin decomposition and coloring are likely to occur, which is not preferable. If the glass transition temperature of the resin is too high, the difference between the mold temperature and the resin glass transition temperature will become large with a general-purpose mold temperature control machine. Therefore, in applications where strict surface accuracy is required for the product, it is difficult to use a resin with too high a glass transition temperature, which is not preferable. Also, from the viewpoints of molding fluidity and molding heat resistance, the lower limit value of Tg is preferably 130°C, more preferably 135°C, the upper limit value of Tg is preferably 160°C, and more preferably 150°C. The optical molded article obtained by using the polycarbonate resin of the present invention preferably has a total light transmittance of 85% or more, and more preferably 88% or more. If the total light transmittance is 85% or more, it is comparable to bisphenol A type polycarbonate resin and the like. The polycarbonate resin of the present invention has high heat and humidity resistance. The heat and humidity resistance can be evaluated by performing a "PCT test" (pressure cooker test) on an optical molded article obtained by using the polycarbonate resin and measuring the total light transmittance of the optical molded article after the test. The PCT test can be performed by holding an injection molded article with a diameter of 50 mm and a thickness of 3 mm under the conditions of 120°C, 0.2 Mpa, 100% RH, and 20 hours. The polycarbonate resin of the present invention preferably has a total light transmittance of 60% or more, more preferably 70% or more, even more preferably 75% or more, further more preferably 80% or more, and particularly preferably 85% or more after the PCT test. If the total light transmittance is 60% or more, it can be said that it has high heat and humidity resistance compared to conventional polycarbonate resins. Also, when the temperature exceeds 180°C, the melting temperature of the resin becomes high, and resin decomposition and coloring are likely to occur, which is not preferable. If the glass transition temperature of the resin is too high, the difference between the mold temperature and the resin glass transition temperature will become large with a general-purpose mold temperature control machine. Therefore, in applications where strict surface accuracy is required for the product, it is difficult to use a resin with too high a glass transition temperature, which is not preferable. Also, from the viewpoints of molding fluidity and molding heat resistance, the lower limit value of Tg is preferably 130°C, more preferably 135°C, the upper limit value of Tg is preferably 160°C, and more preferably 150°C. Also, when the temperature exceeds 180°C, the melting temperature of the resin becomes high, and resin decomposition and coloring are likely to occur, which is not preferable. If the glass transition temperature of the resin is too high, the difference between the mold temperature and the resin glass transition temperature will become large with a general-purpose mold temperature control machine. Therefore, in applications where strict surface accuracy is required for the product, it is difficult to use a resin with too high a glass transition temperature, which is not preferable. Also, from the viewpoints of molding fluidity and molding heat resistance, the lower limit value of Tg is preferably 130°C, more preferably 135°C, the upper limit value of Tg is preferably 160°C, and more preferably 150°C. Also, when the temperature exceeds 180°C, the melting temperature of the resin becomes high, and resin decomposition and coloring are likely to occur, which is not preferable. If the glass transition temperature of the resin is too high, the difference between the mold temperature and the resin glass transition temperature will become large with a general-purpose mold temperature control machine. Therefore, in applications where strict surface accuracy is required for the product, it is difficult to use a resin with too high a glass transition temperature, which is not preferable. Also, from the viewpoints of molding fluidity and molding heat resistance, the lower limit value of Tg is preferably 130°C, more preferably 135°C, the upper limit value of Tg is preferably 160°C, and more preferably 150°C. Also, when the temperature exceeds 180°C, the melting temperature of the resin becomes high, and resin decomposition and coloring are likely to occur, which is not preferable. If the glass transition temperature of the resin is too high, the difference between the mold temperature and the resin glass transition temperature will become large with a general-purpose mold temperature control machine. Therefore, in applications where strict surface accuracy is required for the product, it is difficult to use a resin with too high a glass transition temperature, which is not preferable. Also, from the viewpoints of molding fluidity and molding heat resistance, the lower limit value of Tg is preferably 130°C, more preferably 135°C, the upper limit value of Tg is preferably 160°C, and more preferably 150°C.

[0030] The optical molded article obtained by using the polycarbonate resin of the present invention preferably has a total light transmittance of 85% or more, and more preferably 88% or more. If the total light transmittance is 85% or more, it is comparable to bisphenol A type polycarbonate resin and the like. The optical molded article obtained by using the polycarbonate resin of the present invention preferably has a total light transmittance of 85% or more, and more preferably 88% or more. If the total light transmittance is 85% or more, it is comparable to bisphenol A type polycarbonate resin and the like. The optical molded article obtained by using the polycarbonate resin of the present invention preferably has a total light transmittance of 85% or more, and more preferably 88% or more. If the total light transmittance is 85% or more, it is comparable to bisphenol A type polycarbonate resin and the like.

[0031] The polycarbonate resin of the present invention has high heat and humidity resistance. The heat and humidity resistance can be evaluated by performing a "PCT test" (pressure cooker test) on an optical molded article obtained by using the polycarbonate resin and measuring the total light transmittance of the optical molded article after the test. The PCT test can be performed by holding an injection molded article with a diameter of 50 mm and a thickness of 3 mm under the conditions of 120°C, 0.2 Mpa, 100% RH, and 20 hours. The polycarbonate resin of the present invention preferably has a total light transmittance of 60% or more, more preferably 70% or more, even more preferably 75% or more, further more preferably 80% or more, and particularly preferably 85% or more after the PCT test. If the total light transmittance is 60% or more, it can be said that it has high heat and humidity resistance compared to conventional polycarbonate resins. The polycarbonate resin of the present invention has high heat and humidity resistance. The heat and humidity resistance can be evaluated by performing a "PCT test" (pressure cooker test) on an optical molded article obtained by using the polycarbonate resin and measuring the total light transmittance of the optical molded article after the test. The PCT test can be performed by holding an injection molded article with a diameter of 50 mm and a thickness of 3 mm under the conditions of 120°C, 0.2 Mpa, 100% RH, and 20 hours. The polycarbonate resin of the present invention preferably has a total light transmittance of 60% or more, more preferably 70% or more, even more preferably 75% or more, further more preferably 80% or more, and particularly preferably 85% or more after the PCT test. If the total light transmittance is 60% or more, it can be said that it has high heat and humidity resistance compared to conventional polycarbonate resins. The polycarbonate resin of the present invention has high heat and humidity resistance. The heat and humidity resistance can be evaluated by performing a "PCT test" (pressure cooker test) on an optical molded article obtained by using the polycarbonate resin and measuring the total light transmittance of the optical molded article after the test. The PCT test can be performed by holding an injection molded article with a diameter of 50 mm and a thickness of 3 mm under the conditions of 120°C, 0.2 Mpa, 100% RH, and 20 hours. The polycarbonate resin of the present invention preferably has a total light transmittance of 60% or more, more preferably 70% or more, even more preferably 75% or more, further more preferably 80% or more, and particularly preferably 85% or more after the PCT test. If the total light transmittance is 60% or more, it can be said that it has high heat and humidity resistance compared to conventional polycarbonate resins. The polycarbonate resin of the present invention has high heat and humidity resistance. The heat and humidity resistance can be evaluated by performing a "PCT test" (pressure cooker test) on an optical molded article obtained by using the polycarbonate resin and measuring the total light transmittance of the optical molded article after the test. The PCT test can be performed by holding an injection molded article with a diameter of 50 mm and a thickness of 3 mm under the conditions of 120°C, 0.2 Mpa, 100% RH, and 20 hours. The polycarbonate resin of the present invention preferably has a total light transmittance of 60% or more, more preferably 70% or more, even more preferably 75% or more, further more preferably 80% or more, and particularly preferably 85% or more after the PCT test. If the total light transmittance is 60% or more, it can be said that it has high heat and humidity resistance compared to conventional polycarbonate resins. The polycarbonate resin of the present invention has high heat and humidity resistance. The heat and humidity resistance can be evaluated by performing a "PCT test" (pressure cooker test) on an optical molded article obtained by using the polycarbonate resin and measuring the total light transmittance of the optical molded article after the test. The PCT test can be performed by holding an injection molded article with a diameter of 50 mm and a thickness of 3 mm under the conditions of 120°C, 0.2 Mpa, 100% RH, and 20 hours. The polycarbonate resin of the present invention preferably has a total light transmittance of 60% or more, more preferably 70% or more, even more preferably 75% or more, further more preferably 80% or more, and particularly preferably 85% or more after the PCT test. If the total light transmittance is 60% or more, it can be said that it has high heat and humidity resistance compared to conventional polycarbonate resins. The polycarbonate resin of the present invention has high heat and humidity resistance. The heat and humidity resistance can be evaluated by performing a "PCT test" (pressure cooker test) on an optical molded article obtained by using the polycarbonate resin and measuring the total light transmittance of the optical molded article after the test. The PCT test can be performed by holding an injection molded article with a diameter of 50 mm and a thickness of 3 mm under the conditions of 120°C, 0.2 Mpa, 100% RH, and 20 hours. The polycarbonate resin of the present invention preferably has a total light transmittance of 60% or more, more preferably 70% or more, even more preferably 75% or more, further more preferably 80% or more, and particularly preferably 85% or more after the PCT test. If the total light transmittance is 60% or more, it can be said that it has high heat and humidity resistance compared to conventional polycarbonate resins. The polycarbonate resin of the present invention has high heat and humidity resistance. The heat and humidity resistance can be evaluated by performing a "PCT test" (pressure cooker test) on an optical molded article obtained by using the polycarbonate resin and measuring the total light transmittance of the optical molded article after the test. The PCT test can be performed by holding an injection molded article with a diameter of 50 mm and a thickness of 3 mm under the conditions of 120°C, 0.2 Mpa, 100% RH, and 20 hours. The polycarbonate resin of the present invention preferably has a total light transmittance of 60% or more, more preferably 70% or more, even more preferably 75% or more, further more preferably 80% or more, and particularly preferably 85% or more after the PCT test. If the total light transmittance is 60% or more, it can be said that it has high heat and humidity resistance compared to conventional polycarbonate resins. The polycarbonate resin of the present invention has high heat and humidity resistance. The heat and humidity resistance can be evaluated by performing a "PCT test" (pressure cooker test) on an optical molded article obtained by using the polycarbonate resin and measuring the total light transmittance of the optical molded article after the test. The PCT test can be performed by holding an injection molded article with a diameter of 50 mm and a thickness of 3 mm under the conditions of 120°C, 0.2 Mpa, 100% RH, and 20 hours. The polycarbonate resin of the present invention preferably has a total light transmittance of 60% or more, more preferably 70% or more, even more preferably 75% or more, further more preferably 80% or more, and particularly preferably 85% or more after the PCT test. If the total light transmittance is 60% or more, it can be said that it has high heat and humidity resistance compared to conventional polycarbonate resins. The polycarbonate resin of the present invention has high heat and humidity resistance. The heat and humidity resistance can be evaluated by performing a "PCT test" (pressure cooker test) on an optical molded article obtained by using the polycarbonate resin and measuring the total light transmittance of the optical molded article after the test. The PCT test can be performed by holding an injection molded article with a diameter of 50 mm and a thickness of 3 mm under the conditions of 120°C, 0.2 Mpa, 100% RH, and 20 hours. The polycarbonate resin of the present invention preferably has a total light transmittance of 60% or more, more preferably 70% or more, even more preferably 75% or more, further more preferably 80% or more, and particularly preferably 85% or more after the PCT test. If the total light transmittance is 60% or more, it can be said that it has high heat and humidity resistance compared to conventional polycarbonate resins.

[0032] The b value of the polycarbonate resin of the present invention is preferably 5 or less. The smaller the b value, the weaker the yellowness is, indicating that the hue is good.

[0033] The amount of residual phenol contained in the polycarbonate resin of the present invention is preferably 500 ppm or less, more preferably 300 ppm or less, and even more preferably 50 ppm or less.

[0034] The amount of residual diphenyl carbonate (DPC) contained in the polycarbonate resin of the present invention is preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less.

[0035] (Amount of vinyl end groups) As described later, the polycarbonate resin of the present invention is represented by the following general formula (4) [Chemical formula] (In general formula (4), X represents an alkylene group having 1 to 4 carbon atoms, and a and b each independently represent an integer of 1 to 10.) is a resin obtained by using a compound represented by the formula as a dihydroxy component and reacting it with a carbonate precursor such as a carbonic acid diester. However, when producing the resin, a polymer having a terminal structure represented by the following formula (A) and a compound represented by the formula (B ) are generated as by-products and contained in the polycarbonate resin of the present invention, or after the polymer of formula (1) is obtained, the terminal is modified to a vinyl group and becomes a polymer having a terminal structure represented by the following formula (A). ) There are cases where it becomes a polymer having a terminal structure represented by the following formula (A). (A) [Chemistry] [In formulas (A) and (B), X represents an alkylene group having 1 to 4 carbon atoms, a and b each independently represent an integer from 1 to 10, Hm are each a hydrogen atom, * is a polymer chain]

[0036] According to a preferred embodiment of the present invention, the total content of the polymer having the terminal structure represented by the general formula (A) and the compound represented by the general formula (B) contained in the polycarbonate resin is such that, when the 1H-NMR spectrum of the polycarbonate resin is measured, it is preferably an amount that satisfies the following relationship (that is, "the amount of fluorene-based vinyl end groups 1"). 1 [Mathematics]

[0037] The amount of fluorene-based vinyl end groups 1 calculated by formula (I) is more preferably 0.0 01 to 0.8, and particularly preferably 0.01 to 0.5. When the amount of fluorene-based vinyl end groups 1 calculated by formula (I) is within the above range, the polycarbonate resin is preferably excellent in fluidity and strength, for example, flexural strength and tensile strength.

[0038] Formula (I) corresponds to the following formula. [Mathematics]

[0039] In the above formula, "Ha in the repeating unit derived from the compound of formula (4)" means all the hydrogen atoms contained in X of formula ( 4). For example, when X is an ethylene group, Ha The position is as follows. When the compound represented by the general formula (5) and / or (6) is further used as the dihydroxy component, the integrals of "Hb in the repeating unit derived from the compound of formula (5)" and "Hc in the repeating unit derived from the compound of formula (6)" are added to the denominator of the above formula, which will be described later. [Chemical formula]

[0040] Here, the "integral value of the proton peak" and the "peak integral value" refer to the area value of the signal of the NMR spectrum, that is, the integral value, measured by NMR (nuclear magnetic resonance ) spectroscopy for the hydrogen nucleus 1 H in the NMR spectrum of 1 1H-NMR spectrum). Generally, NMR spectroscopy is a measurement method focusing on the atomic nuclei of substances, and the nuclei of each molecule can be quantitatively measured. That is, in the case of 1H-NMR, the integral value of the observed signal indicates the abundance of 1H in the molecule. In the present invention, the assignment of 1H is inferred from the chemical shift value of the 1H-NMR spectrum, and the integral value of the 1H signal is obtained for each chemical shift value. 1 1 1 The polycarbonate resin of the present invention preferably contains, in addition to the compound represented by the above general formula (4), the following general formula (5) and / or (6) 1 1

[0041] [Chemical formula] (In the general formula (5), Y represents an alkylene group having 1 to 4 carbon atoms, and c and d are each independently​​​​​​​​​​​ represents an integer from 1 to 10.) [Chemical formula] (In general formula (6), Z represents an alkylene group having 1 to 4 carbon atoms, R 1 ~R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalko xyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.) e and f each independently represent an integer from 0 to 5.) A resin obtained by using the compound represented by as a dihydroxy component and reacting it with a carbonate precursor such as a diester carbonate. However, when producing such a resin from the compounds of the above general formula (5) and / or (6), polymers having terminal structures represented by the following formula (C) and / or (E) and compounds represented by formula (D) and / or (F) are generated as by-products and contained in the polycarbonate resin of the present invention. Also, after the polymer is obtained, the terminal may be modified to a vinyl group and become a polymer having a terminal structure represented by the following formula (C) and / or (E). [Chemical formula] [In formulas (C) to (F), Y and Z each independently represent an alkylene group having 1 to 4 carbon atoms, R 1 ~R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalko​​​ represents a xylyl group, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, c and d each independently represent an integer from 1 to 10, e represents an integer from 1 to 5, f represents an integer from 0 to 5, and f - 1 is 0 or more, Hn and Ho are each a hydrogen atom; * is a polymer chain]

[0042] According to a preferred embodiment of the present invention, the total content of the polymer having a terminal structure represented by the general formula (C) contained in the polycarbonate resin and the compound represented by the general formula (D) is the H of the poly carbonate resin - When measuring the NMR spectrum, it is preferably an amount that satisfies the following relationship (that is, "the amount of binaphthol-based vinyl end groups"). 1

Number

[0043] The amount of binaphthol-based vinyl end groups calculated by formula (II) is more preferably 0. 05 to 0.8, particularly preferably 0.1 to 0.6. If the amount of binaphthol-based vinyl end groups calculated by formula (II) is within the above range, the polycarbonate resin is preferably excellent in fluidity and strength.

[0044] Formula (II) corresponds to the following formula.

Number

[0045] In the above formula, "Hb in the repeating unit derived from the compound of formula (5)" and "formula ( ​​​"Hc" in the repeating unit derived from the compound of (6) means all hydrogen atoms contained in Y and Z of formulas (5) and (6), respectively. For example, when Y and Z are ethylene groups, the positions of Hb and Hc are as follows. respectively.

Chemical formula

[0046] According to a preferred embodiment of the present invention, the total content of the polymer having the terminal structure represented by the general formula (E) contained in the polycarbonate resin and the compound represented by the general formula (F) is preferably an amount satisfying any of the following relationships when measuring the 1H-NMR spectrum of the polycarbonate resin (that is, "the amount of fluorene-based vinyl end groups 2" and "the amount of fluorene-based vinyl end groups 3"). - NMR spectrum of the carbonate resin 1 is measured, it is preferably an amount that satisfies any of the following relationships (that is, "the amount of fluorene-based vinyl end groups 2" and "the amount of fluorene-based vinyl end groups 3").

Number

[0047] Here, when any of R~R in formulas (5'), (E) and (F) is not an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms, the above formula (III) is applicable, and when at least one of R~R in formulas (5'), (E) and (F) is an aryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, the above formula (IV) is applicable. 1 ~R 4 is not an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms, the above formula (III) is applied. When at least one of R~R in formulas (5'), (E) and (F) is an aryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, the above formula (IV) 1 ~R 4 is applied. 0 carbon atoms is an aryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, the above formula (IV) is applied.

[0048] The amount of fluorene-based vinyl end groups 2 calculated by formula (III) is more preferably 0 .001 to 0.8, particularly preferably 0.01 to 0.5. According to formula (III),​​​ If the amount 2 of the fluorene-based vinyl end group calculated by the formula (IV) is within the above range, the polycarbonate resin is preferred because of its excellent fluidity and strength.

[0049] The amount 3 of the fluorene-based vinyl end group calculated by the formula (IV) is more preferably 0. 001 to 0.8, and particularly preferably 0.01 to 0.5. If the amount 3 of the fluorene-based vinyl end group calculated by the formula (IV) is within the above range, the polycarbonate resin is preferred because of its excellent fluidity and strength.

[0050] The formulas (III) and (IV) correspond to the following formulas.

Number

[0051] (2) Method for producing polycarbonate resin The polycarbonate resin having the structural unit represented by the general formula (1) according to the present invention is obtained by using the compound represented by the following general formula (4) as a dihydroxy component and reacting it with a carbonate precursor such as a carbonic acid diester. Specifically, the compound represented by the general formula (4) and a carbonate precursor such as a carbonic acid diester are subjected to melt polycondensation in the presence of a basic compound catalyst or an ester exchange catalyst or a mixed catalyst composed of both, or without a catalyst.

Chemical formula

[0052] ​​​​​Examples of the compound of the general formula (4) include 9,9-bis(hydroxy(poly)alkoxynaphthyl fluorenes. For example, as the compound of the general formula (4), 9,9-bis [6-(1-hydroxymethoxy)naphthalen-2-yl]fluorene, 9,9-bis[6 [2-hydroxyethoxy)naphthalen-2-yl]fluorene, 9,9-bis[6- (3-hydroxypropoxy)naphthalen-2-yl]fluorene, and 9,9-bis [6-(4-hydroxybutoxy)naphthalen-2-yl]fluorene, etc. may be mentioned. Among them, 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluoro rene is preferable. These may be used alone or in combination of two or more.

[0053] When producing the compound of the general formula (4), a compound in which either a or b is 0 may be by-produced as an impurity. The content of such impurities is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 200 ppm or less, and particularly preferably 100 ppm or less in total in the monomer containing the compound of the general formula (4) as the main component. Furthermore, in addition to such impurities, fluorenone, which is one of the raw materials, may also be contained as an impurity. The content of fluorenone is preferably 1000 ppm or less, more preferably 100 ppm or less, still more preferably 50 ppm or less, and particularly preferably 10 ppm or less in the monomer containing the compound of the general formula (4) as the main component. Fluorenone contained in the monomer containing the compound of the general formula (4) as the main component may remain in the resin after polymerization. ​The lower the fluorene content, the better the hue of the resin, which is preferable. Furthermore , although not an impurity, the compound in which a and b in the general formula (4) are not the same (i.e., a≠b) should be 50 ppm or less in total in the monomer containing the compound of the general formula (4) preferably, and more preferably 20 ppm or less.

[0054] The compound of the general formula (4) can be produced by various synthesis methods. For example, as described in Japanese Patent No. 54 42800, (a) a method of reacting fluorenones with hydroxynaphthalenes in the presence of hydrogen chloride gas and mercaptocarboxylic acid, (b) a method of reacting 9-fluorenone with hydroxynaphthalenes in the presence of an acid catalyst (and alkyl mercaptan), (c) a method of reacting fluorenones with hydroxynaphthalenes in the presence of hydrochloric acid and thiols (such as mercaptocarboxylic acid), (d) a method of reacting fluorenones with hydroxynaphthalenes in the presence of sulfuric acid and thiols (such as mercaptocarboxylic acid), and crystallizing with a crystallization solvent composed of hydrocarbons and a polar solvent to produce bisnaphthol fluorene to obtain 9,9-bis(hydroxynaphthyl)fluorenes, and then reacting them with compounds corresponding to the [XO]a group and the [XO]b group (such as alkylene oxide and haloalkano l) can be used to produce them. For example, 9,9-bis[6- (2-hydroxyethoxy)naphthyl]fluorene can be obtained by reacting 9,9-bis[6-hydroxynaph thyl]fluorene with 2-chloroethanol under alkaline conditions .

[0055] ​​​​​The polycarbonate resin having a structural unit represented by the general formula (1) according to the present invention is generally In addition to the compound of the formula (4), an aromatic dihydroxy compound or an aliphatic dihydroxy compound (e.g. For example, a dihydroxy compound having a fluorene skeleton or binaphthols) can be used in combination as a dihydroxy component.

[0056] Preferably, the polycarbonate resin of the present invention is in addition to the compound represented by the above general formula (4), The compound represented by the following general formula (5) and / or the compound represented by the following general formula (6) can be used as a dihydroxy component for production. [Chemical formula] (In the general formula (5), Y represents an alkylene group having 1 to 4 carbon atoms, and c and d each independently represent an integer of 1 to 10.) [Chemical formula] (In the general formula (6), Z represents an alkylene group having 1 to 4 carbon atoms, R 1 ~R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, and e and f each independently represent an integer of 0 to 5.)

[0057] Examples of the dihydroxy compound represented by the formula (5) include 2,2'-bis(1-hydroxy methoxy)-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-1 ​​,1'-Binaphthalene, 2,2'-bis(3-hydroxypropyloxy)-1,1'- binaphthalene, 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthalene, etc. Among them, 2,2'-bis(2-hydroxyethoxy)-1,1'- binaphthalene (hereinafter sometimes abbreviated as "BHEBN") is preferable. These may be used alone or in combination of two or more.

[0058] When producing the compound of general formula (5), a compound in which either c or d is 0 may be by-produced as an impurity. The content of such an impurity is preferably 1000 ppm or less in total in the monomer containing the compound of general formula (5) as the main component, more preferably 500 ppm or less, still more preferably 200 ppm or less, and particularly preferably 100 ppm or less. Further, although not an impurity, a compound in which c and d in general formula (5) are not the same (i.e., c≠d) is preferably 50 ppm or less in total in the monomer containing the compound of general formula (5) as the main component, more preferably 20 ppm or less. (5) Examples of the dihydroxy compound represented by formula (6) include 9,9-bis[4-(2-hydroxy ethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-

[0059] 3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3- tert-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)- 3-isopropylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy -3- tert-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy )-3-Cyclohexylphenyl]fluorene, 9,9-bis[4-(2-hydroxyeth xy)-3-phenylphenyl]fluorene (hereinafter sometimes abbreviated as "BPPEF" ) and the like. Among them, 9,9-bis[4-(2-hydroxyethoxy)phenyl]f luorene and 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]f luorene are preferred. These may be used alone or in combination of two or more .

[0060] When producing the compound of the general formula (6), a compound in which either e or f is 0 may be by-produced as an impurity. The content of such impurities is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 200 ppm or less, and particularly preferably 100 ppm or less in total in the monomer containing the compound of the general formula (6) as the main component. Furthermore, although not an impurity, the compound in which e and f in the general formula (6) are not the same (i.e., e≠f) is preferably 50 ppm or less, more preferably 20 ppm or less in total in the monomer containing the compound of the general formula (6) as the main component. In addition to the above, examples of aromatic dihydroxy compounds that can be used in combination include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisph

[0061] enol TMC, and bisphenol Z and the like. A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisph enol TMC, and bisphenol Z and the like are exemplified.

[0062] Examples of the carbonic acid diester used in the present invention include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and the like. Among these, diphenyl carbonate is particularly preferred. Diphenyl carbonate is preferably used in a ratio of 0.97 to 1.20 moles per 1 mole of the total amount of the dihydroxy compound, and more preferably in a ratio of 0.98 to 1.10 moles.

[0063] Among the transesterification catalysts, examples of the basic compound catalyst include particularly alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.

[0064] Examples of the alkali metal compound used in the present invention include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, or alkoxides of alkali metals. Specifically, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenylborohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, disodium salt of bisphenol A, dipotassium salt, ​​2 cesium salts or 2 lithium salts, sodium salts, potassium salts, cesium salts or lithium salts, etc. are used.

[0065] As the alkaline earth metal compound, for example, organic acid salts, inorganic salts of alkaline earth metal compounds, oxides, hydroxides, hydrides or alkoxides, etc. can be mentioned. Specifically, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium phosphate, calcium benzoate, magnesium phenyl phosphate, etc. are used.

[0066] As the nitrogen-containing compound, for example, quaternary ammonium hydroxides and their salts, amines and the like can be mentioned. Specifically, quaternary ammonium hydroxides having alkyl groups such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, etc.; tertiary amines such as triethylamine, dimethyl benzylamine, triphenylamine, etc.; secondary amines such as diethylamine, dibutylamine etc.; primary amines such as propylamine, butylamine, etc.; imidazoles such as 2-methylimidazole, 2-phenylimidazole, benzimidazole, etc.; or ammonia, tetramethylammonium borohydride, tetrabutylammonium Muborohydride, tetrabutylammonium tetraphenylborate, tetraphenyl Bases or basic salts such as ammonium tetraphenylborate are used.

[0067] As the transesterification catalyst, salts of zinc, tin, zirconium, lead, etc. are preferably used , and these can be used alone or in combination.

[0068] Specifically, as the transesterification catalyst, zinc acetate, zinc benzoate, 2-ethylhexyl zinc acid, tin(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate, dibutyl tin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, acetic lead(II) acetate, lead(IV) acetate, etc. are used.

[0069] These catalysts are used in a ratio of 1×10 -9 ~1×10 -3 mol, preferably 1×10 -7 ~1×10 -4 mol ratio.

[0070] The melt polycondensation method uses the above-mentioned raw materials and catalysts, under heating, and further under normal pressure or reduced pressure, Melt polycondensation is carried out while removing by-products by transesterification reaction.

[0071] In the melt polycondensation of this composition system, the compound represented by the general formula (4) and the carbonic acid diester are reacted After melting in a reaction vessel, the reaction is preferably carried out in a state where the by-produced monohydroxy compound is retained. In order to retain it, the reaction apparatus is blocked, or the pressure is reduced or increased, etc. pressure The force can be controlled. The reaction time of this step is 20 minutes or more and 240 minutes or less, preferably 40 minutes or more and 180 minutes or less, particularly preferably 60 minutes or more and 150 minutes or less. At this time, if the by-produced monohydroxy compound is distilled off immediately after its formation, the finally obtained polycarbonate resin has a low content of high molecular weight polymer. However, if the by-produced monohydroxy compound is allowed to remain in the reaction vessel for a certain period of time, a polycarbonate resin with a high content of high molecular weight polymer can be obtained.

[0072] The melt polycondensation reaction may be carried out continuously or batchwise. The reaction apparatus used in the reaction may be a vertical type equipped with an anchor type stirring blade, a max blend stirring blade, a helical ribbon type stirring blade, etc., or a horizontal type equipped with a paddle blade, a lattice blade, a glasses blade, etc., or an extruder type equipped with a screw. Also, in consideration of the viscosity of the polymer, it is preferably implemented to use a reaction apparatus in which these reaction apparatuses are appropriately combined.

[0073] In the method for producing a polycarbonate resin used in the present invention, after the polymerization reaction is completed, in order to maintain thermal stability and hydrolysis stability, the catalyst may be removed or deactivated. A method of deactivating the catalyst by adding a known acidic substance can be preferably implemented. Specific examples of the acidic substance include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid ; aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid ; triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, etc. ​Di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, mono Octyl phosphite esters such as octyl; triphenyl phosphate, diphenyl phosphate, mono Phenyl phosphate, dibutyl phosphate, dioctyl phosphate, monooctyl phosphate, etc. Phosphite esters; diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphonic acid, etc. Phosphonic acid esters such as diethyl phenylphosphonate; triphenylphosphine Phosphines such as bis(diphenylphosphino)ethane; boric acid, phenylboric acid, etc. Boric acid esters; aromatic sulfonate salts such as tetrabutylphosphonium dodecylbenzenesulfonate Organic halides such as stearic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride Alkyl sulfates such as dimethyl sulfate; organic halides such as benzyl chloride Compounds are preferably used. These deactivators are used in an amount of 0.01 to 50 moles, Preferably 0.3 to 20 moles, based on the amount of catalyst. If the amount is less than 0.01 mole Based on the amount of catalyst, the deactivation effect is insufficient, which is not preferable. Also, if the amount is more than 50 moles Based on the amount of catalyst, the heat resistance of the resin decreases, and the molded article tends to be colored, which is not preferable.

[0074] After catalyst deactivation, a step of devolatilizing and removing low-boiling compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 35 0 °C may be provided. For this step, a horizontal device equipped with a stirring blade with excellent surface renewal ability, such as a paddle blade, a lattice blade, a mega Ned blade, or a thin-film evaporator is preferably used. It is preferably used.

[0075] The polycarbonate resin of the present invention desirably has as little foreign matter content as possible, and filtration of the molten raw material, Filtration of the catalyst solution, etc. are preferably carried out. The mesh of the filter is 5 μm or less. It is preferable that the particle size is 1 μm or less, and more preferable that the particle size is 1 μm or less. Filtration using a polymer filter is preferably performed. The mesh of the polymer filter is 100 μm. The particle size of the resin pellets is preferably 30 μm or less, and more preferably 30 μm or less. The collection process must be carried out in a low-dust environment, preferably class 6 or less. More preferably, it is class 5 or lower.

[0076] In another embodiment of the present invention, a polycarbonate having structural units represented by general formulas (1) to (3) is A carbonyl resin or a polycarbonate resin containing structural units represented by the general formulas (1) and (2) In the case of producing a carboxylate resin, the compounds represented by the general formulas (4) to (6) are used to form a carboxylate resin represented by the general formula (1 ) to (3) or structural units represented by general formulas (1) and (2) Copolymers may be produced by polymerizing the compounds represented by the general formulas (4) to (6) separately. Manufactured as a ternary or binary resin containing homopolymers of each structural unit Alternatively, a copolymer containing the structural units represented by the general formulas (1) and (2) and a general A homopolymer containing a constitutional unit represented by formula (3) may be polymerized and then blended. A copolymer containing structural units represented by general formulas (1) and (2) and a copolymer containing structural units represented by general formulas (1) and (3). Copolymers containing such structural units may be polymerized and then blended.

[0077] (3) Optical molded body The polycarbonate resin of the present invention can be used to produce optical molded articles. For example, by injection molding, The molding may be performed by any method, such as compression molding, extrusion molding, or solution casting. The polycarbonate resin has excellent moldability and heat resistance, so injection molding is not required. It can be particularly advantageously used in the optical lens. During molding, the polycarbonate resin of the present invention can be mixed with other resins such as other polycarbonate resins and polyester resins and used. In addition, additives such as antioxidants, processing stabilizers, light stabilizers, polymerization metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, mold release agents, ultraviolet absorbers, plasticizers, and compatibilizers may be mixed. Examples of the antioxidant include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, and 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane. The polycarbonate

[0078] The content of the antioxidant in the resin is preferably 0.001 to 0.3 parts by weight based on 100 parts by weight of the polycarbonate resin.

[0079] Examples of the processing stabilizer include phosphorus-based processing heat stabilizers, sulfur-based processing heat stabilizers, etc. Phosphorus Examples of the phosphorus-based processing heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and their esters such as. Specifically, triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, tridecyl phosphite , trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, bis(nonylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate , triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate , diisopropyl phosphate, dimethyl benzene phosphonate, benzene phosphonic acid dimethyl, etc. , monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, bis(nonylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate , bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, bis(nonylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate , 2,2-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, bis(nonylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate , bis(nonylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate , bis(2,4-dicumylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate , bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate , distearyl pentaerythritol diphosphite, tributyl phosphate , triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate , diisopropyl phosphate, dimethyl benzene phosphonate, benzene phosphonic acid , dimethyl benzene phosphonate, benzene phosphonic acid Diethyl, dipropyl benzene phosphonate, tetrakis(2,4-di-t-butylphenyl )-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-t-butylf enyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-t-butyl lphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert- butylphenyl)-4-phenyl-phenyl phosphonite and bis(2,4-di-ter t-butylphenyl)-3-phenyl-phenyl phosphonite and the like. The content of the phosphorus-based processing heat stabilizer in the polycarbonate resin is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

[0080] Examples of the sulfur-based processing heat stabilizer include pentaerythritol-tetrakis(3-laurylthio propionate), pentaerythritol-tetrakis(3-myristylthiopropionate), pentaerythritol-tetrakis(3-stearylthiopropionate), di lauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropio nate, distearyl-3,3'-thiodipropionate and the like. The content of the sulfur-based processing heat stabilizer in the polycarbonate resin is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

[0081] As the release agent, those in which 90% by weight or more thereof is composed of an ester of an alcohol and a fatty acid are preferred. Specific examples of the ester of an alcohol and a fatty acid include esters of monohydric alcohols and fatty acids, partial esters or full esters of polyhydric alcohols and fatty acids. ​​​It can be obtained. As the ester of the above monohydric alcohol and fatty acid, an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferred. Further, as the partial ester or total ester of a polyhydric alcohol and a fatty acid, a partial ester or total ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferred. Specifically, as the ester of a monohydric alcohol and a saturated fatty acid, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. can be mentioned. As the partial ester or total ester of a polyhydric alcohol and a saturated fatty acid, monoglyceride stearate, monoglyceride stearate, diglyceride stearate, triglyceride stearate, monosorbitate stearate, monoglyceride behenate,

[0082] monoglyceride caprylate, monoglyceride laurate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetraperargonate, propylene glycol monostearate, biphenylbiphenate, sorbitan monostearate, 2-ethylhexyl stearate, and total esters or partial esters of dipentaerythritol such as dipentaerythritol hexastearate can be mentioned. The content of these mold release agents is preferably in the range of 0.005 to 2.0 parts by weight, more preferably in the range of 0.01 to 0.6 parts by weight, and even more preferably in the range of 0.02 to 0.5 parts by weight with respect to 100 parts by weight of the polycarbonate resin. As the ultraviolet absorber, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, etc.

[0083] ​ An absorbent, a triazine-based ultraviolet absorber, a cyclic iminoester-based ultraviolet absorber, and a cyanoacrylate At least one ultraviolet absorber selected from the group consisting of a relato-based ultraviolet absorber is preferred That is, any of the following ultraviolet absorbers may be used alone, or two or more May be used in combination.

[0084] Examples of benzotriazole-based ultraviolet absorbers include 2-(2-hydroxy-5-methylphenyl) Benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl) Benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenz Zotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetra Methylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotri Zole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotri Zole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole , 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-( 2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebi (4-cumyl-6-benzotriazolylphenyl), 2,2'-p-phenylenebis( 1,3-benzoxazin-4-one), 2-[2-hydroxy-3-(3,4,5,6 -tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole and the like are exemplified. For example.

[0085] Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2- hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy -5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytoluidine hydride rate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy -4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy -5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy -2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like can be mentioned. .

[0086] Examples of triazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol, 2-(4,6-bis(2 ,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-[(octyl) oxy]-phenol and the like can be mentioned.

[0087] Examples of cyclic iminoester-based ultraviolet absorbers include 2,2'-bis(3,1-benzoxazine-4-one), 2,2'-p-phenylene bis(3,1-benzoxazine-4-one) ), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), 2,2 '-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one), 2,2 '-(2,6-naphthalene)bis(3,1-benzoxazin-4-one), 2,2'- (1,5-naphthalene)bis(3,1-benzoxazin-4-one), 2,2'-(2 -methyl-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'- (2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one) and 2, 2'-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one) and the like can be mentioned.

[0088] Examples of the cyanoacrylate-based ultraviolet absorber include 1,3-bis-[(2'-cyano-3' ,3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-di phenylacryloyl)oxy]methyl)propane, and 1,3-bis-[(2-cyano -3,3-diphenylacryloyl)oxy]benzene and the like.

[0089] The content of the ultraviolet absorber is preferably 0 .01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, and still more preferably 0.05 to 0.8 parts by weight with respect to 100 parts by weight of the polycarbonate resin. Within such a compounding amount range, depending on the application, it is possible to impart sufficient weather resistance to the poly carbonate resin.

[0090] The polycarbonate resin of the present invention has a high refractive index and a low Abbe number. Furthermore, in addition to optical lenses, it is used for transparent conductors used in liquid crystal displays, organic EL displays, solar cells, etc. ​It can be advantageously used as an optical molded article suitable for structural materials or functional material applications of optical components such as electrical substrates, optical discs, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor-deposited plastic mirrors, displays, etc. For the applications of structural materials or functional materials of optical components such as electrical substrates, optical discs, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor-deposited plastic mirrors, displays, etc. It can be advantageously used as an optical molded article suitable for such applications.

[0091] On the surface of the optical molded article, an anti-reflection layer or a hard coat layer or other coating layers may be provided as necessary. The anti-reflection layer may be a single layer or a multi-layer, and may be an organic substance or an inorganic substance, but it is preferably an inorganic substance. Specifically, Examples thereof include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, magnesium fluoride, etc. For the applications of structural materials or functional materials of optical components such as electrical substrates, optical discs, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor-deposited plastic mirrors, displays, etc. Examples thereof include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, magnesium fluoride, etc. Examples thereof include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, magnesium fluoride, etc.

[0092] (4) Optical lens The optical lens produced using the polycarbonate resin of the present invention has a high refractive index, a low Abbe number, and high moisture and heat resistance. Therefore, it can be used in fields where expensive high refractive index glass lenses have been conventionally used, such as telescopes, binoculars, television projectors, etc., and is extremely useful. If necessary, it is preferably used in the form of an aspherical lens. Since an aspherical lens can substantially make the spherical aberration zero with a single lens, it is not necessary to remove the spherical aberration by combining a plurality of spherical lenses, and weight reduction and reduction of production costs become possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses. The optical lens is molded by an arbitrary method such as an injection molding method, a compression molding method, an injection compression molding method, etc. According to the present invention, a high refractive index, low birefringence, and aspherical lens, which is technically difficult to process with a glass lens, can be obtained more simply. If necessary, it is preferably used in the form of an aspherical lens. Since an aspherical lens can substantially make the spherical aberration zero with a single lens, it is not necessary to remove the spherical aberration by combining a plurality of spherical lenses, and weight reduction and reduction of production costs become possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses. If necessary, it is preferably used in the form of an aspherical lens. Since an aspherical lens can substantially make the spherical aberration zero with a single lens, it is not necessary to remove the spherical aberration by combining a plurality of spherical lenses, and weight reduction and reduction of production costs become possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses. If necessary, it is preferably used in the form of an aspherical lens. Since an aspherical lens can substantially make the spherical aberration zero with a single lens, it is not necessary to remove the spherical aberration by combining a plurality of spherical lenses, and weight reduction and reduction of production costs become possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses. If necessary, it is preferably used in the form of an aspherical lens. Since an aspherical lens can substantially make the spherical aberration zero with a single lens, it is not necessary to remove the spherical aberration by combining a plurality of spherical lenses, and weight reduction and reduction of production costs become possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses. The optical lens is molded by an arbitrary method such as an injection molding method, a compression molding method, an injection compression molding method, etc. According to the present invention, a high refractive index, low birefringence, and aspherical lens, which is technically difficult to process with a glass lens, can be obtained more simply. According to the present invention, a high refractive index, low birefringence, and aspherical lens, which is technically difficult to process with a glass lens, can be obtained more simply. According to the present invention, a high refractive index, low birefringence, and aspherical lens, which is technically difficult to process with a glass lens, can be obtained more simply.

[0093] In order to avoid foreign matter from entering the optical lens as much as possible, the molding environment should naturally be a low-dust environment, preferably Class 6 or lower, more preferably Class 5 or lower.

[0094] (5) Optical film The optical film produced using the polycarbonate resin of the present invention is excellent in transparency and heat resistance and is preferably used for films for liquid crystal substrates, optical memory cards, etc.

[0095] In order to avoid foreign matter from entering the optical film as much as possible, the molding environment should naturally be a low-dust environment, preferably Class 6 or lower, more preferably Class 5 or lower.

[0096] <Example> The present invention will be described below with reference to examples, but the present invention is not limited to these examples in any way. The measured values in the examples were measured using the following methods or apparatuses. 1) Polystyrene-reduced weight average molecular weight (Mw): Gel permeation chromatography (GPC) was used, and tetrahydrofuran was used as the eluent. A calibration curve was created using standard polystyrene with a known molecular weight (molecular weight distribution = 1). Based on this calibration curve, Mw was calculated from the retention time of GPC. 2) Refractive index (nD): For a 0.1 mm-thick film made of the polycarbonate resin produced in the example, the refractive index was measured using an Abbe refractometer by the method of JIS-K-7142. 3) Abbe number (ν): For a 0.1 mm-thick film made of the polycarbonate resin produced in the example, the refractive indices at wavelengths of 486 nm, 589 nm, and 656 nm at 23°C were measured using an Abbe refractometer, and the Abbe number was calculated using the following formula. ν = (nD - 1) / (nF - nC) nD: Refractive index at a wavelength of 589 nm nC: Refractive index at a wavelength of 656 nm nF: Refractive index at a wavelength of 486 nm 4) Glass transition temperature (Tg): Measured by a differential scanning calorimeter (DSC). 5) Total light transmittance: For a 3 mm thick plate made of polycarbonate resin prepared for the measurement of the following b value, using a SE2000 type spectrophotometric color difference meter manufactured by Nippon Denshoku Industries Co., Ltd., it was measured by the method of JIS-K-7361-1. 6) b value: After the manufactured resin was vacuum dried at 120 °C for 4 hours, it was injection molded at a cylinder temperature of 270 °C and a mold temperature of Tg - 10 °C using an injection molding machine (FANUC ROB OSHOT α-S30iA) to obtain a disc-shaped test plate piece with a diameter of 50 mm and a thickness of 3 mm. Using this plate piece, the b value was measured according to JIS K7105. A smaller b value indicates a weaker yellow color, and the hue is better. For the measurement of the molded plate, a SE2000 type spectrophotometric color difference meter manufactured by Nippon Denshoku Industries Co., Ltd. was used. 7) Vinyl end group content: 1 The 1H-NMR measurement was carried out under the following conditions. · 1 1H-NMR measurement conditions Apparatus: Bruker AVANZE III HD 500 MHz Flip angle: 30 degrees Waiting time: 1 second Number of integrations: 500 times Measurement temperature: Room temperature (298 K) Concentration: 5 wt% Solvent: Deuterated chloroform Internal standard substance: Tetramethylsilane (TMS) 0.05 wt% 8) Residual phenol and residual diphenyl carbonate (DPC) content: The weighed polycarbonate Accurately weigh 1.0 g of the polycarbonate resin, dissolve it in 10 ml of dichloromethane, and gradually add it to 100 ml of methanol with stirring to reprecipitate the resin. After sufficient stirring, the precipitate was filtered off, and 1.0 g of the standard substance solution was accurately weighed and added to the solid obtained by concentrating the filtrate with an evaporator. Furthermore, 1 g of chloroform was added and the diluted solution was quantified by GC-MS . Standard substance solution: 200 ppm, chloroform solution of 2,4,6-trimethylphenol Measuring device (GC-MS): Agilent HP6890 / 5973MSD Column: capillary column DB-5MS, 30 m × 0.25 mm I.D., film thickness 0.5 μm Temperature rising condition: 50 °C (hold for 5 min) ~ 300 °C (hold for 15 min), 10 °C / min Inlet temperature: 300 °C, injection volume: 1.0 μl (split ratio 25) Ionization method: EI method Carrier gas: He, 1.0 ml / min Aux temperature: 300 °C Mass scan range: 33 - 700 9) Residual amount of BHEBN and residual amount of BPPEF: Dissolve 0.5 g of the weighed polycarbonate resin in 50 ml of tetrahydrofuran (THF) to prepare a sample solution. A calibration curve was prepared from the pure products of each compound as standards, and 2 μL of the sample solution was quantified by LC-MS under the following measurement conditions. The detection limit value under these measurement conditions is 0 .01 ppm. LC-MS measurement conditions: Measuring device (LC part): Agilent Infinity 1260 LC System Column: ZORBAX Eclipse XDB-18, and guard cartridge Mobile phase: A: 0.01 mol / L - ammonium acetate aqueous solution ​​​​B: 0.01 mol / L ammonium acetate methanol solution C: THF Gradient program of the mobile phase:

Table 1

[0097] ​​[Production of Polycarbonate Resin] (Example 1) As raw materials, 18.85 g (0.035 mol) of 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene (hereinafter sometimes abbreviated as "BNEF"), 18.35 g (0.049 mol) of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (hereinafter sometimes abbreviated as "BHE BN"), 7.02 g (0.016 mol) of 9,9-bis[4-( 2-hydroxyethoxy)phenyl]fluorene (hereinafter sometimes abbreviated as "BPEF"), 21.70 g (0.101 mol) of diphenyl carbonate (hereinafter sometimes abbreviated as "DPC"), and 32 μl (8.0×10 mol) of a 2.5×10 mol / liter -2 aqueous sodium hydrogen carbonate solution, that is, 8.0×10 mol (i.e., 8.0×10 -7 mol per 1 mol of the total of dihydroxy compounds) were placed in a 300 m l four-necked flask equipped with a stirrer and a distillation apparatus, and heated to 180°C under a nitrogen atmosphere of 760 mmHg. After 10 minutes from the start of heating, complete dissolution of the raw materials was confirmed, and then stirring was carried out for 110 minutes under the same conditions. Then, -6 while adjusting the degree of reduced pressure to 200 mmHg, the temperature was raised to 200°C at a rate of 60°C / hr. At this time, the start of distillation of by-produced phenol was confirmed. Then, the reaction was carried out while maintaining at 200°C for 20 minutes. Further, the temperature was raised to 230°C at a rate of 75°C / hr, and 10 minutes after the completion of the temperature rise, while maintaining at that temperature, the degree of reduced pressure was reduced to 1 mmHg or less over 1 hour. Then, while adjusting the degree of reduced pressure to 200 mmHg, the temperature was raised to 200°C at a rate of 60°C / hr. At this time, the start of distillation of by-produced phenol was confirmed. Then, the reaction was carried out while maintaining at 200°C for 20 minutes. Further, the temperature was raised to 230°C at a rate of 75°C / hr, and 10 minutes after the completion of the temperature rise, while maintaining at that temperature, the degree of reduced pressure was reduced to 1 mmHg or less over 1 hour. Then, 10 minutes after the start of heating, complete dissolution of the raw materials was confirmed, and then stirring was carried out for 110 minutes under the same conditions. Then, while adjusting the degree of reduced pressure to 200 mmHg, the temperature was raised to 200°C at a rate of 60°C / hr. At this time, the start of distillation of by-produced phenol was confirmed. Then, the reaction was carried out while maintaining at 200°C for 20 minutes. Further, the temperature was raised to 230°C at a rate of 75°C / hr, and 10 minutes after the completion of the temperature rise, while maintaining at that temperature, the degree of reduced pressure was reduced to 1 mmHg or less over 1 hour. Then, the reaction was carried out while maintaining at 200°C for 20 minutes. Further, the temperature was raised to 230°C at a rate of 75°C / hr, and 10 minutes after the completion of the temperature rise, while maintaining at that temperature, the degree of reduced pressure was reduced to 1 mmHg or less over 1 hour. Then, the reaction was carried out while maintaining at 200°C for 20 minutes. Further, the temperature was raised to 230°C at a rate of 75°C / hr, and 10 minutes after the completion of the temperature rise, while maintaining at that temperature, the degree of reduced pressure was reduced to 1 mmHg or less over 1 hour. Then, 10 minutes after the completion of the temperature rise, while maintaining at that temperature, the degree of reduced pressure was reduced to 1 mmHg or less over 1 hour. Then, the temperature was raised to 245°C at a rate of 60°C / hr, and stirring was further carried out for 30 minutes. After the completion of the reaction, nitrogen was introduced into the reactor to return to normal pressure, and the produced polycarbonate resin was taken out. .

[0098] The physical property values of the obtained resin are shown in Table 2. Also, the ratio of the H 1 -NMR spectrum of the resin was confirmed. As a result, (peak integral value of 4.75 - 4.69 ppm) / (peak integral value of 4.85 - 2.80 pp m) × 100 = 0.029, (peak integral value of 4.59 - 4.55 ppm) / (peak integral value of 4.85 - 2.80 ppm) × 100 = not detected, (peak integral value of 3.62 - 3.26 ppm) / (peak integral value of 4.85 - 2.80 ppm) × 100 = 0.18 9, (peak integral value of 4.83 - 4.76 ppm) / (peak integral value of 4.85 - 2.80 ppm peak inte gral value) × 100 = 0.026. The b value was 4.1, the residual phenol amount in the resin was 300 ppm, and the residual DPC amount was 50 ppm. The obtained NMR chart is shown in Figure 1.

[0099] (Example 2) As raw materials, 17.77 g (0.033 mol) of BNEF, 18.72 g (0 .050 mol) of BHEBN, 10.04 g (0.017 mol) of 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl ene]fluorene (hereinafter sometimes abbreviated as "BPPEF"), 21.70 g (0.101 -2 mol / L sodium hydrogen carbonate aqueous solution of 32 μl (8.0×10 -7 mol, that is, 8.0×10 mol per 1 mol of the total of dihydroxy compounds) were used, and the same operation as in Example 1 was performed -6 except for this. was carried out.

[0100] The physical property values of the obtained resin are shown in Table 2. Also, the ratio of the H 1 -NMR spectrum of the resin was Upon confirmation, (peak integration value of 4.75 - 4.69 ppm) / (peak integration value of 4.85 - 2.80 ppm) × 100 = not detected, (peak integration value of 4.59 - 4.55 ppm) / (peak integration value of 4.85 - 2.80 ppm) × 100 = 0.068, (peak integration value of 3.62 - 3.2 6 ppm) / (peak integration value of 4.85 - 2.80 ppm) × 100 = 0.1 84, (peak integration value of 4.83 - 4.76 ppm) / (peak integration value of 4.85 - 2.80 ppm) × 100 = 0.022, and the b value is 4.2, the residual phenol amount in the resin is 30 0 ppm, and the residual DPC amount is 50 ppm. The obtained NMR chart is shown in Figure 2. (Example 3)

[0101] (Example 3) As raw materials, 8.08 g (0.015 mol) of BNEF, 50.21 g (0 .085 mol) of BPPEF, 21.70 g (0.101 mol) of DPC, and 2.5×10 -2 mol / liter of sodium bicarbonate aqueous solution 32 μl (8.0×10 -7 mol, that is, for a total of 1 mol of dihydro xy compounds, 8.0×10 -6 mol) were used, and the same operations as in Example 1 were performed. The physical property values of the obtained resin are shown in Table 2.

[0102] (Example 4) As raw materials, 29.62 g (0.055 mol) of BNEF, 26.58 g ( 0.045 mol) of BPPEF, 21.70 g (0.101 mol) of DPC, and 2.5×10 -2 mol / liter of sodium bicarbonate aqueous solution 32 μl (8.0×10 -7 mol, that is, for a total of 1 mol of dihydro xy compounds, 8.0×10 -6 mol) were used, and otherwise the same operations as in Example 1 were performed. ​​The same procedure was repeated. The physical properties of the resulting resin are shown in Table 2.

[0103] Example 5 As raw materials, 40.40 g (0.075 mol) of BNEF and 14.77 g ( 0.025 mol), 21.70 g (0.101 mol) of DPC, and 2.5 × 10 -2 Mole 32 μl (8.0 × 10 -7 Mole, i.e., dihydride 8.0×10 for 1 mole of total alkoxy compounds -6 The same procedure as in Example 1 was repeated except that 100 moles of ethyl acetate was used. The same procedure was repeated. The physical properties of the resulting resin are shown in Table 2.

[0104] Example 6 The raw materials were 8.08 g (0.015 mol) of BNEF and 18.72 g (0. 050 mol), BPEF 15.35 g (0.035 mol), DPC 21.70 g (0. 101 moles), and 2.5 x 10 -2 32μ moles / liter of sodium bicarbonate solution l(8.0×10 -7 moles, i.e., 8.0 x moles per mole of dihydroxy compounds in total 10 -6 The same procedure as in Example 1 was carried out except that a 100% ethylenediaminetetraacetate (100% by weight) was used. The physical properties of the obtained resin were As shown in Table 2.

[0105] Example 7 As raw materials, 29.62 g (0.055 mol) of BNEF and 13.11 g (0 .035 mol), BPEF 4.39g (0.010 mol), DPC 21.70g (0. 101 moles), and 2.5 x 10 -2 32μ moles / liter of sodium bicarbonate solution l(8.0×10 -7 moles, i.e., 8.0 x moles per mole of dihydroxy compounds in total 10 -6 The same operations as in Example 1 were carried out except that 0.075 mol of BNEF was used. The physical property values of the obtained resin are shown in Table 2.

[0106] (Example 8) As raw materials, 40.40 g (0.075 mol) of BNEF, 7.49 g (0. 020 mol) of BHEBN, 2.19 g (0.005 mol) of BPEF, 21.70 g (0.10 1 mol), and 32 μl of an aqueous sodium hydrogen carbonate solution with a concentration of 2.5×10 -2 mol / liter ( 8.0×10 -7 mol, that is, 8.0×10 -6 mol) were used. The same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 2 as follows.

[0107] (Example 9) As raw materials, 8.08 g (0.015 mol) of BNEF, 16.85 g (0. 045 mol) of BHEBN, 23.63 g (0.040 mol) of BPPEF, 21.70 g (0. 101 mol), and 32 μ -2 l of an aqueous sodium hydrogen carbonate solution with a concentration of 2.5×10 mol / liter (8.0×10 -7 mol, that is, 8.0× 10 -6 mol) were used. The same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 2.

[0108] (Example 10) As raw materials, 29.62 g (0.055 mol) of BNEF, 14.98 g (0 .040 mol) of BHEBN, 2.95 g (0.005 mol) of BPPEF, 21.70 g (0. 101 mol), and 2.5×10 -232 μl of an aqueous sodium hydrogen carbonate solution at a molarity of l (8.0×10 -7 moles, that is, 8.0× 10 -6 moles) were used, and the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 2.

[0109] (Example 11) As raw materials, 40.40 g (0.075 moles) of BNEF, 7.49 g (0. 020 moles) of BHEBN, 2.95 g (0.005 moles) of BPPEF, 21.70 g (0.1 01 moles) of DPC, and 32 μl of an aqueous sodium hydrogen carbonate solution at a molarity of 2.5×10 -2 moles / liter (8.0×10 -7 moles, that is, 8.0×1 0 -6 moles) were used, and the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 2.

[0110] (Example 12) As raw materials, 10.77 g (0.020 moles) of BNEF and 29.95 g (0 .080 moles) of BHEBN were used, and the same operations as in Example 1 were carried out except that BPEF was not used. The physical property values of the obtained resin are shown in Table 2.

[0111] (Example 13) As raw materials, 18.64 g (0.035 moles) of BNEF, 23.70 g (0 .063 moles) of BHEBN, 21.30 g (0.099 moles) of DPC, and 32 μl of an aqueous sodium hydrogen carbonate solution at a molarity of 2.5×10 -2 moles / liter (8.0×10 -7 moles, that is, dihydro xy compounds in total of 1 mole, 8.1×10 -6Except for using 29.28 g (0.054 mol) of BNEF, the same operations as in Example 12 were carried out. The physical property values of the obtained resin are shown in Table 2.

[0112] (Example 14) As raw materials, 29.28 g (0.054 mol) of BNEF, 16.41 g (0 .044 mol) of BHEBN, 21.30 g (0.099 mol) of DPC, and 32 μl (8.0×10 -2 mol / liter) of an aqueous sodium hydrogen carbonate solution were used. Except for using -7 8.0×10 mol, that is, 8.1×10 -6 mol) per 1 mol of the total of dihydroxy compounds, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 2. In addition, when the ratio of the H -NMR spectrum of the resin was confirmed, (peak integral value at 4.75 - 4.6 1 9 ppm) / (peak integral value at 4.85 - 2.80 ppm)×100 = not detected, and (peak integral value at 4.59 - 4.55 ppm) / (peak integral value at 4.85 - 2.80 ppm)×100 = not detected, (peak integral value at 3.62 - 3.26 ppm) / (peak integral value at 4.85 - 2 .80 ppm)×100 = 0.4925, (peak integral value at 4.83 - 4.76 ppm) / (peak integral value at 4.85 - 2.80 ppm)×100 = 0.023. The obtained NMR chart is shown in Figure 3. .80 ppm)×100 = 0.4925, (peak integral value at 4.83 - 4.76 ppm) / (peak integral value at 4.85 - 2 80 ppm)×100 = 0.023. The obtained NMR chart is shown in Figure 3. . The obtained NMR chart is shown in Figure 3.

[0113] (Example 15) As raw materials, 40.00 g (0.074 mol) of BNEF, 9.12 g (0. 024 mol) of BHEBN, 21.40 g (0.100 mol) of DPC, and 32 μl (8.0×10 -2 mol / l iter) of an aqueous sodium hydrogen carbonate solution were used. -7 8.0×10 For 1 mol of the total amount of Si compounds, 8.1×10 -6 mol) was used, and the same operation as in Example 1 was carried out except for this. The physical property values of the obtained resin are shown in Table 2.

[0114] (Example 16) As raw materials, 8.0 kg (14.85 mol) of BNEF, 7.5 kg (20. 03 mol) of BHEBN, 7.5 kg (12.70 mol) of BPPEF, 10.5 kg (49.0 2 mol), and 16 milliliters of an aqueous sodium hydrogen carbonate solution with a concentration of 2.5×10 -2 mol / L (4.0×10 mol, that is, 8. -4 4×10 mol) were placed in a 50 L reactor equipped with a stirrer and a distillation device, and heated to 180 °C under a nitrogen atmosphere of 760 mmHg. -6 After 30 minutes from the start of heating, complete dissolution of the raw materials was confirmed, and then stirring was carried out for 120 minutes under the same conditions. Then, while adjusting the degree of vacuum to 200 mmHg, the temperature was raised to 200 °C at a rate of 60 °C / hr. At this time, the distillation start of the by-produced phenol was confirmed. Then, the reaction was carried out while maintaining at 200 °C for 20 minutes. Further, the temperature was raised to 230 °C at a rate of 75 °C / hr, and 10 minutes after the completion of the temperature rise, while maintaining at that temperature, the degree of vacuum was reduced to 1 mmHg or less over 2 hours Then, the temperature was raised to 245 °C at a rate of 60 °C / hr, and stirring was carried out for another 40 minutes. After the reaction was completed, nitrogen was introduced into the reactor to return to normal pressure, and the produced polycarbonate resin was pelletized and taken out. The b value of the obtained resin was 4. 2, the residual phenol amount in the resin was 100 ppm, the residual DPC amount was 50 ppm, the residual BHE BN was 20 ppm, and the residual BPPEF was 5 ppm.

[0115] (Example 17)​​ As raw materials, 6.9 kg (12.81 mol) of BNEF, 9.3 kg (24. 84 mol) of BHEBN, 5.9 kg (9.99 mol) of BPPEF, 10.5 kg (49.02 mol), and 16 ml (4.0×10 -2 mol, that is, 8.4×10 mol) of an aqueous sodium hydrogen carbonate solution with a concentration of 2.5×10 -4 mol / liter were used. Except for this, the same operations as in Example 16 were performed, and the produced polycarbonate resin was pelletized and taken out. The b value of the obtained resin was 2.7, the residual phenol -6 amount in the resin was 200 ppm, the residual DPC amount was 160 ppm, the residual BHEBN was 15 ppm, and the residual BPPEF was 5 ppm.

[0116] (Comparative Example 1) As raw materials, 28.05 g (0.075 mol) of BHEBN, 10.96 g (0 .025 mol) of BPEF, 21.70 g (0.101 mol) of DPC, and 32 μl (8.0×10 -2 mol, that is, 8.0×10 mol) of an aqueous sodium hydrogen carbonate solution with a concentration of 2.5×10 -7 mol / liter were used. Except for this, the same operations as in Example 1 were performed. -6

[0117] The physical property values of the obtained resin are shown in Table 2. Also, when the ratio of the H 1 -NMR spectrum of the resin was confirmed, (peak integral value at 4.75 - 4.69 ppm) / (peak integral value at 4.85 - 2.80 pp m)×100 = 1.013, (peak integral value at 4.59 - 4.55 ppm) / (peak integral value at 4.85 - 2.80 ppm)×100 = not detected, (3.62 - 3.26 ppm peak integral value) / (4.85~2.80ppm peak integral value)×100=1.61 5. (Peak integral value from 4.83 to 4.76 ppm) / (Peak integral value from 4.85 to 2.80 ppm) The b value was 5.3.

[0118] Comparative Example 2 As raw materials, 28.05 g (0.075 mol) of BHEBN and 14.77 g ( 0.025 mol), 21.70 g (0.101 mol) of DPC, and 2.5 × 10 -2 Mole 32 μl (8.0 × 10 -7 Mole, i.e., dihydride 8.0×10 for 1 mole of total alkoxy compounds -6 The same procedure as in Example 1 was repeated except that 100 moles of ethyl acetate was used. The same operation was carried out.

[0119] The physical properties of the resin obtained are shown in Table 2. 1 -NMR spectrum ratio After checking, the peak integral value of 4.75-4.69 ppm was calculated as (4.85-2.80 ppm) / (4.75-4.69 ppm). m peak integral value) × 100 = no detection, (4.59 to 4.55 ppm peak integral value) / ( 4.85~2.80ppm peak integral value) × 100 = 1.120, 0.021, (3.6 2~3.26ppm peak integral value) / (4.85~2.80ppm peak integral value)×10 0=1.570, (peak integral value from 4.83 to 4.76 ppm) / (4.85 to 2.80 ppm m) × 100 = not detected, and the b value was 6.0.

[0120] Comparative Example 3 The raw materials were 5.6 kg (12.81 mol) of BPEF and 9.3 kg (24. 84 mol), 5.9 kg of BPPEF (9.99 mol), 10.5 kg of DPC (49.02 mol), and 16 milliliters of a 2.5×10 -2 mol / liter aqueous sodium hydrogen carbonate solution (4.0×10 -4 mol, that is, 8.4×10 ×10 -6 mol) were used, and the same operations as in Example 16 were carried out. The produced polycarbonate resin was pelletized and taken out. The b value of the obtained resin was 4.1. The physical property values of the obtained resin are shown in Table 2.

[0121] [Table 2]

Claims

1. A method for producing a polycarbonate resin, comprising: performing melt polycondensation of a monomer composition of a polycarbonate containing a compound represented by the following general formula (4) and a compound represented by the following general formula (5) and a carbonic acid diester; 【Chemical 1】 (In general formula (4), X represents an alkylene group having 1 to 4 carbon atoms, and a and b each independently represent an integer of 1 to 10.) 【Chemical 2】 (In general formula (5), Y represents an alkylene group having 1 to 4 carbon atoms, and c and d each independently represent an integer of 1 to 10.) The monomer composition contains a compound in which either a or b in the compound of general formula (4) is 0, and the content thereof is 1000 ppm or less in the monomer composition containing the compound of general formula (4).

2. The method according to claim 1, comprising performing melt polycondensation using a transesterification catalyst selected from an alkali metal compound, an alkaline earth metal compound, and a nitrogen-containing compound.

3. The method according to claim 2, wherein the transesterification catalyst is selected from sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenylborohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, the disodium salt, dipotassium salt, dicesium salt or dilithium salt of bisphenol A, the sodium salt, potassium salt, cesium salt or lithium salt of phenol, and combinations thereof.

4. The transesterification catalyst is used in a ratio of 1×10 －７ to 1×10 －４ moles per 1 mole of the total dihydroxy compound, according to the method of claim 2 or 3.

5. The method according to any one of claims 1 to 4, wherein the melt polycondensation is carried out at a temperature of 180 to 245°C.

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