Bisphenol composition and polycarbonate resin

Abstract

To provide a bisphenol composition that excels in methanol dissolution color, molten color difference, thermal color tone stability, and thermal decomposition stability.SOLUTION: Provided is a bisphenol composition that has a bisphenol content of at least 95 mass% and contains at least 200 ppm by mass of a compound represented by general formula (II). Also provided is a polycarbonate resin production method using the bisphenol composition. In general formula (II), one of R21 and R22 represents a hydrogen atom and the other represents a methyl group. R23 to R25 each independently represent a hydrogen atom or a C1-20 alkyl group. R23, R24 and R25 may have a bond or a crosslink between two of the groups.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a bisphenol composition, a polycarbonate resin, and a method for producing the same. The bisphenol composition of the present invention is useful as a raw material for resins such as polycarbonate resins, epoxy resins, and aromatic polyester resins, as well as an additive such as a curing agent, a color developer, an anti-fading agent, and other disinfectants, antibacterial and antifungal agents. [Background technology]

[0002] Bisphenols are useful as raw materials for polymeric materials such as polycarbonate resins, epoxy resins, aromatic polyester resins, etc. Known representative bisphenols include, for example, 2,2-bis(4-hydroxyphenyl)propane and 2,2-bis(4-hydroxy-3-methylphenyl)propane (Patent Documents 1 and 2).

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 62-138443 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-40376

[0004] Polycarbonate resin, a typical application of bisphenol, is required to be colorless and transparent. The color tone of polycarbonate resin is greatly influenced by the color tone of the raw material. Therefore, the color tone of the raw material, bisphenol, is also required to be colorless. Since it is difficult to directly quantify the color of bisphenol, in the present invention, bisphenol is dissolved in methanol, the color difference is quantified, and this color tone is called the "methanol-dissolved color."

[0005] In the production of polycarbonate resins, particularly in the melt process, bisphenols are melted to produce polycarbonate resins, which expose them to high temperatures, and therefore thermal color stability of the bisphenols is also required. In the present invention, this color tone is referred to as "melt color difference."

[0006] In the production of polycarbonate resins, the polymerization reaction is carried out after melting the bisphenol, and therefore thermal color stability is also required before the start of polymerization. In the present invention, this color tone is referred to as "thermal color tone stability."

[0007] In the production of polycarbonate resin, if bisphenol is thermally decomposed before the start of polymerization, the amount of bisphenol will decrease, and the ratio of the amount of bisphenol to the raw material diphenyl carbonate will deviate from the specified ratio, making it impossible to obtain a polycarbonate resin with the desired molecular weight. Therefore, thermal stability of bisphenol is also required. In the present invention, this stability is referred to as "thermal decomposition stability."

[0008] Polycarbonate resins having a designed molecular weight and good color tone are required. To produce such polycarbonate resins, bisphenols as raw materials are required that have excellent methanol solubility color, melt color difference, thermal color stability, and thermal decomposition stability. Summary of the Invention

[0009] An object of the present invention is to provide a bisphenol composition that exhibits excellent methanol dissolution color, melt color difference, thermal color stability, and thermal decomposition stability. Another object of the present invention is to provide a polycarbonate resin that exhibits excellent color using the bisphenol composition.

[0010] The present inventors have found that a bisphenol composition containing a specific compound in a specified proportion has excellent methanol solubility color, melt color difference, thermal color stability, and thermal decomposition stability, and that a polycarbonate resin containing a specified proportion of structural units derived from this specific compound has excellent color tone.

[0011] The gist of the first aspect of the present invention lies in the following [1] to

[14] .

[0012] [1] A bisphenol composition containing 95% by mass or more of bisphenol and 200 ppm by mass or more of a compound represented by the following general formula (II):

[0013] [ka]

[0014] In general formula (II), R 21 and R 22 is a methyl group or a hydrogen atom, and R 21 If is a hydrogen atom, R 22 is a methyl group, and R 21 If R is a methyl group 22 is a hydrogen atom. R 23 ~R 25 R is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 23 and R 24 and R 25 may be bonded or bridged to each other between the two groups.

[0015] [2] The bisphenol composition according to [1], wherein the bisphenol is a bisphenol represented by the following general formula (I):

[0016] [ka]

[0017] In general formula (I), R 11 R is a halogen atom, an alkyl group, an alkoxy group, or an aryl group. 12 ~R 14 R are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group. 15 and R 16 R are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an aryl group. 15 and R 16 may be bonded or bridged to each other between the two groups, provided that R 15 and R16 and bonded or bridged to adjacent carbon atoms are excluded.

[0018] [3] The bisphenol composition according to [1] or [2], containing 5000 mass ppm or less of the compound represented by the general formula (II).

[0019] [4] The bisphenol composition according to any one of [1] to [3], wherein the compound represented by the general formula (II) is 1-(4-hydroxy-3-methylphenyl)-6-hydroxy-1,3,3,7-tetramethylindan.

[0020] [5] The bisphenol composition according to any one of [1] to [4], wherein the bisphenol composition has a methanol-dissolved color (Hazen color scale) of 2 or less.

[0021] [6] The bisphenol composition according to any one of [1] to [5], wherein the iron content in the bisphenol composition is 0.5 ppm by mass or less.

[0022] [7] The bisphenol composition according to any one of [1] to [6], wherein the aluminum content in the bisphenol composition is 0.1 ppm by mass or less.

[0023] [8] The bisphenol composition according to any one of [1] to [7], wherein the bisphenol is 2,2-bis(4-hydroxy-3-methylphenyl)propane and / or bis(4-hydroxy-3-methylphenyl)cyclohexane.

[0024] [9] The method for producing a bisphenol composition according to any one of [1] to [8], wherein the compound represented by the general formula (II) is produced as a by-product during the production of bisphenol.

[0025]

[10] A method for producing a polycarbonate resin using the bisphenol composition according to any one of [1] to [8].

[0026]

[11] A polycarbonate resin having at least a repeating structural unit represented by the following general formula (A), wherein a compound obtained by alkaline hydrolysis of the polycarbonate resin contains a bisphenol represented by the following general formula (I) and a compound represented by the following general formula (II), and the content of the compound represented by the following general formula (II) obtained by alkaline hydrolysis is 5 ppm by mass or more relative to the polycarbonate resin:

[0027] [ka]

[0028] In general formula (A), R 1 ~R 6 R are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group, and the alkyl group, alkoxy group, and aryl group may be substituted or unsubstituted. 5 and R 6 may be bonded or bridged to each other between two groups, and R 5 and R 6 and may be bonded together with adjacent carbon atoms to form a cycloalkylidene group which may contain heteroatoms.

[0029] [ka]

[0030] In general formula (I), R 11 R is a halogen atom, an alkyl group, an alkoxy group, or an aryl group. 12 ~R 14 R are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group. 15 and R 16 R are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an aryl group. 15 and R 16 may be bonded or bridged to each other between the two groups, provided that R 15 and R16 and bonded or bridged to adjacent carbon atoms are excluded.

[0031] [ka]

[0032] In general formula (II), R 21 and R 22 is a methyl group or a hydrogen atom, and R 21 If is a hydrogen atom, R 22 is a methyl group, and R 21 If R is a methyl group 22 is a hydrogen atom. R 23 ~R 25 R is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 23 and R 24 and R 25 may be bonded or bridged to each other between the two groups.

[0033]

[12] The polycarbonate resin according to

[11] , wherein the compound represented by the general formula (II) is 1-(4-hydroxy-3-methylphenyl)-6-hydroxy-1,3,3,7-tetramethylindan.

[0034]

[13] The polycarbonate resin according to

[11] or

[12] , wherein the compound obtained by alkaline hydrolysis of the polycarbonate resin contains 2,2-bis(4-hydroxy-3-methylphenyl)propane and / or 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane.

[0035]

[14] The polycarbonate resin according to any one of

[11] to

[13] , which has a viscosity average molecular weight of 15,000 or more and 35,000 or less.

[0036] The second aspect of the present invention resides in the following

[15] to

[20] .

[0037]

[15] A bisphenol composition containing 95% by mass or more of bisphenol and 10 ppm by mass or more of 1-(4-hydroxy-3-methylphenyl)-6-hydroxy-1,3,3,5-tetramethylindan.

[0038]

[16] The bisphenol composition according to

[15] , containing 1-(4-hydroxy-3-methylphenyl)-6-hydroxy-1,3,3,5-tetramethylindan in an amount of 200 ppm by mass or less.

[0039]

[17] The bisphenol composition according to

[15] or

[16] , wherein the bisphenol is 2,2-bis(4-hydroxy-3-methylphenyl)propane.

[0040]

[18] The method for producing a bisphenol composition according to any one of

[15] to

[17] , wherein 1-(4-hydroxy-3-methylphenyl)-6-hydroxy-1,3,3,5-tetramethylindan is by-produced during the production of bisphenol.

[0041]

[19] A method for producing a polycarbonate resin using the bisphenol composition according to any one of

[15] to

[17] .

[0042]

[20] The method for producing a polycarbonate resin according to

[19] , which produces a polycarbonate resin having a viscosity average molecular weight of 15,000 or more and 35,000 or less.

[0043] In this specification, the first and second aspects are collectively referred to as "the present invention." [Effects of the Invention]

[0044] According to the present invention, by containing a specific compound in a predetermined ratio, a bisphenol composition is provided which has good methanol dissolution color, melt color difference, thermal color stability, and thermal decomposition stability. According to the present invention, this bisphenol composition is used to provide a polycarbonate resin with excellent color tone. [Brief explanation of the drawings]

[0045] [Figure 1] FIG. 1 is a chart showing the 1H NMR spectrum of the high performance liquid chromatography fraction (retention time: 28.28 minutes) of the bisphenol C composition obtained in Example I-1. [Figure 2] FIG. 2 is a chart showing the 13 C NMR spectrum of the high performance liquid chromatography fraction (retention time: 28.28 minutes) of the bisphenol C composition obtained in Example I-1. [Figure 3] FIG. 3 is a chart showing the HH COSY spectrum of the high performance liquid chromatography fraction (retention time: 28.28 minutes) of the bisphenol C composition obtained in Example I-1. [Figure 4] FIG. 4 is a chart showing the HMQC spectrum of the high performance liquid chromatography fraction (retention time: 28.28 minutes) of the bisphenol C composition obtained in Example I-1. [Figure 5] FIG. 5 is a chart showing the HMBC spectrum of the high performance liquid chromatography fraction (retention time: 28.28 minutes) of the bisphenol C composition obtained in Example I-1. [Figure 6] FIG. 6 is a chart showing the DEPT135 spectrum of a high performance liquid chromatography fraction (retention time: 28.28 minutes) of the bisphenol C composition obtained in Example I-1. [Figure 7] FIG. 7 is a chart showing the 1H NMR spectrum of the high performance liquid chromatography fraction (retention time: 28.87 minutes) of the bisphenol C composition obtained in Example II-1. [Figure 8] FIG. 8 is a chart showing the 13C NMR spectrum of the high performance liquid chromatography fraction (retention time: 28.87 minutes) of the bisphenol C composition obtained in Example II-1. [Figure 9] FIG. 9 is a chart showing the HH COSY spectrum of the high performance liquid chromatography fraction (retention time: 28.87 minutes) of the bisphenol C composition obtained in Example II-1. [Figure 10] FIG. 10 is a chart showing the HMQC spectrum of the high performance liquid chromatography fraction (retention time: 28.87 minutes) of the bisphenol C composition obtained in Example II-1. [Figure 11] FIG. 11 is a chart showing the HMBC spectrum of the high performance liquid chromatography fraction (retention time: 28.87 minutes) of the bisphenol C composition obtained in Example II-1. [Figure 12] FIG. 12 is a chart showing the DEPT135 spectrum of the high performance liquid chromatography fraction (retention time: 28.87 minutes) of the bisphenol C composition obtained in Example II-1. DETAILED DESCRIPTION OF THE INVENTION

[0046] The following is a detailed description of an embodiment of the present invention. The following description of the components is an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as it does not deviate from the gist of the present invention. In this specification, when the expression "to" is used, it is intended to be used as an expression that includes the numerical values ​​or physical property values ​​before and after it.

[0047] [First embodiment of bisphenol composition and polycarbonate resin] [Bisphenol composition] The bisphenol composition of the first embodiment is characterized by containing 95% by mass or more of bisphenol and 200 ppm by mass or more of a compound represented by the following general formula (II) (hereinafter, sometimes referred to as "compound (II)"):

[0048] [ka]

[0049] In general formula (II), R 21 and R 22 is a methyl group or a hydrogen atom, and R 21 If is a hydrogen atom, R 22 is a methyl group, and R 21If R is a methyl group 22 is a hydrogen atom. R 23 ~R 25 R is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 23 and R 24 and R 25 may be bonded or bridged to each other between the two groups.

[0050] The content of compound (II) in the bisphenol composition of the first embodiment is preferably 250 ppm by mass or more, and preferably 5000 ppm by mass or less, more preferably 3000 ppm by mass or less, and even more preferably 1400 ppm by mass or less.

[0051] If the content of compound (II) in the bisphenol composition is less than the above lower limit, it is impossible to obtain a bisphenol composition having good methanol dissolution color, melt color difference, thermal color stability, and thermal decomposition stability. If the content of compound (II) in the bisphenol composition is the above or less, the following problems can be suppressed. 1) When producing polycarbonate resin, the molar ratio with diphenyl carbonate is off, which affects the polymerization reaction. 2) It reduces the brittleness (Izod) of polycarbonate resin and the high surface hardness that is characteristic of polycarbonate resin containing structural units derived from bisphenol (I), as described below.

[0052] Preferred examples of the compound (II) contained in the bisphenol composition of the first embodiment include 1-(4-hydroxy-3-methylphenyl)-6-hydroxy-1,3,3,7-tetramethylindan represented by the following structural formula (IIa) (hereinafter referred to as "indan C1") and 1-(4-hydroxy-3-methylphenyl)-6-hydroxy-1,3,3,5-tetramethylindan represented by the following structural formula (IIb) (hereinafter referred to as "indan C2").

[0053] [ka]

[0054] Compound (II) can be detected and quantified using a standard reversed-phase column with a particle size of 3 μm for high-speed analysis.

[0055] The content of compound (II) in the bisphenol composition can be adjusted by adding an appropriate amount of compound (II) to purified bisphenol that does not contain or contains a low concentration of compound (II). As will be described later, compound (II) can be produced together with bisphenol in the reaction system during the production of bisphenol, and a bisphenol product containing compound (II) can be prepared as the bisphenol composition of the first embodiment.

[0056] <Bisphenol> The bisphenol contained in the bisphenol composition of the first embodiment (hereinafter may be referred to as "bisphenol of the first embodiment") is usually a compound represented by the following general formula (1). The bisphenol of the first embodiment is preferably a bisphenol represented by the following general formula (I) (hereinafter may be referred to as "bisphenol (I)").

[0057] [ka]

[0058] R in general formula (1) 1 ~R 6 is R in general formulas (3) and (4) described below. 1 ~R 6 and preferred examples and specific examples thereof are as explained in the description of general formulas (3) and (4) below.

[0059] [ka]

[0060] In general formula (I), R 11 R is a halogen atom, an alkyl group, an alkoxy group, or an aryl group. 12 ~R 14R are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group. 15 and R 16 R are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an aryl group. 15 and R 16 may be bonded or bridged to each other between the two groups, provided that R 15 and R 16 and bonded or bridged to adjacent carbon atoms are excluded.

[0061] Specific examples of the bisphenol represented by the general formula (1) or the general formula (I) include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 3,3-bis(4-hydroxyphenyl)pentane, 3,3-bis(4-hydroxy-3-methylphenyl)pentane, 2 ,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxy-3-methylphenyl)pentane, 3,3-bis(4-hydroxyphenyl)heptane, 3,3-bis(4-hydroxy-3-methylphenyl)heptane, 2,2-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxy-3-methylphenyl)heptane, 4,4-bis(4-hydroxyphenyl)heptane, 4,4-bis(4-hydroxy-3-methylphenyl)heptane, and the like, but are not limited to these.

[0062] Among these, the bisphenol of the first embodiment is preferably 2,2-bis(4-hydroxy-3-methylphenyl)propane or 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, and particularly preferably 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C).

[0063] The bisphenol composition of the first embodiment contains 95% by mass or more, preferably 99% by mass or more, and more preferably 99.5% by mass or more of such bisphenol. If the bisphenol content is less than the above lower limit, it is not preferable for use as bisphenol. The upper limit of the bisphenol content in the bisphenol composition of the first embodiment is usually about 99.9% by mass, from the viewpoints of ensuring the content of compound (II), production costs, adjusting the ratio of substances relative to diphenyl carbonate in the polycarbonate resin production reaction, and mechanical properties of the polycarbonate resin, such as surface hardness and brittleness.

[0064] Bisphenol detection and quantification can be performed using standard high-performance analytical reversed-phase columns.

[0065] <Color of bisphenol composition dissolved in methanol> The color of a bisphenol composition dissolved in methanol is used to evaluate the color tone of the bisphenol composition at room temperature. The lower the Hazen color number of the methanol-dissolved color of the bisphenol composition, the better the color tone of the bisphenol composition (closer to white). Causes that deteriorate the methanol-dissolved color of the bisphenol composition include the inclusion of organic coloring components and metals.

[0066] The color of a bisphenol composition dissolved in methanol is measured at room temperature (approximately 20°C) after dissolving the bisphenol composition in methanol to form a homogeneous solution. Measurement methods include a method of visually comparing the Hazen color number with a standard solution, or a method of measuring the Hazen color number using a colorimeter such as the SE6000 manufactured by Nippon Denshoku Industries Co., Ltd. The mass ratio of the solvent methanol, bisphenol, and solvent used here is preferably selected appropriately depending on the type of bisphenol.

[0067] The Hazen color scale of the methanol-dissolved color of the bisphenol composition of the first embodiment is preferably 2 or less, more preferably 1 or less, and particularly preferably 0 or less.

[0068] <Melting color difference of bisphenol composition> The melt color difference of a bisphenol composition is used to evaluate the color tone of the bisphenol composition at a temperature close to the polymerization temperature of polycarbonate. The temperature for measuring the melt color difference is the melting point of bisphenol + 50°C. The lower the Hazen color number of the melt color difference of a bisphenol composition, the better the color tone of the bisphenol composition (closer to white). Causes that worsen the melt color difference of a bisphenol composition include the inclusion of organic coloring components and metals, as well as components that become colored by heating.

[0069] The melt color difference of the bisphenol composition is measured by melting the bisphenol composition at a temperature close to the polymerization temperature and allowing the temperature to stabilize. The measurement method includes a visual comparison with a standard solution of Hazen color number, or a method of measuring the Hazen color number using a color difference meter such as the "SE6000" manufactured by Nippon Denshoku Industries Co., Ltd.

[0070] The Hazen color number of the bisphenol composition of the first embodiment is preferably 40 or less, more preferably 30 or less, and particularly preferably 20 or less.

[0071] <Thermal color stability of bisphenol composition> The thermal color stability of a bisphenol composition, like the melt color difference of a bisphenol composition, is evaluated by holding the composition at a temperature close to the polymerization temperature of polycarbonate for a predetermined time. The measurement temperature for the thermal color stability of a bisphenol composition is the melting point of bisphenol + 50°C.

[0072] The lower the Hazen color number, the better the thermal color stability of the bisphenol composition. Causes of deterioration of the thermal color stability of the bisphenol composition include not only the inclusion of organic coloring components and metals, but also components that color upon heating and acidic or basic substances at concentrations of about several ppm.

[0073] The thermal color stability of a bisphenol composition is measured by melting the bisphenol composition at a temperature close to the polymerization temperature and measuring the time until the temperature stabilizes. The thermal color stability of the bisphenol composition is maintained for 4 hours. Measurement methods include visual comparison with a standard Hazen color number solution, or measuring the Hazen color number using a color difference meter such as the SE6000 manufactured by Nippon Denshoku Industries Co., Ltd.

[0074] The Hazen color number of the bisphenol composition of the first embodiment is preferably 50 or less, more preferably 45 or less, and particularly preferably 35 or less.

[0075] <Thermal decomposition stability of bisphenol composition> The thermal decomposition stability of a bisphenol composition, like the thermal color stability of a bisphenol composition, is evaluated by holding the composition at a temperature close to the polymerization temperature of the polycarbonate for a predetermined period of time. The preferred measurement temperature for the thermal decomposition stability of a bisphenol composition is the melting point of bisphenol + 50°C. The thermal decomposition stability of a bisphenol composition is such that the smaller the amount of decomposition products produced, the more stable the bisphenol composition.

[0076] The decomposition products of the bisphenol composition in terms of thermal decomposition stability vary depending on the type of bisphenol, but include aromatic alcohols, which are raw materials for the bisphenol composition, and adducts of the aromatic alcohols with ketones or aldehydes, which are raw materials for the bisphenol composition. Causes of deterioration in the thermal decomposition stability of the bisphenol composition include organic coloring components and metal contamination, as well as components that become colored by heating and acidic or basic substances with concentrations of about several ppm.

[0077] Detection and quantification of the decomposition products of bisphenol compositions can be achieved using standard high performance analytical reversed phase columns.

[0078] The amount of isopropenyl cresol produced as a decomposition product of the bisphenol composition of the first embodiment, as measured in the Examples described below, is preferably 200 mass ppm or less.

[0079] The methanol-dissolved color of a bisphenol composition is a method for evaluating the color tone of the bisphenol composition itself. When the bisphenol composition is a final product, a bisphenol composition with a good methanol-dissolved color is important. Since polycarbonate resins inherit the color tone of their raw materials, a bisphenol composition with a good color tone is important for polycarbonate resins that are required to be colorless and transparent.

[0080] In the melt polymerization method, which is one of the methods for producing polycarbonate resins, the polymerization reaction is carried out at high temperatures, so the color tone of the bisphenol composition when melted (melt color difference of the bisphenol composition) and the color stability of the bisphenol composition in the molten state (thermal color stability of the bisphenol composition) are important. In this melt polymerization method, the bisphenol composition is kept in a molten state at a high temperature until the polymerization reaction begins. If the bisphenol composition decomposes at a high temperature in this melt polymerization method, the mass ratio of the bisphenol composition to diphenyl carbonate deviates from the specified mass ratio, making it difficult to obtain a polycarbonate resin with polymerization activity and a specified molecular weight. Therefore, resistance to thermal decomposition (thermal decomposition stability of the bisphenol composition) is important.

[0081] In particular, in order to produce a polycarbonate resin having a predetermined molecular weight and good color tone, the methanol-dissolved color of the bisphenol composition, the melt color difference of the bisphenol composition, the thermal color stability of the bisphenol composition, and the thermal decomposition stability of the bisphenol composition are important.

[0082] <Iron content in bisphenol composition> The iron content in the bisphenol composition of the first embodiment is preferably 0.5 ppm by mass or less, more preferably 0.4 ppm by mass or less, and particularly preferably 0.3 ppm by mass or less. Iron in the bisphenol composition has a structure in which bisphenol is coordinated, and therefore has absorption in the visible region. Therefore, the iron causes coloring of the bisphenol composition, and a high iron content deteriorates the methanol dissolution color and melt color difference. Because the iron exhibits catalytic activity, a high iron content deteriorates the thermal color stability and thermal decomposition stability. Therefore, the iron content in the bisphenol composition of the first embodiment is preferably equal to or less than the upper limit described above.

[0083] The iron in the bisphenol composition may be present as iron dissolved in the aromatic alcohol, which is the raw material for bisphenol, or as iron mixed in from the reaction tank or equipment above the reaction tank during the reaction to produce bisphenol. Depending on the form of the iron, this iron is appropriately removed by a purification method described below, such as repeated washing with water under acidic conditions or repeated washing with water under basic conditions.

[0084] The iron content in the bisphenol composition is measured by the method described in the Examples section below.

[0085] <Aluminum content in bisphenol composition> The aluminum content in the bisphenol composition of the first embodiment is preferably 0.1 ppm by mass or less, more preferably 0.09 ppm by mass or less, and particularly preferably 0.08 ppm by mass or less. The aluminum in the bisphenol composition has a structure in which bisphenol is coordinated, and therefore has absorption in the visible region. Therefore, the aluminum causes coloration of the bisphenol composition, and a high aluminum content deteriorates the methanol dissolution color and melt color difference. Because the aluminum exhibits catalytic activity, a high aluminum content deteriorates the thermal color stability and thermal decomposition stability. Therefore, the aluminum content in the bisphenol composition of the first embodiment is preferably equal to or less than the upper limit described above.

[0086] The aluminum in the bisphenol composition may originate from aluminum dissolved in the aromatic alcohol that is the raw material for bisphenol, or from aluminum oxide that is mixed in from the outside during the removal process after obtaining the bisphenol solid or during supply to a dryer, etc. Depending on the form of the aluminum, this aluminum is appropriately removed by a purification method described below, such as repeated washing with water under acidic conditions or repeated washing with water under basic conditions.

[0087] The aluminum content in the bisphenol composition is measured by the method described in the Examples section below.

[0088] <Method of producing bisphenol composition> There are no particular limitations on the method for producing the bisphenol composition of the first embodiment containing 95% by mass or more of bisphenol and compound (II) in a predetermined proportion, but examples thereof include the following methods. (1) A method of adding a predetermined amount of compound (II) to solid bisphenol (2) A method of adding a predetermined amount of compound (II) to molten bisphenol (3) A method for obtaining a bisphenol product containing compound (II) by producing compound (II) during the production of bisphenol.

[0089] In the methods (1) and (2) of adding compound (II) to solid or molten bisphenol, compound (II) must be prepared separately. Therefore, the method (3) of by-producing compound (II) in the reaction system for producing bisphenol and allowing the bisphenol product to contain compound (II) in a predetermined ratio is preferred.

[0090] When the amount of compound (II) by-produced in the bisphenol reaction system is too large, the obtained bisphenol product can be further purified by crystallization, suspension washing, sprinkle washing, or the like to remove a portion of compound (II) contained in the bisphenol product, thereby controlling the amount of compound (II) to be within the specified range of the first aspect.

[0091] <Method for obtaining a bisphenol product containing compound (II)> As a method for producing a bisphenol composition of the first embodiment by producing compound (II) together with bisphenol in a reaction system during the production of bisphenol and thereby obtaining a bisphenol product containing compound (II), there may be mentioned a method for producing bisphenol by condensing a ketone or aldehyde with an aromatic alcohol in the presence of an acid catalyst and a thiol co-catalyst. According to this method, compound (II) can be produced in the reaction system. This method will be described below.

[0092] In this process, bisphenols are produced by condensing an aromatic alcohol with a ketone or aldehyde in the presence of an acid catalyst. The reaction for producing this bisphenol proceeds according to the following reaction formula (2).

[0093] [ka]

[0094] In reaction formula (2), R 1 ~R 6 has the same meaning as in general formula (1).

[0095] (aromatic alcohol) The raw material aromatic alcohol used in the production of bisphenol is usually a compound represented by the following general formula (3).

[0096] [ka]

[0097] In general formula (3), R 1 ~R 4 R each independently includes a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, etc. The alkyl group, alkoxy group, aryl group, etc. may be substituted or unsubstituted. 1 ~R4 Examples of the alkyl group include a hydrogen atom, a fluoro group, a chloro group, a bromo group, an iodo group, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an i-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, and a t-butoxy group. Examples of such groups include an oxy group, an n-pentyloxy group, an i-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, an n-undecyloxy group, an n-dodecyloxy group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecyl group, a benzyl group, a phenyl group, a tolyl group, and a 2,6-dimethylphenyl group.

[0098] Of these, R 2 and R 3 If R is sterically bulky, the condensation reaction does not proceed easily, so it is preferably a hydrogen atom. 1 ~R 4 More preferably, R are each independently a hydrogen atom or an alkyl group. 1 ,R 4 are each independently a hydrogen atom or an alkyl group, and R 2 ,R 3 is more preferably a hydrogen atom.

[0099] Specific examples of the compound represented by general formula (3) include phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, methoxyphenol, ethoxyphenol, propoxyphenol, butoxyphenol, benzylphenol, and phenylphenol.

[0100] Among these, any one selected from the group consisting of phenol, cresol, and xylenol is preferred, cresol or xylenol is more preferred, and cresol is even more preferred.

[0101] (ketone or aldehyde) The starting ketone or aldehyde used in the production of bisphenol is usually a compound represented by the following general formula (4).

[0102] [ka]

[0103] In general formula (4), R 5 and R 6 R each independently includes a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, etc. The alkyl group, alkoxy group, aryl group, etc. may be substituted or unsubstituted. 5 ,R 6 Examples of the alkyl group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an i-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a t-butoxy group, an n -pentyloxy group, i-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, benzyl group, phenyl group, tolyl group, and 2,6-dimethylphenyl group.

[0104] R 5 and R 6 R may be bonded or bridged to each other between the two groups. 5 and R 6and may be bonded together with adjacent carbon atoms to form a cycloalkylidene group, which may contain heteroatoms. A cycloalkylidene group is a divalent group formed by removing two hydrogen atoms from one carbon atom of a cycloalkane.

[0105] R 5 and R 6 Examples of cycloalkylidene groups formed by bonding together with adjacent carbon atoms include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, 3,3,5-trimethylcyclohexylidene, cycloheptylidene, cyclooctylidene, cyclononylidene, cyclodecylidene, cycloundecylidene, cyclododecylidene, fluorenylidene, xanthonylidene, and thioxanthonylidene.

[0106] Specific examples of the compound represented by general formula (4) include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde, nonylaldehyde, decylaldehyde, undecylaldehyde, and dodecylaldehyde; ketones such as acetone, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, undecanone, and dodecanone; benzaldehyde, phenaldehyde, phenanthroline ... aryl alkyl ketones such as phenyl methyl ketone, phenyl ethyl ketone, phenyl propyl ketone, cresyl methyl ketone, cresyl ethyl ketone, cresyl propyl ketone, xylyl methyl ketone, xylyl ethyl ketone, and xylyl propyl ketone; cyclic alkane ketones such as cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cycloundecanone, and cyclododecanone; and the like. Of these, acetone is preferred.

[0107] In the condensation reaction of an aromatic alcohol with a ketone or aldehyde, if the molar ratio of the aromatic alcohol to the ketone or aldehyde is low, the ketone or aldehyde will polymerize, but if it is high, the aromatic alcohol will be lost unreacted. For these reasons, the molar ratio of the aromatic alcohol to the ketone or aldehyde is preferably 1.5 or more, more preferably 1.6 or more, and even more preferably 1.7 or more, and is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

[0108] The ketone and aldehyde may be supplied all at once or in portions. Since the reaction for producing bisphenol is an exothermic reaction, it is preferable to supply the ketone and aldehyde in portions, such as by adding them dropwise little by little.

[0109] (acid catalyst) Examples of acid catalysts used in the production of bisphenol include sulfuric acid, hydrochloric acid, hydrogen chloride gas, phosphoric acid, aromatic sulfonic acids such as p-toluenesulfonic acid, and aliphatic sulfonic acids such as methanesulfonic acid.

[0110] If the molar ratio of the acid catalyst to the ketone or aldehyde used in the condensation ((moles of acid catalyst / moles of ketone) or (moles of acid catalyst / moles of aldehyde)) is low, the acid catalyst is diluted with water by-produced as the condensation reaction proceeds, and the reaction takes a long time. If this molar ratio is high, the ketone or aldehyde may be polymerized. For these reasons, the molar ratio of the acid catalyst to the ketone or aldehyde used in the condensation is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more, and is preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less.

[0111] The acid catalyst is preferably any one selected from the group consisting of sulfuric acid, hydrochloric acid, hydrogen chloride gas, phosphoric acid, aromatic sulfonic acids such as p-toluenesulfonic acid, and aliphatic sulfonic acids such as methanesulfonic acid.

[0112] If the molar ratio of hydrogen chloride to ketone or aldehyde used in the reaction ((moles of hydrogen chloride / moles of ketone) or (moles of hydrogen chloride / moles of aldehyde)) is low, the hydrogen chloride will be diluted with water by-produced during the condensation reaction, requiring a long reaction time. If this molar ratio is high, the ketone or aldehyde may polymerize. For these reasons, the molar ratio of hydrogen chloride to ketone or aldehyde is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more, and is preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less.

[0113] Sulfuric acid is an acidic liquid with the chemical formula H2SO4. Generally, sulfuric acid is used as an aqueous solution diluted with water, and depending on its concentration, it is called concentrated sulfuric acid or dilute sulfuric acid. For example, dilute sulfuric acid is an aqueous solution of sulfuric acid with a mass concentration of less than 90% by mass.

[0114] If the concentration of sulfuric acid used (concentration of aqueous sulfuric acid solution) is low, the amount of water increases, making it difficult for the bisphenol production reaction to proceed, lengthening the reaction time for producing bisphenol, and making it difficult to efficiently produce bisphenol. Therefore, the concentration of sulfuric acid used is preferably 70% by mass or more, more preferably 75% by mass or more, and even more preferably 80% by mass or more. The upper limit of the concentration of sulfuric acid used is usually 99.5% by mass or less, or 99% by mass or less.

[0115] (thiol) In the production of bisphenols, a thiol can be used as a promoter in the condensation reaction of a ketone or aldehyde with an aromatic alcohol.

[0116] The use of a thiol as a co-catalyst, for example, in the production of 2,2-bis(4-hydroxy-3-methylphenyl)propane, has the effects of suppressing the production of the 24 isomer and increasing the selectivity for the 44 isomer, as well as enhancing the polymerization activity during the production of polycarbonate resin and improving the color tone of the resulting polycarbonate resin. Although the details of why the polymerization activity during the production of a polycarbonate resin is improved and the color tone of the resulting polycarbonate resin is improved are not clear, it is presumed that the use of a thiol can suppress the production of substances that inhibit the polymerization reaction for producing a polycarbonate resin and also suppress the production of substances that deteriorate the color tone.

[0117] Examples of thiols used as co-catalysts include mercaptocarboxylic acids such as mercaptoacetic acid, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, and 4-mercaptobutyric acid; alkyl thiols such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan (decanethiol), undecyl mercaptan (undecanethiol), dodecyl mercaptan (dodecanethiol), tridecyl mercaptan, tetradecyl mercaptan, and pentadecyl mercaptan; and aryl thiols such as mercaptophenol.

[0118] If the molar ratio of the thiol promoter to the ketone or aldehyde used in the condensation ((moles of thiol promoter / moles of ketone) or (moles of thiol promoter / moles of aldehyde)) is low, the effect of improving the reaction selectivity of bisphenol by using a thiol promoter cannot be obtained. If this molar ratio is high, the thiol promoter may be mixed into the bisphenol, resulting in a deterioration in quality. For these reasons, the molar ratio of the thiol promoter to the ketone and aldehyde is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and preferably 1 or less, more preferably 0.5 or less, even more preferably 0.1 or less.

[0119] The thiol promoter is preferably mixed with the ketone or aldehyde in advance before being subjected to the reaction. The method of mixing the thiol and the ketone or aldehyde may be to mix the thiol with the ketone or aldehyde, or to mix the thiol with the ketone or aldehyde. The method of mixing the mixed solution of thiol and ketone or aldehyde with the acid catalyst may be to mix the mixed solution of thiol and ketone or aldehyde with the acid catalyst, or to mix the mixed solution of thiol and ketone or aldehyde with the acid catalyst, but it is preferable to mix the mixed solution of thiol and ketone or aldehyde with the acid catalyst.Furthermore, it is more preferable to supply the mixed solution of thiol and ketone or aldehyde to the reaction vessel after supplying the acid catalyst and aromatic alcohol to the reaction vessel and then supplying the mixed solution of thiol and ketone or aldehyde to the reaction vessel and mixing them.

[0120] (organic solvent) In the production of bisphenol, an organic solvent is usually used to dissolve or disperse the bisphenol produced.

[0121] The organic solvent is not particularly limited as long as it does not inhibit the bisphenol production reaction, and examples thereof include aromatic hydrocarbons, aliphatic alcohols, and aliphatic hydrocarbons. Here, the aromatic alcohol, which is the substrate, and the bisphenol, which is the product, are removed from the organic solvent. These solvents may be used alone or in combination of two or more.

[0122] Examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, and mesitylene. These solvents may be used alone or in combination of two or more. After being used in the production of bisphenol, aromatic hydrocarbons can be recovered and purified by distillation or the like and reused. When reusing aromatic hydrocarbons, those with a low boiling point are preferred. One preferred aromatic hydrocarbon is toluene.

[0123] The aliphatic alcohol is an alkyl alcohol in which an alkyl group and a hydroxyl group are bonded. The aliphatic alcohol may be a monohydric aliphatic alcohol in which an alkyl group and one hydroxyl group are bonded, or a polyhydric aliphatic alcohol in which an alkyl group and two or more hydroxyl groups are bonded. The alkyl group may be linear or branched, and may be unsubstituted or may have some of the carbon atoms of the alkyl group substituted with oxygen atoms.

[0124] The aliphatic alcohol preferably has 12 or less carbon atoms, more preferably 8 or less, because as the number of carbon atoms increases, the alcohol becomes more lipophilic and less likely to mix with sulfuric acid, making it more difficult to produce the monoalkyl sulfate described below.

[0125] The aliphatic alcohol is preferably an alcohol in which an alkyl group and one hydroxyl group are bonded, more preferably an alcohol in which an alkyl group having 1 to 8 carbon atoms and one hydroxyl group are bonded, and even more preferably an alcohol in which an alkyl group having 1 to 5 carbon atoms and one hydroxyl group are bonded.

[0126] Specific examples of the aliphatic alcohol include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, n-pentanol, i-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, ethylene glycol, diethylene glycol, triethylene glycol, etc. One preferred aliphatic alcohol is methanol.

[0127] Examples of aliphatic hydrocarbons include linear hydrocarbons having 5 to 18 carbon atoms, such as n-pentane, n-hexane, n-heptane, and n-octane; branched hydrocarbons having 5 to 18 carbon atoms, such as isooctane; and cyclic hydrocarbons having 5 to 18 carbon atoms, such as cyclohexane, cyclooctane, and methylcyclohexane.

[0128] If the mass ratio of the organic solvent to the ketone or aldehyde used in the condensation ((mass of ketone / mass of organic solvent) or (mass of aldehyde / mass of organic solvent)) is too high, the ketone or aldehyde and the aromatic alcohol do not react easily, and the reaction takes a long time. If this mass ratio is too low, the polymerization of the ketone or aldehyde is promoted, and the resulting bisphenol may solidify. For these reasons, the mass ratio of the organic solvent to the ketone or aldehyde at the time of charging is preferably 0.5 or more, more preferably 1 or more, and is preferably 100 or less, more preferably 50 or less.

[0129] Dispersing the produced bisphenol in the organic solvent rather than completely dissolving it makes the bisphenol less likely to decompose. It is also preferable to use a solvent in which bisphenol has a low solubility, since this can reduce losses when recovering bisphenol from the reaction solution after the reaction is complete (for example, losses to the filtrate during crystallization). Examples of solvents in which bisphenol has a low solubility include aromatic hydrocarbons. For this reason, the organic solvent preferably contains aromatic hydrocarbons as a main component, and the organic solvent preferably contains 55% by mass or more of aromatic hydrocarbons, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0130] When the acid catalyst contains sulfuric acid, if the organic solvent contains an aliphatic alcohol, the sulfuric acid and the aliphatic alcohol react to produce a monoalkyl sulfate, and this monoalkyl sulfate can also provide catalytic activity. Therefore, when the acid catalyst contains sulfuric acid, the organic solvent is preferably an organic solvent containing an aliphatic alcohol. As the number of carbon atoms in an aliphatic alcohol increases, its lipophilicity increases, making it less likely to mix with sulfuric acid and less likely to produce a monoalkyl sulfate, so alkyl alcohols with 8 or fewer carbon atoms are preferred. In this way, by reacting sulfuric acid with an aliphatic alcohol to produce a monoalkyl sulfate, the acid strength of the acid catalyst can be controlled, and the condensation (polymerization) and coloration of the raw material ketone or aldehyde can be suppressed. As a result, the production of by-products is suppressed, and bisphenol with reduced coloration can be produced simply and efficiently.

[0131] When sulfuric acid is reacted with an aliphatic alcohol to produce a monoalkyl sulfate and its catalytic action is also utilized, a low molar ratio of the aliphatic alcohol to sulfuric acid (moles of aliphatic alcohol / moles of sulfuric acid) results in significant condensation (polymerization) of the raw material ketone or aldehyde and coloration. A high molar ratio reduces the sulfuric acid concentration and slows the reaction. For these reasons, the molar ratio of the aliphatic alcohol to sulfuric acid is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.

[0132] For the above reasons, the organic solvent may contain, for example, an aromatic hydrocarbon and an aliphatic alcohol, and the organic solvent may contain 1 to 95 mass % of aromatic hydrocarbon and 0.1 to 10 mass % of aliphatic alcohol.

[0133] (Preparation of reaction solution) The method for preparing the reaction solution is not particularly limited, and examples thereof include a method of supplying an acid catalyst to a mixed solution obtained by mixing an aromatic alcohol, an organic solvent, and a ketone or an aldehyde, and a method of supplying a ketone or an aldehyde to a mixed solution obtained by mixing an acid catalyst, an aromatic alcohol, and an organic solvent.

[0134] In order to suppress the polymerization due to the self-condensation of the ketone or aldehyde, it is preferable to mix a solution containing an aromatic alcohol, an acid catalyst, and an organic solvent with a solution containing a ketone or aldehyde. In this case, the solution containing a ketone or aldehyde may contain only a ketone or aldehyde, or may contain a thiol or an organic solvent. The solution containing a ketone or aldehyde preferably contains a thiol.

[0135] (Reaction conditions) The reaction for producing bisphenol is a condensation reaction, but if the reaction temperature is too high, the oxidative decomposition of thiol will proceed, and if it is too low, the time required for the reaction will increase. Therefore, the reaction temperature is preferably 0°C or higher and 50°C or lower.

[0136] If the reaction time for the production reaction is too long, the produced bisphenol will decompose, so it is preferably within 30 hours, more preferably within 25 hours, and even more preferably within 20 hours. The lower limit of the reaction time is usually 0.5 hours or more. The reaction can be stopped by adding water in an amount equal to or greater than the amount of sulfuric acid used, or by adding an aqueous sodium hydroxide solution so that the sulfuric acid concentration is 45 mass % or less.

[0137] (purification) The bisphenol product obtained by the bisphenol production reaction can be purified by a conventional method. For example, purification can be performed by simple means such as crystallization or column chromatography. Specifically, after the condensation reaction, the reaction solution is separated and the resulting organic phase is washed with water or saline, and if necessary, neutralized and washed with sodium bicarbonate water. The washed organic phase is then cooled and crystallized. When a large amount of aromatic alcohol is used, the excess aromatic alcohol is distilled off before the crystallization.

[0138] In the first embodiment, compound (II) produced as a by-product in the bisphenol production reaction system is left behind, and a bisphenol product containing compound (II) is obtained as the bisphenol composition of the first embodiment. Therefore, in the above-mentioned method for purifying a bisphenol product, it is preferable to adjust the purification conditions so that a predetermined amount of compound (II) remains in the purified bisphenol product, for example, by appropriately combining crystallization, suspension washing, and spray washing.

[0139] (An example of a refining process) As an example of a purification step suitable for the present invention, a method of purifying a bisphenol product obtained by a condensation reaction by washing in a washing step and then precipitating in a crystallization step will be described below.

[0140] In this case, after the condensation reaction, the organic phase containing bisphenol obtained from the reaction solution is washed with demineralized water, and the washed organic phase is cooled to cause crystallization. Washing is performed multiple times as follows. Crystallization may also be performed multiple times.

[0141] <Cleaning process> The cleaning step includes at least the following first and second steps. First step: The organic phase (O1) containing bisphenol obtained from the reaction step is mixed with demineralized water, and then the mixture is separated into an organic phase (O2) containing bisphenol and an aqueous phase (W1). The aqueous phase (W1) is removed to obtain an organic phase (O2) containing bisphenol. Second step: After mixing the organic phase (O2) containing bisphenol obtained in the first water washing step with demineralized water, the mixture is separated into an organic phase (O3) containing bisphenol and an aqueous phase (W2). The aqueous phase (W2) is removed to obtain an organic phase (O3) containing bisphenol. The first step is preferably carried out so that the pH of the aqueous phase (W1) is 8.5 or higher, and the second step is preferably carried out so that the electrical conductivity of the aqueous phase (W2) is 10 μS / cm. Demineralized water is water that has been ion-exchanged, pure water, or other water with an electrical conductivity of 1.5 μS / cm or less. The measurement temperature of the aqueous phase (W1) is preferably room temperature (20 to 30°C), for example, 25°C.

[0142] If the pH of the aqueous phase is lower than 7, washing can be performed using a basic substance such as sodium hydroxide or sodium bicarbonate, followed by another water wash. The organic phase obtained after washing with a basic substance is washed again with water so that the pH of the aqueous phase is 8.5 or higher. Here, since a weakly basic aqueous phase (low pH) results in a low washing effect, the pH is preferably 8.5 or higher, more preferably 9 or higher. On the other hand, a strongly basic aqueous phase (high pH) results in bisphenols becoming bisphenol salts, increasing the amount of loss during water washing. Therefore, the upper limit of the pH of the aqueous phase (W1) is usually 14 or lower, preferably 13 or lower, and more preferably 12 or lower.

[0143] The temperature at which the electrical conductivity of the aqueous phase (W2) in the second water-washing step is measured is preferably room temperature (20 to 30°C), for example, 25°C. The electrical conductivity of the aqueous phase (W2) in the second water washing step is preferably 10 μS / cm or less, more preferably 9 μS / cm or less, and even more preferably 8 μS / cm or less.

[0144] In the washing step, the organic phase containing bisphenol is first washed with water until the pH of the resulting aqueous phase becomes basic, at pH 8.5 or higher, and then washing is repeated as necessary until the electrical conductivity of the resulting aqueous phase becomes 10 μS / cm or lower, and the aqueous phase is then preferably subjected to the crystallization step.

[0145] By performing washing with demineralized water so that the pH of the aqueous phase (W1) in the first water washing step is above the lower limit and the electrical conductivity of the aqueous phase (W2) in the second water washing step is below the upper limit, impurities such as by-products, residual catalyst, and residual thiol in the produced bisphenol can be thoroughly removed, resulting in a bisphenol composition with a good color. When used as a raw bisphenol for polycarbonate resin, this composition can produce polycarbonate resins with high polymerization reaction efficiency and excellent color. In particular, in condensation reactions using thiol as a co-catalyst, acidic thionium is produced from the thiol, which is contained in the bisphenol composition and inhibits the polymerization reaction during polycarbonate resin production. However, by performing washing steps in which the pH of the aqueous phase (W1) and the electrical conductivity of the aqueous phase (W2) are controlled as described above, the thionium can be efficiently removed and polymerization inhibition by thionium can be prevented.

[0146] The temperature in the washing step is preferably 90°C or lower, particularly 85°C or lower, and 50°C or higher, particularly 55°C or higher, so that bisphenol can be efficiently precipitated by cooling in the crystallization step described below without evaporating the solvent. The time required for one washing (the time required to add demineralized water to the organic phase and mix) is usually about 1 to 120 minutes.

[0147] <Crystallization process> The cooling temperature in the crystallization step is 10 to 120° C. lower than the temperature of the organic phase (O3) obtained from the washing step, and is preferably 40° C. or lower, particularly 30° C. or lower, and −20° C. or higher, particularly −10° C. or higher. By cooling the organic phase (O3) after washing to such a temperature, the bisphenol composition can be efficiently precipitated.

[0148] The bisphenol composition precipitated in the crystallization step can be recovered by solid-liquid separation such as filtration, centrifugation, decantation, or the like.

[0149] Even when the above washing step and crystallization step are carried out, it is preferable to control the purification conditions so that a predetermined proportion of compound (II) remains in the bisphenol composition obtained after purification.

[0150] <Uses of bisphenol compositions> The bisphenol composition of the first embodiment can be used as a constituent, curing agent, additive, or precursor thereof for various thermoplastic resins such as polyether resins, polyester resins, polyarylate resins, polycarbonate resins, polyurethane resins, and acrylic resins, and various thermosetting resins such as epoxy resins, unsaturated polyester resins, phenolic resins, polybenzoxazine resins, and cyanate resins, which are used in a variety of applications including optical materials, recording materials, insulating materials, transparent materials, electronic materials, adhesive materials, and heat-resistant materials. The bisphenol composition of the first embodiment is also useful as an additive for color developers and anti-fading agents for thermal recording materials and the like, as well as for disinfectants, antibacterial and antifungal agents, and the like.

[0151] The bisphenol composition of the first embodiment is preferably used as a raw material (monomer) for thermoplastic resins and thermosetting resins, and more preferably as a raw material for polycarbonate resins and epoxy resins, because it can impart good mechanical properties. The bisphenol composition of the first embodiment is also preferably used as a color developer, and more preferably used in combination with a leuco dye and a discoloration temperature regulator.

[0152] [Polycarbonate resin] The polycarbonate resin of the first embodiment is a polycarbonate resin having at least the repeating structural unit represented by the following general formula (A), and the compound obtained by alkaline hydrolysis of the polycarbonate resin (hereinafter sometimes referred to as the "alkaline hydrolysis product") contains bisphenol (I) and compound (II), preferably indane C1 or indane C2, and the content of compound (II) obtained by alkaline hydrolysis relative to the polycarbonate resin is 5 ppm by mass or more. The polycarbonate resin of the first embodiment can be produced using the bisphenol composition of the first embodiment.

[0153] [ka]

[0154] In general formula (A), R 1 ~R 6 has the same meaning as in general formula (1).

[0155] If the content of compound (II) in the alkaline hydrolysis product of a polycarbonate resin is less than the lower limit of the polycarbonate resin, a polycarbonate resin having a good hue cannot be obtained. The content of this compound (II) in the polycarbonate resin is preferably 25 ppm by mass or more, more preferably 50 ppm by mass or more, and preferably 200 ppm by mass or less, more preferably 150 ppm by mass or less.

[0156] A method for producing the polycarbonate resin of the first embodiment using the bisphenol composition of the first embodiment includes a method in which the bisphenol composition of the first embodiment is subjected to a transesterification reaction with diphenyl carbonate or the like in the presence of an alkali metal compound and / or an alkaline earth metal compound.

[0157] The bisphenol composition of the first embodiment may contain only one type of bisphenol, or may contain two or more types. By using two or more types of bisphenol, a copolymer polycarbonate resin can be produced. A dihydroxy compound other than the bisphenol composition of the first embodiment can also be used in combination and reacted.

[0158] The above transesterification reaction can be carried out by appropriately selecting a known method. An example of a method for producing a polycarbonate resin using the bisphenol composition of the first embodiment and diphenyl carbonate as raw materials will be described below.

[0159] In the above-mentioned method for producing a polycarbonate resin, it is preferable to use an excess amount of diphenyl carbonate relative to the bisphenol in the bisphenol composition of the first embodiment. The amount of diphenyl carbonate used relative to the bisphenol is preferably large, in order to reduce the number of terminal hydroxyl groups in the produced polycarbonate resin and to improve the thermal stability of the polymer. The amount of diphenyl carbonate used relative to the bisphenol is preferably small, in order to increase the transesterification reaction rate and facilitate the production of a polycarbonate resin with the desired molecular weight. For these reasons, the amount of diphenyl carbonate used relative to 1 mole of bisphenol is typically 1.001 moles or more, preferably 1.002 moles or more, and typically 1.3 moles or less, preferably 1.2 moles or less.

[0160] As a method for supplying the raw materials, the bisphenol composition of the first embodiment and diphenyl carbonate can be supplied in solid form, but it is preferable to melt one or both and supply them in a liquid state.

[0161] When producing a polycarbonate resin by the transesterification reaction of diphenyl carbonate and bisphenol, a transesterification catalyst is usually used. In the above-mentioned method for producing a polycarbonate resin, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound as the transesterification catalyst. These may be used alone or in any combination and ratio of two or more. In practice, it is desirable to use an alkali metal compound.

[0162] The amount of catalyst used is usually 0.05 μmol or more, preferably 0.08 μmol or more, more preferably 0.10 μmol or more, and usually 100 μmol or less, preferably 50 μmol or less, more preferably 20 μmol or less, per mole of bisphenol or diphenyl carbonate. When the amount of catalyst used is within the above range, it is easy to obtain the polymerization activity required to produce a polycarbonate resin having a desired molecular weight, and it is easy to obtain a polycarbonate resin that has excellent polymer color, does not undergo excessive polymer branching, and has excellent fluidity during molding.

[0163] To produce a polycarbonate resin by the above method, it is preferable to continuously feed both of the raw materials into a raw material mixing tank, and then continuously feed the resulting mixture and the transesterification catalyst into a polymerization tank. In the production of polycarbonate resins by the transesterification method, the two raw materials are usually supplied to a raw material mixing tank, stirred uniformly, and then supplied to a polymerization tank to which a transesterification catalyst is added, thereby producing a polymer.

[0164] In the production of polycarbonate resins using the bisphenol composition of the first embodiment, the polymerization reaction temperature is preferably 80°C or higher, particularly 150°C or higher, and 400°C or lower, particularly 350°C or lower. The polymerization time is adjusted appropriately depending on the ratio of raw materials, the molecular weight of the desired polycarbonate resin, and the like. Since a long polymerization time can cause deterioration in quality, such as deterioration in color tone, the polymerization time is preferably 10 hours or shorter, more preferably 8 hours or shorter. The lower limit of the polymerization time is usually 0.1 hours or longer, or 0.3 hours or longer.

[0165] The bisphenol composition of the first embodiment can produce a polycarbonate resin with good color and excellent transparency. For example, a polycarbonate resin with good color and excellent transparency having a viscosity average molecular weight (Mv) of 10,000 or more, preferably 15,000 or more, and 100,000 or less, preferably 35,000 or less, and a pellet YI of 10 or less can be produced in a short period of time.

[0166] [Second embodiment of bisphenol composition and polycarbonate resin] [Bisphenol composition] The bisphenol composition of the second embodiment is a bisphenol composition containing 95% by mass or more of bisphenol and 10 ppm by mass or more of 1-(4-hydroxy-3-methylphenyl)-6-hydroxy-1,3,3,5-tetramethylindan (hereinafter referred to as "indan C2") represented by the following structural formula (IIb):

[0167] [ka]

[0168] The content of indane C2 in the bisphenol composition of the second embodiment is preferably 15 ppm by mass or more, and preferably 200 ppm by mass or less, more preferably 150 ppm by mass or less.

[0169] If the content of indane C2 in the bisphenol composition is less than the above lower limit, it will be impossible to obtain a bisphenol composition with good methanol solubility color, melt color difference, thermal color stability, and thermal decomposition stability. If the content of indane C2 in the bisphenol composition exceeds the above upper limit, the molar ratio with diphenyl carbonate may be off during the production of polycarbonate resin, potentially affecting the polymerization reaction. If the content of indane C2 in the bisphenol composition exceeds the above upper limit, it may result in a decrease in the brittleness (Izod) of the polycarbonate resin or a decrease in the high surface hardness specific to polycarbonate resins containing structural units derived from 2,2-bis(4-hydroxy-3-methylphenyl)propane or 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane.

[0170] Detection and quantification of indan C2 can be achieved using a standard high-performance analytical reversed-phase column with a particle size of 3 μm.

[0171] <Bisphenol> The bisphenol contained in the bisphenol composition of the second embodiment is the same as the bisphenol contained in the bisphenol composition of the first embodiment described above, and specific examples, preferred examples, and the bisphenol content in the bisphenol composition are also the same as those in the bisphenol composition of the first embodiment described above. The same explanation applies, except that "compound (II)" in the explanation of the first embodiment described above is replaced with "indan C2".

[0172] The explanations and preferred ranges for the methanol-dissolved color, melting color difference, thermal color stability, and thermal decomposition stability of the bisphenol composition of the first embodiment also apply to the "methanol-dissolved color of the bisphenol composition," "melting color difference of the bisphenol composition," "thermal color stability of the bisphenol composition," and "thermal decomposition stability of the bisphenol composition." However, the Hazen color scale of the methanol-dissolved color of the bisphenol composition of the second embodiment is preferably 20 or less, more preferably 10 or less, and particularly preferably 5 or less.

[0173] <Method of producing bisphenol composition> There are no particular limitations on the method for producing the bisphenol composition of the second embodiment containing 95% by mass or more of bisphenol and a predetermined proportion of indan C2, but examples thereof include the following methods. (1) Adding a predetermined amount of indan C2 to solid bisphenol (2) Adding a specified amount of indan C2 to molten bisphenol (3) A method for obtaining a bisphenol product containing indan C2 by producing indan C2 during the production of bisphenol.

[0174] In the methods (1) and (2) of adding indan C2 to solid or molten bisphenol, it is necessary to prepare indan C2 separately, and therefore the method (3) of by-producing indan C2 in the reaction system for producing bisphenol and containing indan C2 in a predetermined ratio in the bisphenol product is preferred.

[0175] If the amount of indan C2 by-produced in the bisphenol reaction system is too large, the resulting bisphenol product can be further purified by crystallization, suspension washing, sprinkle washing, or the like to remove a portion of the indan C2 contained in the bisphenol product, thereby controlling the amount of indan C2 to be obtained within the specified range of the second aspect.

[0176] <Method for obtaining bisphenol products containing indane C2> As a method for producing indan C2 together with bisphenol in a reaction system during the production of bisphenol, and thereby obtaining a bisphenol product containing indan C2 as the bisphenol composition of the second embodiment, there is mentioned a method for producing bisphenol by condensing a ketone or aldehyde with an aromatic alcohol in the presence of an acid catalyst and a thiol co-catalyst, and according to this method, indan C2 can be produced in the reaction system.

[0177] The method for producing the bisphenol composition of the second embodiment containing indane C2 by generating indane C2 in a reaction system is the same as the method for producing the bisphenol composition of the first embodiment containing compound (II) described above. The same explanation applies except that "compound (II)" in the description of the first embodiment is replaced with "indane C2."

[0178] <Uses of bisphenol compositions> The uses of the bisphenol composition of the second embodiment are the same as those of the bisphenol composition of the first embodiment described above, and the preferred uses thereof are also the same.

[0179] [Manufacturing method of polycarbonate resin] A method for producing a polycarbonate resin using the bisphenol composition of the second embodiment includes a method in which the bisphenol composition of the second embodiment is subjected to a transesterification reaction with diphenyl carbonate or the like in the presence of an alkali metal compound and / or an alkaline earth metal compound.

[0180] The bisphenol composition of the second embodiment may contain only one type of bisphenol, or may contain two or more types. By using two or more types of bisphenol, a copolymer polycarbonate resin can be produced. A dihydroxy compound other than the bisphenol composition of the second embodiment can also be used in combination and reacted.

[0181] The transesterification reaction can be carried out by appropriately selecting a known method. The method for producing a polycarbonate resin using the bisphenol composition of the second embodiment and diphenyl carbonate as raw materials is the same as the method for producing a polycarbonate resin using the bisphenol composition of the first embodiment and diphenyl carbonate as raw materials described above, and the same explanation applies with the exception that "the bisphenol composition of the first embodiment" is replaced with "the bisphenol composition of the second embodiment." The viscosity average molecular weight (Mv) and pellet YI of the produced polycarbonate resin are also the same as those of the polycarbonate resin produced using the bisphenol composition of the first embodiment described above. [Example]

[0182] The present invention will be described in more detail below with reference to examples and comparative examples. The present invention is not limited to the following examples as long as the gist of the invention is not exceeded.

[0183] [Raw materials and reagents] In the following examples and comparative examples, orthocresol, toluene, sodium hydroxide, sulfuric acid, dodecanethiol, acetone, sodium bicarbonate, cesium carbonate, acetonitrile, methylene chloride, acetic acid, and ammonium acetate were used as reagents manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Diphenyl carbonate used was a product manufactured by Mitsubishi Chemical Corporation.

[0184] 〔analysis〕 <Composition of bisphenol C production reaction solution, analysis of indan C1 and indan C2 in bisphenol C composition, analysis of indan C1 and indan C2 in alkaline hydrolysis product of polycarbonate resin> The composition analysis of the bisphenol C production reaction solution, the analysis of indan C1 and indan C2 in the bisphenol C composition, and the analysis of indan C1 and indan C2 in the alkaline hydrolysis product of polycarbonate resin were carried out by high performance liquid chromatography according to the following procedures and conditions. Equipment: Shimadzu Corporation "LC-2010A" Imtakt ScherzoSM-C18 3μm 250mm×3.0mmID Low-pressure gradient method ·Analysis temperature: 40℃ ·Eluent composition: Solution A: Ammonium acetate: acetic acid: demineralized water = 3.000 g: 1 mL: 1 L solution Solution B: Ammonium acetate: acetic acid: acetonitrile: demineralized water = 1.500 g: 1 mL: 900 mL: 150 mL solution At analysis time 0 minutes, the eluent composition is solution A:solution B = 60:40 (volume ratio, same below). During the analysis time from 0 to 41.67 minutes, the ratio of A to B was gradually changed to 10:90. During the analysis time from 41.67 to 50 minutes, the ratio of A to B was maintained at 10:90. The analysis was carried out at a flow rate of 0.34 mL / min.

[0185] <Isolation of Indan C1 and Indan C2> The separation of indan C1 and indan C2 in the bisphenol C composition was carried out by preparative high performance liquid chromatography under the following procedures and conditions. Equipment: Shimadzu Corporation "LC10A" Capcellpak C18 MGIII 150×20mm×5μm ·Analysis temperature: 40℃ ·Eluent composition: A liquid water Solution B: Acetonitrile At analysis time 0 minutes, the eluent composition is solution A:solution B = 30:70 (volume ratio, same below). During the analysis time from 0 to 15 minutes, the ratio of A to B was gradually changed to 10:90. For analysis times of 15 to 20 minutes, the ratio of A solution to B solution is maintained at 10:90. The analysis was carried out at a flow rate of 12.0 mL / min. -Injection volume was 400μL per injection, performed 15 times.

[0186] <nmr> For nuclear magnetic resonance (NMR) measurements, the solutions obtained by separating indan C1 and indan C2 were dried in an evaporator, and the resulting solution was dissolved in deuterated chloroform and analyzed using a JEOL Ltd. "JNM-ECS400" analyzer. 1 H NMR, 13 C NMR, HH COSY, HMQC, HMBC, and DEPT135 were performed.

[0187] <Preparation of analytical solution for indan C1 and indan C2 in alkaline hydrolysis products of polycarbonate resin> A 100 mL Erlenmeyer flask equipped with a stirrer was charged with 0.5 g of polycarbonate resin pellets and 5 mL of methylene chloride to prepare a homogeneous solution. 45 mL of methanol was added, followed by 5 mL of 25% aqueous sodium hydroxide solution. The Erlenmeyer flask was immersed in a water bath at 70-75°C and stirred for 30 minutes. The Erlenmeyer flask was then removed from the water bath, neutralized with hydrochloric acid, and water and methanol were added to prepare a homogeneous solution. This analytical solution was then subjected to measurement by high-performance liquid chromatography.

[0188] <Molecular weight measurement of Indan C1 and Indan C2> The molecular weights of Indan C1 and Indan C2 were measured using high performance liquid chromatography mass spectrometry (LCMS), which was carried out according to the following procedure and conditions. Separation device: Agilent Technologies "Agilent1200" Imtakt ScherzoSM-C18 3μm 150mm×4.6mmID Low-pressure gradient method ·Analysis temperature: 40℃ ·Eluent composition: Solution A: Ammonium acetate: acetic acid: demineralized water = 3.000 g: 1 mL: 1 L solution Solution B: Ammonium acetate: acetic acid: acetonitrile = 1.500 g: 1 mL: 1 L solution At analysis time 0 minutes, the eluent composition was solution A:solution B = 60:40 (volume ratio, same below). During the analysis time from 0 to 25 minutes, the ratio of A to B was gradually changed to 90:10. For analysis time of 25 to 30 minutes, the ratio of A solution to B solution is maintained at 90:10. The analysis was carried out at a flow rate of 1.0 mL / min. Detection wavelength: 280nm Mass spectrometer: Agilent LC / MS 6130 manufactured by Agilent Technologies, Inc. Ion source: ESI (Postive / Negative) AJS probe used

[0189] <Analysis of bisphenol C in bisphenol C compositions> The analysis of bisphenol C in the bisphenol C composition was carried out in the same manner as in <Composition of the bisphenol C production reaction solution, analysis of indan C1 and indan C2 in the bisphenol C composition, and analysis of indan C1 and indan C2 in the alkaline hydrolysis product of polycarbonate resin>. The purity of bisphenol C in the bisphenols in the bisphenol C composition produced by the present invention is usually 99% by mass or more, and the amount of bisphenols other than bisphenol C produced is extremely small, so the bisphenol C content in the bisphenol C composition can be considered to be the bisphenol content.

[0190] <Identification of isopropenylcresol> Isopropenylcresol was identified using a gas chromatograph mass spectrometer according to the following procedure and conditions. Equipment: Agilent Technologies "Agilent 6890" Column: Agilent Technologies DB-1MS (inner diameter 0.25 mm x 30 m x 0.25 μm) Carrier gas: Helium Flow rate: 1cm per minute 3 ·Inlet temperature: 280℃ Transfer temperature: 250℃ Ion source temperature: 250℃ · Heating pattern of the column: First, hold at 50°C for 3 minutes, then heat up to 320°C at 10°C per minute, and hold at 280°C for 5 minutes.

[0191] <Measurement of pH> The pH was measured using a pH meter "pH METER ES-73" manufactured by Horiba, Ltd. for the aqueous phase at 25°C taken out from the flask.

[0192] <C <Electrical conductivity> The electrical conductivity was measured using a conductivity meter "COND METER D-71" manufactured by Horiba, Ltd. for the aqueous phase at 25°C taken out from the flask.

[0193] <Methanol dissolution color of bisphenol C composition> The methanol dissolution color of the bisphenol C composition was evaluated by measuring the Hazen color number using "SE6000" manufactured by Nippon Denshoku Industries Co., Ltd. at room temperature (about 20°C) after putting 10 g of the bisphenol C composition and 10 g of methanol into a test tube "P-24" (24 mm φ × 200 mm) manufactured by Nippon Electric Glass Co., Ltd. to form a homogeneous solution.

[0194] <Melting color difference of bisphenol C composition> The melting color difference of the bisphenol C composition was evaluated by measuring the Hazen color number using "SE6000" manufactured by Nippon Denshoku Industries Co., Ltd. after putting 20 g of the bisphenol C composition into a test tube "P-24" (24 mm φ × 200 mm) manufactured by Nippon Electric Glass Co., Ltd. and melting it at 190°C for 30 minutes.

[0195] <Thermal color stability of bisphenol C composition> The thermal color stability of the bisphenol C composition was evaluated by measuring the Hazen color number using "SE6000" manufactured by Nippon Denshoku Industries Co., Ltd. after putting 20 g of the bisphenol C composition into a test tube "P-24" (24 mm φ × 200 mm) manufactured by Nippon Electric Glass Co., Ltd. and melting it at 190°C for 4 hours.

[0196] <Thermal decomposition stability of bisphenol C composition> The thermal decomposition stability of the bisphenol C composition was evaluated by placing 20 g of the bisphenol C composition in a test tube "P-24" (24 mmφ×200 mm) manufactured by Nichiden Rika Glass Co., Ltd., melting it at 190°C for 2 hours, and measuring the amount of isopropenyl cresol produced in the same manner as in the composition analysis of the bisphenol C production reaction liquid.

[0197] <Analysis of iron and aluminum in bisphenol C composition> Approximately 1 g of a bisphenol C composition was collected, sulfuric acid was added, and the mixture was dry ashed. Hydrofluoric acid was then added to the resulting sample, which was then dried. Nitric acid and pure water were then added to dissolve the sample. The resulting sample was adjusted to a constant volume, appropriately diluted, and quantitatively measured for iron and aluminum in the bisphenol C composition using an ICP-MS ("ELEMENT2" manufactured by Thermo Fisher Scientific).

[0198] <Viscosity average molecular weight> The polycarbonate resin was dissolved in methylene chloride (concentration: 6.0 g / L), and the specific viscosity (ηsp) at 20° C. was measured using an Ubbelohde viscometer, and the viscosity average molecular weight (Mv) was calculated using the following formula. ηsp / C=[η](1+0.28ηsp) [η]=1.23×10 -4 Mv 0.83

[0199] <Pellet YI> Pellet YI (transparency of polycarbonate resin) was evaluated by measuring the YI value (yellowness index value) of reflected light of polycarbonate resin pellets in accordance with ASTM D 1925. The instrument used was a spectrophotometer "CM-5" manufactured by Konica Minolta, and the measurement conditions were a measurement diameter of 30 mm and SCE. The CM-A212 Petri dish calibration glass was fitted into the measurement unit, and the CM-A124 zero calibration box was placed over it to perform zero calibration. Then, the built-in white calibration plate was used to perform white calibration. Measurements were then performed using the CM-A210 white calibration plate, confirming that L* was 99.40±0.05, a* was 0.03±0.01, b* was -0.43±0.01, and YI was -0.58±0.01. YI was measured by filling a cylindrical glass container with an inner diameter of 30 mm and a height of 50 mm with pellets to a depth of about 40 mm. The pellets were removed from the glass container and the measurement was repeated twice, and the average of the three measurements was used.

[0200] [Reference example 1] A 500 mL eggplant-shaped flask equipped with a stirrer, thermometer, and distillation apparatus was charged with 85 g of bisphenol C composition and 4.5 g of sodium hydroxide and immersed in an oil bath heated to 195°C. After confirming that the bisphenol C in the eggplant-shaped flask had melted, the flask was gradually depressurized using a vacuum pump until a full vacuum was achieved. After a while, evaporation began, and vacuum distillation was continued until the distillation ceased. Gas chromatography equipped with a mass spectrometer detector revealed that the resulting fraction was a mixture of cresol and isopropenyl cresol produced by thermal decomposition of bisphenol C. The resulting fraction was used to confirm the retention time of isopropenyl cresol under the composition analysis conditions for the bisphenol C production reaction solution.

[0201] [Examples of the first embodiment and comparative examples] [Example I-1] (1) Preparation of the first mixed solution 320 g of toluene, 15 g of methanol, and 230 g (2.13 mol) of ortho-cresol were placed in a separable flask equipped with a thermometer, a dropping funnel, a jacket, and an anchor-type stirring blade under a nitrogen atmosphere, and the internal temperature was adjusted to 10°C or below. Then, 95 g of 98 wt% sulfuric acid was slowly added over 0.3 hours with stirring, and the mixture was cooled to 5°C or below.

[0202] (2) Preparation of the second mixture A second mixed liquid (dropping liquid) was prepared by mixing 50 g of toluene, 65 g (1.12 mol) of acetone, and 5.4 g of dodecanethiol in a 500 mL Erlenmeyer flask.

[0203] (3) Preparation of reaction solution After the internal temperature of the first mixed solution was reduced to 5°C or lower, the second mixed solution was added using the dropping funnel over 1 hour so that the internal temperature did not exceed 10°C, thereby preparing a reaction solution.

[0204] (4) Reaction The prepared reaction solution was stirred at an internal temperature of 10°C for 2.5 hours.

[0205] (5) Purification (washing) After the reaction was completed, 190 g of a 25% aqueous sodium hydroxide solution was added and the temperature was raised to 80°C. After reaching 80°C, the mixture was allowed to stand, and the lower aqueous phase was removed. 400 g of demineralized water was added to the obtained first organic phase, mixed for 30 minutes, allowed to stand, and the aqueous phase was removed. 120 g of a 1.5% by mass sodium bicarbonate solution was added to the obtained second organic phase, mixed for 30 minutes, allowed to stand, and the lower phase was removed. Another 120 g of a 1.5% by mass sodium bicarbonate solution was added to the obtained third organic phase, mixed for 30 minutes, allowed to stand, and the lower phase was removed. The obtained fourth organic phase was removed, and its mass was measured and found to be 666 g.

[0206] A portion of the fourth organic phase was taken out, and the composition of the fourth organic phase was confirmed by high-performance liquid chromatography. As a result, it was found that ortho-cresol was produced in an amount of 5.3 mass% (5.3 mass% × mass of organic phase 666 g × molecular weight of ortho-cresol 108 g / mol × amount of ortho-cresol charged 2.1 mol = 15.3 mol%), and bisphenol C was produced in an amount of 31.5 mass% (31.5 mass% × mass of organic phase 666 g × 2 × molecular weight of bisphenol C 256 g / mol × amount of ortho-cresol charged 2.1 mol = 78.0 mol%).

[0207] (6) Purification (washing and crystallization) 200 g of demineralized water was added to the resulting fourth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (first aqueous phase) was removed to obtain a fifth organic phase. The pH of the first aqueous phase was 9.7. 200 g of demineralized water was added to the resulting fifth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (second aqueous phase) was removed to obtain a sixth organic phase. 200 g of demineralized water was added to the resulting sixth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (third aqueous phase) was removed. The electrical conductivity of the third aqueous phase was 2.7 μS / cm.

[0208] The resulting sixth organic phase was cooled from 80°C to 20°C and maintained at 20°C to precipitate bisphenol C. It was then cooled to 10°C, and after reaching 10°C, solid-liquid separation was performed using a centrifuge to obtain a crude wet cake. 500g of toluene was sprinkled onto the resulting wet cake to wash it, and solid-liquid separation was performed using a centrifuge to obtain a purified wet cake. The resulting purified wet cake was distilled off low-boiling components under reduced pressure at an oil bath temperature of 100°C using an evaporator equipped with an oil bath, yielding 190g of a white bisphenol C composition.

[0209] The methanol dissolution color of the obtained bisphenol C composition was measured, and the Hazen color number was 0. The melt color difference of the obtained bisphenol C composition was measured, and the Hazen color number was 3. The thermal color stability of the obtained bisphenol C composition was measured, and the Hazen color number was 26. The thermal decomposition stability of the obtained bisphenol C composition was measured, and the amount of isopropenyl cresol produced was 186 ppm by mass.

[0210] The iron and aluminum contents of the resulting bisphenol C composition were measured and found to be 0.05 ppm by mass and 0.05 ppm by mass.

[0211] The quality of the obtained bisphenol C composition was confirmed, and a characteristic peak was detected at a retention time of 28.28 minutes on a high-performance liquid chromatograph. To identify the component of this peak, a high-performance liquid chromatograph equipped with a mass meter was used to measure it, and the molecular weight was found to be 296 g / mol.

[0212] 1.6 g of the resulting bisphenol C composition was dissolved in acetonitrile, and the characteristic peaks were separated using preparative liquid chromatography. The solution obtained by separation was dried, and the resulting dried product was dissolved in deuterated chloroform and subjected to various NMR measurements (Figures 1 to 6). The product was confirmed to be 1-(4-hydroxy-3-methylphenyl)-6-hydroxy-1,3,3,7-tetramethylindan (indan C1) having the structure shown in the following structural formula (IIa) and 1-(4-hydroxy-3-methylphenyl)-6-hydroxy-1,3,3,5-tetramethylindan (indan C2) having the structure shown in the following structural formula (IIb).

[0213] Indane C1; 1 NMR(400MHz, CDCl3) 1.18(Me,s,3H),1.29(Me,s,3H),1.72(Me,s,3H),1.76(Me,s,3H),2.20(Me,s, 3H),2.23(CH2,s,3H),4,66(OH,s,1H),4.68(OH,s,1H),6.62-6.94(CH,m,5H); 13CNMR(400MHz,CDCl3)11.8,16.1,28.0,31.6,31.9,41.9,50.8,62.0,114.5, 114.6,120.2,120.4,123.3,125.0,128.9,143.3,145.2,149.0,151.5,153.3. Indane C2; 1 NMR(400MHz, CDCl3) 1.03(Me,s,3H),1.29(Me,s,3H),1.59(Me,s,6H),2.11(Me,s,3H),2.27(CH2,s,3H),4,62(OH,s,1H),4.64(OH,s,1H),6.47-6.91(CH,m,5H); 13CNMR(400MHz,CDCl3)16.1,29.9,30.8,31.8,59.8,42.3,49.9,111.0,11 4.3,122.7,123.0,124.9,125.4,129.3,143.3,144.5,148.5,151.5,152.8.

[0214] [ka]

[0215] The resulting bisphenol C composition contained 210 ppm by mass of indan C1 and 12 ppm by mass of indan C2. The bisphenol C content in the resulting bisphenol C composition was 99.8 mass %.

[0216] [Example I-2] (1) Preparation of the first mixed solution 320 g of toluene, 15 g of methanol, and 230 g (2.13 mol) of ortho-cresol were placed in a separable flask equipped with a thermometer, a dropping funnel, a jacket, and an anchor-type stirring blade under an air atmosphere, and the internal temperature was adjusted to 10°C or below. Then, 95 g of 98 wt% sulfuric acid was slowly added over 0.3 hours while stirring, and the mixture was cooled to 5°C or below.

[0217] (2) Preparation of the second mixture A second mixed liquid (dropping liquid) was prepared by mixing 50 g of toluene, 65 g (1.12 mol) of acetone, and 5.4 g of dodecanethiol in a 500 mL Erlenmeyer flask.

[0218] (3) Preparation of reaction solution After the internal temperature of the first mixed solution was reduced to 5°C or lower, the second mixed solution was added using the dropping funnel over 1 hour so that the internal temperature did not exceed 10°C, thereby preparing a reaction solution.

[0219] (4) Reaction The prepared reaction solution was stirred at an internal temperature of 10°C for 6 hours.

[0220] (5) Purification (washing) After the reaction was completed, 190 g of a 25% aqueous sodium hydroxide solution was added and the temperature was raised to 80°C. After reaching 80°C, the mixture was allowed to stand, and the lower aqueous phase was removed. 400 g of demineralized water was added to the obtained first organic phase, mixed for 30 minutes, allowed to stand, and the aqueous phase was removed. 120 g of a 1.5% by mass sodium bicarbonate solution was added to the obtained second organic phase, mixed for 30 minutes, allowed to stand, and the lower phase was removed. Another 120 g of a 1.5% by mass sodium bicarbonate solution was added to the obtained third organic phase, mixed for 30 minutes, allowed to stand, and the lower phase was removed. The obtained fourth organic phase was removed, and its mass was measured and found to be 666 g.

[0221] A portion of the fourth organic phase was taken out, and the composition of the fourth organic phase was confirmed by high-performance liquid chromatography. As a result, it was found that ortho-cresol was produced in an amount of 3.9% by mass (3.9% by mass × mass of organic phase 666 g × molecular weight of ortho-cresol 108 g / mol × amount of ortho-cresol charged 2.1 mol = 11.5 mol%), and bisphenol C was produced in an amount of 33.5% by mass (33.5% by mass × mass of organic phase 666 g × 2 × molecular weight of bisphenol C 256 g / mol × amount of ortho-cresol charged 2.1 mol = 83.0 mol%).

[0222] (6) Purification (washing and crystallization) 200 g of demineralized water was added to the resulting fourth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (first aqueous phase) was removed to obtain a fifth organic phase. The pH of the first aqueous phase was 9.7. 200 g of demineralized water was added to the resulting fifth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (second aqueous phase) was removed to obtain a sixth organic phase. 200 g of demineralized water was added to the resulting sixth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (third aqueous phase) was removed. The electrical conductivity of the third aqueous phase was 2.3 μS / cm.

[0223] The resulting sixth organic phase was cooled from 80°C to 20°C and maintained at 20°C to precipitate bisphenol C. It was then cooled to 10°C, and after reaching 10°C, solid-liquid separation was performed using a centrifuge to obtain a crude wet cake. 500g of toluene was sprinkled onto the resulting wet cake to wash it, and solid-liquid separation was performed using a centrifuge to obtain a purified wet cake. The resulting purified wet cake was distilled off low-boiling components under reduced pressure at an oil bath temperature of 100°C using an evaporator equipped with an oil bath, yielding 190g of a white bisphenol C composition.

[0224] The bisphenol C content in the obtained bisphenol C composition was 99.7 mass%, the indane C1 content was 1,349 mass ppm, and the indane C2 content was 20 mass ppm. When the methanol dissolution color of the obtained bisphenol C composition was measured, the Hazen color number was 0. When the melt color difference of the obtained bisphenol C composition was measured, the Hazen color number was 8. When the thermal color stability of the obtained bisphenol C composition was measured, the Hazen color number was 32. When the thermal decomposition stability of the obtained bisphenol C composition was measured, the amount of isopropenyl cresol produced was 166 mass ppm.

[0225] The iron and aluminum contents of the resulting bisphenol C composition were measured and found to be 0.02 ppm by mass and 0.01 ppm by mass.

[0226] [Comparative example I-1] (1) Preparation of the first mixed solution 320 g of toluene, 15 g of methanol, and 230 g (2.13 mol) of ortho-cresol were placed in a separable flask equipped with a thermometer, a dropping funnel, a jacket, and an anchor-type stirring blade under a nitrogen atmosphere, and the internal temperature was adjusted to 10°C or below. Then, 95 g of 98 wt% sulfuric acid was slowly added over 0.3 hours with stirring, and the mixture was cooled to 5°C or below.

[0227] (2) Preparation of the second mixture A second mixed liquid (dropping liquid) was prepared by mixing 50 g of toluene, 65 g (1.12 mol) of acetone, and 5.4 g of dodecanethiol in a 500 mL Erlenmeyer flask.

[0228] (3) Preparation of reaction solution After the internal temperature of the first mixed solution was reduced to 5°C or lower, the second mixed solution was added using the dropping funnel over 1 hour so that the internal temperature did not exceed 10°C, thereby preparing a reaction solution.

[0229] (4) Reaction The prepared reaction solution was stirred at an internal temperature of 10°C for 2 hours.

[0230] (5) Purification (washing) After the reaction was completed, 190 g of a 25% aqueous sodium hydroxide solution was added and the temperature was raised to 80°C. After reaching 80°C, the mixture was allowed to stand, and the lower aqueous phase was removed. 400 g of demineralized water was added to the obtained first organic phase, mixed for 30 minutes, allowed to stand, and the aqueous phase was removed. 120 g of a 1.5% by mass sodium bicarbonate solution was added to the obtained second organic phase, mixed for 30 minutes, allowed to stand, and the lower phase was removed. Another 120 g of a 1.5% by mass sodium bicarbonate solution was added to the obtained third organic phase, mixed for 30 minutes, allowed to stand, and the lower phase was removed. The obtained fourth organic phase was removed, and its mass was measured and found to be 666 g.

[0231] A portion of the fourth organic phase was taken out, and the composition of the fourth organic phase was confirmed by high-performance liquid chromatography. As a result, it was found that ortho-cresol was produced in an amount of 5.3 mass% (5.3 mass% × mass of organic phase 666 g × molecular weight of ortho-cresol 108 g / mol × amount of ortho-cresol charged 2.1 mol = 15.3 mol%), and bisphenol C was produced in an amount of 31.5 mass% (31.5 mass% × mass of organic phase 666 g × 2 × molecular weight of bisphenol C 256 g / mol × amount of ortho-cresol charged 2.1 mol = 78.0 mol%).

[0232] (6) Purification (washing and crystallization) The obtained fourth organic phase was cooled from 80°C to 20°C and maintained at 20°C to precipitate bisphenol C. Thereafter, it was cooled to 10°C, and after reaching 10°C, solid-liquid separation was carried out using a centrifuge to obtain a crude wet cake.

[0233] The entire amount of the crude wet cake obtained and 420 g of toluene were placed in a separable flask equipped with a thermometer, dropping funnel, jacket, and anchor-type stirring blade under a nitrogen atmosphere, and the temperature was raised to 80 °C to obtain a homogeneous solution. 200 g of demineralized water was added to the obtained homogeneous solution, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (first aqueous phase) was removed to obtain a fifth organic phase. The pH of the first aqueous phase was 9.2. 200 g of demineralized water was added to the obtained fifth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (second aqueous phase) was removed to obtain a sixth organic phase. 200 g of demineralized water was added to the obtained sixth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (third aqueous phase) was removed to obtain a seventh organic phase. The electrical conductivity of the third aqueous phase was 2.3 μS / cm.

[0234] The obtained seventh organic phase was cooled from 80°C to 20°C and maintained at 20°C to precipitate bisphenol C. It was then cooled to 10°C. After reaching 10°C, solid-liquid separation was performed using a centrifuge to obtain a wet cake. The obtained wet cake was washed by sprinkling 200g of toluene, and solid-liquid separation was performed using a centrifuge to obtain a purified wet cake. The obtained purified wet cake was distilled at an oil bath temperature of 100°C under reduced pressure to remove low boiling points, thereby obtaining 183g of a white bisphenol C composition.

[0235] The bisphenol C content in the obtained bisphenol C composition was 99.9 mass %, the indan C1 content was 107 mass ppm, and the indan C2 content was 8 mass ppm. The methanol dissolution color of the obtained bisphenol C composition was measured, and the Hazen color scale was 3. The melt color difference of the obtained bisphenol C composition was measured, and the Hazen color scale was 48. The thermal color stability of the obtained bisphenol C composition was measured, and the Hazen color scale was 120. The thermal decomposition stability of the obtained bisphenol C was measured, and the amount of isopropenyl cresol produced was 485 ppm by mass.

[0236] The iron and aluminum contents of the resulting bisphenol C composition were measured and found to be 0.61 ppm by mass and 0.33 ppm by mass.

[0237] [Comparative example I-2] The indan C1 content in the bisphenol C reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was 165 ppm by mass, and indan C2 was not detected. The methanol dissolution color of the bisphenol C of this reagent was measured, giving a Hazen color number of 20. The melt color difference of the bisphenol C of this reagent was measured, giving a Hazen color number of 46. The thermal color stability of the bisphenol C of this reagent was measured, giving a Hazen color number of 114. The thermal decomposition stability of the bisphenol C of this reagent was measured, giving a production amount of isopropenyl cresol of 585 ppm by mass.

[0238] The iron and aluminum contents of the bisphenol C in the reagent were measured and found to be 1.22 ppm by mass and 0.23 ppm by mass.

[0239] Table 1 summarizes the contents of indan C1 and indan C2 in the bisphenol C compositions of Examples I-1 and I-2 and Comparative Examples I-1 and I-2, as well as the methanol dissolution color, melting color difference, thermal color stability, thermal decomposition stability, and metal (iron (Fe) and aluminum (Al)) contents.

[0240] Table 1 shows that the inclusion of 200 mass ppm or more and 1400 mass ppm or less of Indan C1 and Indan C2 improves the methanol dissolution color, melt color difference, and thermal color stability. The inclusion of 200 mass ppm or more and 1400 mass ppm or less of Indan C1 and Indan C2 also improves the thermal decomposition stability.

[0241] [Table 1]

[0242] [Example I-3] A 150 mL glass reactor equipped with a stirrer and a distillation tube was charged with 100.00 g (0.39 mol of bisphenol C) of the bisphenol C composition obtained in Example I-1, 86.49 g (0.4 mol) of diphenyl carbonate, and 479 μL of a 400 ppm by mass aqueous cesium carbonate solution. The pressure in the glass reactor was reduced to approximately 100 Pa, and then the pressure was returned to atmospheric pressure with nitrogen. This operation was repeated three times to replace the inside of the reactor with nitrogen. The reactor was then immersed in a 200°C oil bath to dissolve the contents.

[0243] The agitator rotation speed was set to 100 rpm, and the pressure inside the reactor was reduced from 101.3 kPa absolute pressure to 13.3 kPa over 40 minutes while distilling off phenol, a by-product of the oligomerization reaction of bisphenol C and diphenyl carbonate in the reactor. The pressure inside the reactor was then maintained at 13.3 kPa, and the transesterification reaction was carried out for 80 minutes while further distilling off phenol. The temperature outside the reactor was then raised to 250°C, and the pressure inside the reactor was reduced from 13.3 kPa absolute pressure to 399 Pa over 40 minutes, and the distilled phenol was removed from the system.

[0244] Thereafter, the temperature outside the reactor was raised to 280°C, the absolute pressure inside the reactor was reduced to 30 Pa, and the polycondensation reaction was carried out. The polycondensation reaction was terminated when the agitator in the reactor reached a predetermined stirring power. The time from raising the temperature to 280°C to completing the polymerization (second-stage polymerization time) was 210 minutes.

[0245] Next, the reactor was restored to an absolute pressure of 101.3 kPa with nitrogen, and then the pressure was increased to a gauge pressure of 0.2 MPa, and the polycarbonate resin was withdrawn in the form of strands from the bottom of the reactor to obtain a strand-like polycarbonate resin. Thereafter, the strands were pelletized using a rotary cutter to obtain pelletized polycarbonate resin.

[0246] The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,800, and the pellet YI was 6.9. The amount of indan C1 in the obtained alkaline hydrolysis product of the polycarbonate resin was 49 ppm by mass relative to the polycarbonate resin, and indan C2 was not detected.

[0247] [Example I-4] Example I-3 was carried out in the same manner as in Example I-3, except that 100.00 g (0.39 mol of bisphenol C) of the bisphenol C composition obtained in Example I-2 was used instead of 100.00 g (0.39 mol of bisphenol C) of the bisphenol C composition obtained in Example I-1. The time from raising the temperature to 280°C to completing the polymerization (second-stage polymerization time) was 220 minutes. The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,800, and the pellet YI was 6.5. The amount of indan C1 in the obtained alkaline hydrolysis product of the polycarbonate resin was 147 ppm by mass relative to the polycarbonate resin, and indan C2 was not detected.

[0248] [Comparative example I-3] Example I-3 was carried out in the same manner as in Example I-3, except that 100.00 g (0.39 mol of bisphenol C) of the bisphenol C composition obtained in Comparative Example I-1 was used instead of 100.00 g (0.39 mol of bisphenol C) of the bisphenol C composition obtained in Example I-1. The time from raising the temperature to 280°C to completing the polymerization (second-stage polymerization time) was 230 minutes. The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,800, and the pellet YI was 10.2. In the obtained alkaline hydrolysis product of the polycarbonate resin, indan C1 was 2 ppm by mass relative to the polycarbonate resin, and indan C2 was not detected.

[0249] For Examples I-3 and I-4 and Comparative Example I-3, the ratio of the indan C1 and indan C2 contents in the alkaline hydrolysis products of the polycarbonate resin relative to the polycarbonate resin, and the pellet YI of the obtained polycarbonate resin are summarized in Table 2.

[0250] From Table 2, it can be seen that the pellet YI is improved by including the indan C1 and indan C2 components in the polycarbonate resin.

[0251] [Table 2]

[0252] [Examples of the second embodiment and comparative examples] [Example II-1] (1) Preparation of the first mixed solution 320 g of toluene, 15 g of methanol, and 230 g (2.13 mol) of ortho-cresol were placed in a separable flask equipped with a thermometer, a dropping funnel, a jacket, and an anchor-type stirring blade under a nitrogen atmosphere, and the internal temperature was adjusted to 10°C or below. Then, 95 g of 98 wt% sulfuric acid was slowly added over 0.3 hours with stirring, and the mixture was cooled to 5°C or below.

[0253] (2) Preparation of the second mixture A second mixed liquid (dropping liquid) was prepared by mixing 50 g of toluene, 65 g (1.12 mol) of acetone, and 5.4 g of dodecanethiol in a 500 mL Erlenmeyer flask.

[0254] (3) Preparation of reaction solution After the internal temperature of the first mixed solution was reduced to 5°C or lower, the second mixed solution was added using the dropping funnel over 1 hour so that the internal temperature did not exceed 10°C, thereby preparing a reaction solution.

[0255] (4) Reaction The prepared reaction solution was stirred at an internal temperature of 10°C for 2.5 hours.

[0256] (5) Purification (washing) After the reaction was completed, 190 g of a 25% aqueous sodium hydroxide solution was added and the temperature was raised to 80°C. After reaching 80°C, the mixture was allowed to stand, and the lower aqueous phase was removed. 400 g of demineralized water was added to the obtained first organic phase, mixed for 30 minutes, allowed to stand, and the aqueous phase was removed. 120 g of a 1.5% by mass sodium bicarbonate solution was added to the obtained second organic phase, mixed for 30 minutes, allowed to stand, and the lower phase was removed. Another 120 g of a 1.5% by mass sodium bicarbonate solution was added to the obtained third organic phase, mixed for 30 minutes, allowed to stand, and the lower phase was removed. The obtained fourth organic phase was removed, and its mass was measured and found to be 666 g.

[0257] A portion of the fourth organic phase was taken out, and the composition of the fourth organic phase was confirmed by high-performance liquid chromatography. As a result, it was found that ortho-cresol was produced in an amount of 5.3 mass% (5.3 mass% × mass of organic phase 666 g × molecular weight of ortho-cresol 108 g / mol × amount of ortho-cresol charged 2.1 mol = 15.3 mol%), and bisphenol C was produced in an amount of 31.5 mass% (31.5 mass% × mass of organic phase 666 g × 2 × molecular weight of bisphenol C 256 g / mol × amount of ortho-cresol charged 2.1 mol = 78.0 mol%).

[0258] (6) Purification (washing and crystallization) 200 g of demineralized water was added to the resulting fourth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (first aqueous phase) was removed to obtain a fifth organic phase. The pH of the first aqueous phase was 9.7. 200 g of demineralized water was added to the resulting fifth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (second aqueous phase) was removed to obtain a sixth organic phase. 200 g of demineralized water was added to the resulting sixth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (third aqueous phase) was removed. The electrical conductivity of the third aqueous phase was 2.7 μS / cm.

[0259] The resulting sixth organic phase was cooled from 80°C to 20°C and maintained at 20°C to precipitate bisphenol C. It was then cooled to 10°C, and after reaching 10°C, solid-liquid separation was performed using a centrifuge to obtain a crude wet cake. 500g of toluene was sprinkled onto the resulting wet cake to wash it, and solid-liquid separation was performed using a centrifuge to obtain a purified wet cake. The resulting purified wet cake was distilled off low-boiling components under reduced pressure at an oil bath temperature of 100°C using an evaporator equipped with an oil bath, yielding 190g of a white bisphenol C composition.

[0260] The methanol dissolution color of the obtained bisphenol C composition was measured, and the Hazen color number was 0. The melt color difference of the obtained bisphenol C composition was measured, and the Hazen color number was 3. The thermal color stability of the obtained bisphenol C composition was measured, and the Hazen color number was 26. The thermal decomposition stability of the obtained bisphenol C composition was measured, and the amount of isopropenyl cresol produced was 186 ppm by mass.

[0261] The quality of the obtained bisphenol C composition was confirmed, and a characteristic peak was detected at a retention time of 28.87 minutes on a high-performance liquid chromatograph. To identify the component of this peak, a high-performance liquid chromatograph equipped with a mass spectrometer was used to measure it, and the molecular weight was found to be 296 g / mol.

[0262] 1.6 g of the resulting bisphenol C composition was dissolved in acetonitrile, and the characteristic peak was separated using preparative liquid chromatography. The solution obtained by separation was dried, and the resulting dried product was dissolved in deuterated chloroform and measured by various NMR (Figures 7 to 12). It was confirmed to be 1-(4-hydroxy-3-methylphenyl)-6-hydroxy-1,3,3,5-tetramethylindan (indan C2) having the structure shown in the following structural formula (IIb).

[0263] Indane C2; 1 NMR(400MHz, CDCl3) 1.03(Me,s,3H),1.29(Me,s,3H),1.59(Me,s,6H),2.11(Me,s,3H),2.27(CH2,s,3H),4,62(OH,s,1H),4.64(OH,s,1H),6.47-6.91(CH,m,5H); 13CNMR(400MHz,CDCl3)16.1,29.9,30.8,31.8,59.8,42.3,49.9,111.0,11 4.3,122.7,123.0,124.9,125.4,129.3,143.3,144.5,148.5,151.5,152.8.

[0264] [ka]

[0265] The resulting bisphenol C composition contained 12 ppm by mass of indan C2. The bisphenol C content in the obtained bisphenol C composition was 99.9% by mass. As other bisphenols, monomethylbisphenol A was contained in an amount of 0.1% by mass.

[0266] [Example II-2] (1) Preparation of the first mixed solution 320 g of toluene, 15 g of methanol, and 230 g (2.13 mol) of ortho-cresol were placed in a separable flask equipped with a thermometer, a dropping funnel, a jacket, and an anchor-type stirring blade under an air atmosphere, and the internal temperature was adjusted to 10°C or below. Then, 95 g of 98 wt% sulfuric acid was slowly added over 0.3 hours while stirring, and the mixture was cooled to 5°C or below.

[0267] (2) Preparation of the second mixture A second mixed liquid (dropping liquid) was prepared by mixing 50 g of toluene, 65 g (1.12 mol) of acetone, and 5.4 g of dodecanethiol in a 500 mL Erlenmeyer flask.

[0268] (3) Preparation of reaction solution After the internal temperature of the first mixed solution was reduced to 5°C or lower, the second mixed solution was added using the dropping funnel over 1 hour so that the internal temperature did not exceed 10°C, thereby preparing a reaction solution.

[0269] (4) Reaction The prepared reaction solution was stirred at an internal temperature of 30°C for 2.5 hours.

[0270] (5) Purification (washing) After the reaction was completed, 130 g of a 25% aqueous sodium hydroxide solution was added and the temperature was raised to 80°C. After reaching 80°C, the mixture was allowed to stand, and the lower aqueous phase was removed. 400 g of demineralized water was added to the obtained first organic phase, mixed for 30 minutes, allowed to stand, and the aqueous phase was removed. 120 g of a 1.5% by mass sodium bicarbonate solution was added to the obtained second organic phase, mixed for 30 minutes, allowed to stand, and the lower phase was removed. Another 120 g of a 1.5% by mass sodium bicarbonate solution was added to the obtained third organic phase, mixed for 30 minutes, allowed to stand, and the lower phase was removed. The obtained fourth organic phase was removed, and its mass was measured and found to be 666 g.

[0271] A portion of the fourth organic phase was removed, and the composition of the fourth organic phase was confirmed by high-performance liquid chromatography. As a result, it was found that ortho-cresol was produced in an amount of 3.5% by mass (3.5% by mass × 666 g of organic phase × 2 ÷ molecular weight of bisphenol C 256 g / mol × 2.1 mol of ortho-cresol = 85.5 mol%), and bisphenol C was produced in an amount of 34.5% by mass (34.5% by mass × 666 g of organic phase × 2 ÷ molecular weight of bisphenol C 256 g / mol × 2.1 mol of ortho-cresol = 85.5 mol%).

[0272] (6) Purification (washing and crystallization) 200 g of demineralized water was added to the resulting fourth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (first aqueous phase) was removed to obtain a fifth organic phase. The pH of the first aqueous phase was 9.7. 200 g of demineralized water was added to the resulting fifth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (second aqueous phase) was removed to obtain a sixth organic phase. 200 g of demineralized water was added to the resulting sixth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (third aqueous phase) was removed. The electrical conductivity of the third aqueous phase was 2.8 μS / cm.

[0273] The resulting sixth organic phase was cooled from 80°C to 20°C and maintained at 20°C to precipitate bisphenol C. It was then cooled to 10°C, and after reaching 10°C, solid-liquid separation was performed using a centrifuge to obtain a crude wet cake. 500g of toluene was sprinkled onto the resulting wet cake to wash it, and solid-liquid separation was performed using a centrifuge to obtain a purified wet cake. The resulting purified wet cake was distilled off low-boiling components under reduced pressure at an oil bath temperature of 100°C using an evaporator equipped with an oil bath, yielding 190g of a white bisphenol C composition.

[0274] The bisphenol C content in the obtained bisphenol C composition was 99.7 mass %, and the indan C2 content was 114 mass ppm. The methanol dissolution color of the obtained bisphenol C composition was measured, and the Hazen color number was 0. The melt color difference of the obtained bisphenol C composition was measured, and the Hazen color number was 5. The thermal color stability of the obtained bisphenol C composition was measured, and the Hazen color number was 38. The thermal decomposition stability of the obtained bisphenol C composition was measured, and the amount of isopropenyl cresol produced was 240 ppm by mass.

[0275] [Comparative Example II-1] (1) Preparation of the first mixed solution 320 g of toluene, 15 g of methanol, and 230 g (2.13 mol) of ortho-cresol were placed in a separable flask equipped with a thermometer, a dropping funnel, a jacket, and an anchor-type stirring blade under a nitrogen atmosphere, and the internal temperature was adjusted to 10°C or below. Then, 95 g of 98 wt% sulfuric acid was slowly added over 0.3 hours with stirring, and the mixture was cooled to 5°C or below.

[0276] (2) Preparation of the second mixture A second mixed liquid (dropping liquid) was prepared by mixing 50 g of toluene, 65 g (1.12 mol) of acetone, and 5.4 g of dodecanethiol in a 500 mL Erlenmeyer flask.

[0277] (3) Preparation of reaction solution After the internal temperature of the first mixed solution was reduced to 5°C or lower, the second mixed solution was added using the dropping funnel over 1 hour so that the internal temperature did not exceed 10°C, thereby preparing a reaction solution.

[0278] (4) Reaction The prepared reaction solution was stirred at an internal temperature of 10°C for 2 hours.

[0279] (5) Purification (washing) After the reaction was completed, 190 g of a 25% aqueous sodium hydroxide solution was added and the temperature was raised to 80°C. After reaching 80°C, the mixture was allowed to stand, and the lower aqueous phase was removed. 400 g of demineralized water was added to the obtained first organic phase, mixed for 30 minutes, allowed to stand, and the aqueous phase was removed. 120 g of a 1.5% by mass sodium bicarbonate solution was added to the obtained second organic phase, mixed for 30 minutes, allowed to stand, and the lower phase was removed. Another 120 g of a 1.5% by mass sodium bicarbonate solution was added to the obtained third organic phase, mixed for 30 minutes, allowed to stand, and the lower phase was removed. The obtained fourth organic phase was removed, and its mass was measured and found to be 666 g.

[0280] A portion of the fourth organic phase was taken out, and the composition of the fourth organic phase was confirmed by high-performance liquid chromatography. As a result, it was found that ortho-cresol was produced in an amount of 5.3 mass% (5.3 mass% × mass of organic phase 666 g × molecular weight of ortho-cresol 108 g / mol × amount of ortho-cresol charged 2.1 mol = 15.3 mol%), and bisphenol C was produced in an amount of 31.5 mass% (31.5 mass% × mass of organic phase 666 g × 2 × molecular weight of bisphenol C 256 g / mol × amount of ortho-cresol charged 2.1 mol = 78.0 mol%).

[0281] (6) Purification (washing and crystallization) The obtained fourth organic phase was cooled from 80°C to 20°C and maintained at 20°C to precipitate bisphenol C. Thereafter, it was cooled to 10°C, and after reaching 10°C, solid-liquid separation was carried out using a centrifuge to obtain a crude wet cake.

[0282] The entire amount of the crude wet cake obtained and 420 g of toluene were placed in a separable flask equipped with a thermometer, dropping funnel, jacket, and anchor-type stirring blade under a nitrogen atmosphere, and the temperature was raised to 80 °C to obtain a homogeneous solution. 200 g of demineralized water was added to the obtained homogeneous solution, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (first aqueous phase) was removed to obtain a fifth organic phase. The pH of the first aqueous phase was 9.2. 200 g of demineralized water was added to the obtained fifth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (second aqueous phase) was removed to obtain a sixth organic phase. 200 g of demineralized water was added to the obtained sixth organic phase, mixed for 30 minutes, and allowed to stand. The lower aqueous phase (third aqueous phase) was removed to obtain a seventh organic phase. The electrical conductivity of the third aqueous phase was 2.3 μS / cm.

[0283] The obtained seventh organic phase was cooled from 80°C to 20°C and maintained at 20°C to precipitate bisphenol C. It was then cooled to 10°C. After reaching 10°C, solid-liquid separation was performed using a centrifuge to obtain a wet cake. The obtained wet cake was washed by sprinkling 200g of toluene, and solid-liquid separation was performed using a centrifuge to obtain a purified wet cake. The obtained purified wet cake was distilled at an oil bath temperature of 100°C under reduced pressure to remove low boiling points, thereby obtaining 183g of a white bisphenol C composition.

[0284] The bisphenol C content in the obtained bisphenol C composition was 99.9 mass %, and the indan C2 content was 8 mass ppm. The methanol dissolution color of the obtained bisphenol C composition was measured, and the Hazen color scale was 3. The melt color difference of the obtained bisphenol C composition was measured, and the Hazen color scale was 48. The thermal color stability of the obtained bisphenol C composition was measured, and the Hazen color scale was 120. The thermal decomposition stability of the obtained bisphenol C was measured, and the amount of isopropenyl cresol produced was 485 ppm by mass.

[0285] [Comparative Example II-2] Indan C2 was not detected in the bisphenol C reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (lower limit of quantification: 0.1 ppm by mass). The methanol dissolution color of the bisphenol C of this reagent was measured, giving a Hazen color number of 20. The melt color difference of the bisphenol C of this reagent was measured, giving a Hazen color number of 46. The thermal color stability of the bisphenol C of this reagent was measured, giving a Hazen color number of 114. The thermal decomposition stability of the bisphenol C of this reagent was measured, giving a production amount of isopropenyl cresol of 585 ppm by mass.

[0286] Table 3 shows the content of indan C2 in the bisphenol C composition, the methanol dissolution color, the melting color difference, the thermal color stability, and the thermal decomposition stability for Examples II-1 and II-2 and Comparative Examples II-1 and II-2.

[0287] Table 3 shows that the inclusion of 10 ppm by mass or more and 120 ppm by mass or less of Indan C2 improves the methanol dissolution color, melting color difference, and thermal color stability. The inclusion of 10 ppm by mass or more and 120 ppm by mass or less of Indan C2 also improves the thermal decomposition stability.

[0288] [Table 3]

[0289] [Example II-3] A 150 mL glass reactor equipped with a stirrer and a distillation tube was charged with 100.00 g (0.39 mol of bisphenol C) of the bisphenol C composition obtained in Example II-1, 86.49 g (0.4 mol) of diphenyl carbonate, and 479 μL of a 400 ppm by mass aqueous cesium carbonate solution. The glass reactor was depressurized to approximately 100 Pa, and then the pressure was returned to atmospheric pressure with nitrogen. This operation was repeated three times to replace the inside of the reactor with nitrogen. The reactor was then immersed in a 200°C oil bath to dissolve the contents.

[0290] The agitator rotation speed was set to 100 rpm, and the pressure inside the reactor was reduced from 101.3 kPa absolute pressure to 13.3 kPa over 40 minutes while distilling off phenol, a by-product of the oligomerization reaction of bisphenol C and diphenyl carbonate in the reactor. The pressure inside the reactor was then maintained at 13.3 kPa, and the transesterification reaction was carried out for 80 minutes while further distilling off phenol. The temperature outside the reactor was then raised to 250°C, and the pressure inside the reactor was reduced from 13.3 kPa absolute pressure to 399 Pa over 40 minutes, and the distilled phenol was removed from the system.

[0291] Thereafter, the temperature outside the reactor was raised to 280°C, the absolute pressure inside the reactor was reduced to 30 Pa, and the polycondensation reaction was carried out. The polycondensation reaction was terminated when the agitator in the reactor reached a predetermined stirring power. The time from raising the temperature to 280°C to completing the polymerization (second-stage polymerization time) was 210 minutes.

[0292] Next, the reactor was restored to an absolute pressure of 101.3 kPa with nitrogen, and then the pressure was increased to a gauge pressure of 0.2 MPa, and the polycarbonate resin was withdrawn in the form of strands from the bottom of the reactor to obtain a strand-like polycarbonate resin. Thereafter, the strands were pelletized using a rotary cutter to obtain pelletized polycarbonate resin.

[0293] The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,800, and the pellet YI was 6.9.

[0294] [Comparative Example II-3] Example II-3 was carried out in the same manner as in Example II-3, except that 100.00 g (0.39 mol of bisphenol C) of the bisphenol C composition obtained in Comparative Example II-1 was used instead of 100.00 g (0.39 mol of bisphenol C) of the bisphenol C composition obtained in Example II-1. The time from raising the temperature to 280°C to completing the polymerization (second-stage polymerization time) was 230 minutes. The viscosity average molecular weight (Mv) of the obtained polycarbonate resin was 24,800, and the pellet YI was 10.2.

[0295] Table 4 shows the indane C2 content in the bisphenol C composition used to produce the polycarbonate resin and the pellet YI of the obtained polycarbonate resin for Example II-3 and Comparative Example II-3.

[0296] Table 4 shows that by using a bisphenol C composition containing indan C2 at a predetermined ratio, the pellet YI of the obtained polycarbonate resin is improved.

[0297] [Table 4]

[0298] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2019-047450 filed on March 14, 2019, Japanese Patent Application No. 2019-047453 filed on March 14, 2019, Japanese Patent Application No. 2019-047454 filed on March 14, 2019, Japanese Patent Application No. 2019-234571 filed on December 25, 2019, and Japanese Patent Application No. 2019-234572 filed on December 25, 2019, which are incorporated by reference in their entirety.< / nmr>

Claims

1. A polycarbonate resin having at least a repeating structural unit represented by the following general formula (A), wherein a compound obtained by alkaline hydrolysis of the polycarbonate resin contains a bisphenol represented by the following general formula (I) and a compound represented by the following general formula (II), and the content of the compound represented by the following general formula (II) in the compound obtained by alkaline hydrolysis of the polycarbonate resin is 5 ppm by mass or more and 200 ppm by mass or less, based on the polycarbonate resin. 【Transformation 3】 In general formula (A), R １ is a methyl group. ２ ~R ６ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group, and the alkyl group, alkoxy group, and aryl group may be substituted or unsubstituted. ５ and R ６ may be bonded or bridged to each other between two groups, and R ５ and R ６ and may be bonded together with adjacent carbon atoms to form a cycloalkylidene group which may contain heteroatoms. 【Chemistry 4】 In general formula (I), R １１ is a methyl group. １２ ~R １４ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group. １５ and R １６ are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an aryl group. １５ and R １６ may be bonded or bridged to each other between the two groups. １５ and R １６ and bonded or bridged to adjacent carbon atoms are excluded. 【Transformation 5】 In general formula (II), R ２1 and R ２２ is a methyl group or a hydrogen atom, and R ２１ When R is a hydrogen atom ２２ is a methyl group, and R ２１ When R is a methyl group ２２ is a hydrogen atom. ２３ ~R ２５ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ２３ and R ２４ and R ２５ may be bonded or bridged to each other between the two groups.

2. 2. The polycarbonate resin according to claim 1, wherein the compound represented by the general formula (II) is 1-(4-hydroxy-3-methylphenyl)-6-hydroxy-1,3,3,7-tetramethylindane.

3. The polycarbonate resin according to claim 1 or 2, wherein the compound obtained by alkaline hydrolysis of the polycarbonate resin contains 2,2-bis(4-hydroxy-3-methylphenyl)propane and / or 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane.

4. 4. The polycarbonate resin according to claim 1, which has a viscosity average molecular weight of 15,000 or more and 35,000 or less.

5. 5. The polycarbonate resin according to claim 1, wherein the pellet YI is 10 or less.

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