Polycarbonate Resin

Abstract

Provided is a polycarbonate resin having excellent solubility in low-boiling-point non-halogenated solvents and having a high glass transition temperature.　The polycarbonate resin comprises constituent units (A) represented by general formula (1) and constituent units (B) represented by general formula (2), the molar ratio of the constituent units (A) to the constituent units (B), A / B, being 45 / 55 to 95 / 5.

Description

[Technical field]

[0001] The present invention relates to a polycarbonate resin, and a resin solution and a film using the same. [Background technology]

[0002] Polycarbonate resins are widely used in electrical and electronic equipment, office automation equipment, optical media, automotive parts, building materials, and the like due to their excellent mechanical strength, heat resistance, electrical properties, dimensional stability, flame retardancy, transparency, and the like (for example, Patent Documents 1 to 5). The production of polycarbonate films is roughly divided into extrusion molding and wet molding. Of these, wet molding is used as a method for molding polycarbonate resin, which has a high glass transition temperature, into a film. To perform wet molding efficiently, it is necessary to dissolve the resin at a high concentration (e.g., 20% by mass or more) using an organic solvent with a relatively low boiling point. Traditionally, halogen-based solvents have been used as low-boiling solvents with excellent resin solubility, but in recent years, there has been a demand to use non-halogen-based solvents that do not contain halogens due to environmental considerations. Ketone-based solvents and ester-based solvents are known as low-boiling non-halogenated solvents used in wet molding. However, polycarbonate resins with high glass transition temperatures that have been used in the past may have poor solubility in these solvents, resulting in poor molding efficiency in wet molding. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 63-89540 [Patent Document 2] Japanese Patent Application Publication No. 2-99521 [Patent Document 3] Japanese Patent Application Publication No. 2-128336 [Patent Document 4] JP 2017-031245 A [Patent Document 5] JP 2011-246583 A Summary of the Invention

[0004] Under these circumstances, it is desired to provide a novel polycarbonate resin.

[0005] The present invention is, for example, as follows. [1] A polycarbonate resin comprising a structural unit (A) represented by general formula (1) and a structural unit (B) represented by general formula (2), in which the molar ratio (A / B) of the structural unit (A) to the structural unit (B) is 45 / 55 to 95 / 5. [ka] [In formula (2), R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and an aralkyl group having 7 to 17 carbon atoms, and the alkyl group, the aryl group, the alkenyl group, the alkoxy group, and the aralkyl group each optionally have a substituent; X represents -O-, -S-, -SO-, -SO2-, -CO-, a cycloalkylene group having 6 to 12 carbon atoms, or a divalent group represented by either general formula (3) or general formula (4), the cycloalkylene group being optionally substituted by an alkyl group having 1 to 3 carbon atoms and having 1 to 12 carbon atoms; [ka] (In formula (3), R9 and R 10 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms; R9 and R 10wherein the alkyl group, the alkoxy group, the aryl group, the aralkyl group and the alkenyl group each may have a substituent, R9 and R 10 may be bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, and the carbocyclic ring and the heterocyclic ring each may have a substituent. R9 and R 10 Both of these cannot be methyl groups. n represents an integer from 0 to 20. [ka] (In formula (4), R 11 and R 12 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms, each of which may have a substituent, R 11 and R 12 may be bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, and the carbocyclic ring and the heterocyclic ring each may have a substituent.)] [1a] The resin according to [1], wherein X represents -O-, -S-, -SO-, -SO2-, -CO-, a cyclohexene group substituted with 1 to 12 alkyl groups having 1 to 3 carbon atoms, a cycloalkylene group having 7 to 12 carbon atoms which may be substituted with 1 to 12 alkyl groups having 1 to 3 carbon atoms, or a divalent group represented by any one of the general formula (3) or the general formula (4). [2] The resin according to [1], having a viscosity average molecular weight (Mv) of 16,000 to 80,000. [2a] The resin according to [1], having a viscosity average molecular weight (Mv) of 20,000 to 80,000. [3] The resin according to [1] or [2], having a viscosity average molecular weight (Mv) of 26,000 to 80,000. [4] The resin according to any one of [1] to [3], which has a glass transition temperature (Tg) of 150° C. or higher. [5] The resin according to any one of claims 1 to 4, wherein the structural unit (B) is represented by the following general formula (3A): [ka] (In formula (3A), R9 represents an alkyl group having 1 to 20 carbon atoms; R 10 represents an aryl group having 6 to 12 carbon atoms.

[0006] [6] The resin according to [5], wherein the structural unit (B) is represented by the following general formula (3B): [ka] [7] The resin according to any one of [1] to [4], wherein the structural unit (B) is represented by the following general formula (5A): [ka] (In formula (5A), R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , and R 22 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. [7a] The resin according to any one of [1] to [4], wherein the structural unit (B) is represented by the following general formula (5): [ka] (In formula (5), m represents an integer from 1 to 7; R 13 , R 14 , R 15 , R16 , R 17 , R 18 , R 19 , R 20 , R 21 , and R 22 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. [7b] In formula (5), (i) m is 1, and R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , and R 22 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , and R 22 at least one of is an alkyl group having 1 to 3 carbon atoms; or (ii) m represents an integer of 2 to 7, R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , and R 22 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. [8] R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , and R 22 At least one of the above is an alkyl group having 1 to 3 carbon atoms. [9] The resin according to any one of [1] to [4], wherein X represents a cycloalkylene group having 7 to 12 carbon atoms, and the cycloalkylene group may be substituted with 1 to 12 alkyl groups having 1 to 3 carbon atoms.

[10] X is a divalent group represented by the formula (4), R 11 and R 12 are each independently selected from a hydrogen atom and an aryl group having 6 to 12 carbon atoms.

[11] The resin according to any one of [1] to

[10] , wherein R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0007]

[12] A film comprising the polycarbonate resin according to any one of [1] to

[11] . [12a] A resin composition comprising the polycarbonate resin according to any one of [1] to

[11] .

[13] A resin solution comprising a non-halogenated organic solvent and the polycarbonate resin according to any one of [1] to

[11] dissolved in the non-halogenated solvent.

[14] The resin solution according to

[13] , wherein a concentration of the polycarbonate resin in the resin solution is 20 mass% or more.

[15] The resin solution according to

[13] or

[14] , wherein the non-halogenated organic solvent is at least one of a ketone solvent and an ester solvent. [15a] The resin solution according to

[13] or

[14] , wherein the non-halogenated organic solvent is at least one of methyl ethyl ketone and ethyl acetate.

[16] A film obtained by wet molding the resin solution according to any one of

[13] to

[15] . [16a] A method for producing a film, comprising wet molding using the resin solution according to any one of

[13] to

[15] .

[0008]

[17] The polycarbonate resin according to any one of [1] to

[10] , comprising a terminal structure T selected from a terminal structure represented by formula (T1) (particularly, a terminal structure derived from p-hydroxyphenethyl alcohol (PHEP)), a terminal structure represented by formula (T2) (particularly, a terminal structure represented by formula (T3)), and a terminal structure represented by formula (T4). [ka] (In formula (T1), R A represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms, each of which may have a substituent; R B and R C each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, Z represents an ether bond, a carbonyl group, an ester bond, or a single bond; a is an integer from 1 to 3; * indicates the bonding position with the main chain of the polycarbonate resin.) [ka] (In formula (T2) and formula (T3), R D represents hydrogen or an alkyl group having 1 to 6 carbon atoms; R E represents an alkylene group having 1 to 6 carbon atoms, R F represents a hydrogen atom or a methyl group, R G represents a hydrogen atom or a halogen atom, * indicates the bonding position with the main chain of the polycarbonate resin.) [ka]

[18] The resin according to

[17] , wherein the terminal structure T is contained in an amount of 0.95 mol or more (preferably 1.5 mol or more) and 10 mol or less (preferably 5 mol or less) per 100 mol of a structural unit derived from a dihydroxy compound (e.g., the total of the structural unit (A) represented by general formula (1) and the structural unit (B) represented by general formula (2)).

[0009] According to one embodiment of the present invention, there is provided a polycarbonate resin having excellent solubility in a low-boiling non-halogenated solvent and a high glass transition temperature. The polycarbonate resin of the embodiment has excellent solubility in low-boiling non-halogenated solvents, and therefore enables efficient and inexpensive production of good molded products, thereby improving productivity and being environmentally friendly. In a preferred embodiment, a polycarbonate resin is provided which has excellent solubility in ketone-based solvents and / or ester-based solvents and a high glass transition temperature (for example, 150° C. or higher). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The meanings of the terms used in this specification will be explained below, and the present invention will be described in detail. "Alkyl" means a straight-chain, cyclic or branched saturated aliphatic hydrocarbon group having the specified number of carbon atoms. "Aryl" refers to an aromatic hydrocarbon cyclic group having the specified number of carbon atoms. "Alkenyl" means a straight or branched chain hydrocarbon group having the specified number of carbon atoms and at least one carbon-carbon double bond, including, but not limited to, monoenes, dienes, trienes, and tetraenes. An "alkoxy" is an alkyl group having the specified number of carbon atoms having an oxygen atom (O) attached to the end of the alkyl group. An "aralkyl" is a group in which one of the alkyl hydrogen atoms is replaced by an aryl. "Alkylene" means a divalent linear, cyclic or branched saturated aliphatic hydrocarbon group having the specified number of carbon atoms. "Alkenylene" means a divalent linear or branched hydrocarbon group having the specified number of carbon atoms and at least one carbon-carbon double bond. "Cycloalkylene" means a divalent cyclic alkyl having a specified number of carbon atoms. A "halogen" is a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I).

[0011] 1. Polycarbonate resin One aspect of the present invention provides a polycarbonate resin containing a structural unit (A) represented by general formula (1) and a structural unit (B) represented by general formula (2). In the polycarbonate resin, the molar ratio (A / B) of the structural unit (A) to the structural unit (B) is 45 / 55 to 95 / 5. In one embodiment, the polycarbonate resin is a copolymer containing the structural unit (A) and the structural unit (B). The structure of the copolymer may be any of a random, block, and alternating copolymer. [ka] The polycarbonate resin of this embodiment (hereinafter also simply referred to as "polycarbonate resin") can achieve both a high glass transition temperature (Tg) and excellent solubility in low-boiling non-halogenated solvents. Although the reason why such a high Tg and good solvent solubility are achieved is unclear, the present inventors presume that a polycarbonate resin that simultaneously satisfies both properties can be obtained by copolymerizing a structural unit (A) that shows good solvent solubility and a structural unit (B) that shows a high Tg in a specific ratio.

[0012] In the above formula (2), R1, R2, R3, R4, R5, R6, R7, and R8 (hereinafter sometimes abbreviated as "R1 to R8") are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 7 carbon atoms (preferably having 1 to 5 carbon atoms, more preferably having 1 to 3 carbon atoms), an aryl group having 6 to 12 carbon atoms (preferably having 6 to 10 carbon atoms, more preferably having 6 to 8 carbon atoms), an alkenyl group having 2 to 7 carbon atoms (preferably having 2 to 5 carbon atoms, more preferably having 2 to 3 carbon atoms), an alkoxy group having 1 to 7 carbon atoms (preferably having 1 to 5 carbon atoms, more preferably having 1 to 3 carbon atoms), and an aralkyl group having 7 to 17 carbon atoms (preferably having 7 to 12 carbon atoms, more preferably having 7 to 10 carbon atoms). The alkyl group, the aryl group, the alkenyl group, the alkoxy group and the aralkyl group in R1 to R8 may each have a substituent, which is at least one selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms (preferably having 1 to 10 carbon atoms, more preferably having 1 to 3 carbon atoms) and an aryl group having 6 to 12 carbon atoms (preferably having 6 to 10 carbon atoms, more preferably having 6 to 8 carbon atoms). Among these, from the viewpoints of market availability and price of the raw material monomers and strength (e.g., pencil strength) of the obtained film, R1 to R8 are preferably each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and more preferably a hydrogen atom, a methyl group, or a phenyl group.

[0013] In the above formula (2), X represents -O-, -S-, -SO-, -SO2-, -CO-, a cycloalkylene group having 6 to 12 carbon atoms (preferably having 6 to 10 carbon atoms, more preferably having 6 to 8 carbon atoms), or a divalent group represented by either the following general formula (3) or the following general formula (4).

[0014] The cycloalkylene group represented by X may be substituted with 1 to 12 (preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 3) alkyl groups having 1 to 3 carbon atoms. In a preferred embodiment, the cycloalkylene group as X is substituted with at least one (preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 3) alkyl group having 1 to 3 carbon atoms. In such a case, the glass transition temperature can be increased while maintaining the solvent solubility. In a specific embodiment, the cycloalkylene group as X is cyclohexene substituted with at least one (preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 3) alkyl group having 1 to 3 carbon atoms. In another preferred embodiment, the cycloalkylene group represented by X is a cycloalkylene group having 7 to 12 carbon atoms, which may be substituted with 1 to 12 (preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 3) alkyl groups having 1 to 3 carbon atoms. In such a case, the glass transition temperature can be increased while maintaining the solvent solubility. In another preferred embodiment, X represents a cycloalkylene group having 7 to 12 carbon atoms, and the cycloalkylene group may be substituted with an alkyl group having 1 to 12 carbon atoms and 1 to 3. In such a case, the glass transition temperature can be increased while maintaining the solvent solubility.

[0015] [ka] In the above formula (3), R9 and R 10 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms (preferably having 1 to 10 carbon atoms, more preferably having 1 to 5 carbon atoms), an alkoxy group having 1 to 7 carbon atoms (preferably having 1 to 5 carbon atoms, more preferably having 1 to 3 carbon atoms), an aryl group having 6 to 12 carbon atoms (preferably having 6 to 10 carbon atoms, more preferably having 6 to 8 carbon atoms), an aralkyl group having 7 to 17 carbon atoms (preferably having 7 to 12 carbon atoms, more preferably having 7 to 10 carbon atoms), and an alkenyl group having 2 to 15 carbon atoms (preferably having 2 to 5 carbon atoms, more preferably having 2 to 3 carbon atoms). R9 and R 10The alkyl group, the alkoxy group, the aryl group, the aralkyl group and the alkenyl group in the above may each have a substituent, which is at least one selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms (preferably having 1 to 10 carbon atoms, more preferably having 1 to 5 carbon atoms) and an aryl group having 6 to 12 carbon atoms (preferably having 6 to 10 carbon atoms, more preferably having 6 to 8 carbon atoms).

[0016] In the above formula (3), R9 and R 10 may be bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms (preferably 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms) or a heterocyclic ring having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms). The carbocyclic ring or the heterocyclic ring may each have a substituent. The optional substituent is at least one selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms). In the above formula (3), R9 and R 10 Both of these cannot be methyl groups.

[0017] Among them, R9 and R10 are the most suitable in terms of the market availability and price of the raw material monomers and the strength of the resulting films (e.g. pencil strength). 10 are each independently preferably an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), an aryl group having 6 to 12 carbon atoms (preferably 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms), an aralkyl group having 7 to 17 carbon atoms (preferably 7 to 12 carbon atoms, more preferably 7 to 10 carbon atoms), or an alkenyl group having 2 to 15 carbon atoms (preferably 2 to 5 carbon atoms, more preferably 2 to 3 carbon atoms), and more preferably an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms) or an aryl group having 6 to 12 carbon atoms (preferably 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms).

[0018] In the above formula (3), n represents an integer of 0 to 20. In terms of market availability and price of the raw material monomer and strength (for example, pencil strength) of the obtained film, n is preferably an integer of 1 to 12, and more preferably an integer of 1 to 3.

[0019] [ka] In the above formula (4), R 11 and R 12 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms (preferably having 1 to 9 carbon atoms, more preferably having 1 to 5 carbon atoms), an alkoxy group having 1 to 7 carbon atoms (preferably having 1 to 5 carbon atoms, more preferably having 1 to 3 carbon atoms), an aryl group having 6 to 12 carbon atoms (preferably having 6 to 10 carbon atoms, more preferably having 6 to 8 carbon atoms), an aralkyl group having 7 to 17 carbon atoms (preferably having 7 to 12 carbon atoms, more preferably having 7 to 10 carbon atoms), and an alkenyl group having 2 to 15 carbon atoms (preferably having 2 to 5 carbon atoms, more preferably having 2 to 3 carbon atoms). R 11 and R 12 The alkyl group, the alkoxy group, the aryl group, the aralkyl group and the alkenyl group in the above may each have a substituent, which is at least one selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms (preferably having 1 to 10 carbon atoms, more preferably having 1 to 5 carbon atoms) and an aryl group having 6 to 12 carbon atoms (preferably having 6 to 10 carbon atoms, more preferably having 6 to 8 carbon atoms). In the above formula (4), R 11 and R 12may be bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms (preferably 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms) or a heterocyclic ring having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms). The carbocyclic ring or the heterocyclic ring may each have a substituent. The optional substituent is at least one selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), and an aryl group having 6 to 12 carbon atoms (preferably 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms).

[0020] In particular, in terms of market availability of raw material monomers, 11 and R 12 are each independently preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0021] The structural unit (B) represented by the above general formula (2) preferably contains a ring structure such as a cycloalkane or aryl as X, from the viewpoints of improving heat resistance and improving solubility in non-halogen-based organic solvents. Preferred examples of the structural unit (B) are given below.

[0022] In one embodiment, the structural unit (B) represented by the above general formula (2) is represented by the following general formula (3A). [ka]

[0023] In the above formula (3A), R9 represents an alkyl group having 1 to 20 carbon atoms. Among these, R9 is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and from the viewpoint of marketability and price of the raw material monomer, is further preferably a methyl group, an ethyl group, or a propyl group, and particularly preferably a methyl group. In the above formula (3A), R 10 represents an aryl group having 6 to 12 carbon atoms. 10is preferably an aryl group having 6 to 8 carbon atoms, and from the standpoint of market availability and price of the raw material monomer, a phenyl group is particularly preferred.

[0024] In a preferred embodiment, the structural unit (B) is represented by the following general formula (3B). [ka]

[0025] As shown in formula (3A) or (3B), R 10 When the structure contains an aromatic ring, the rotational potential energy of the molecular chain increases, and the glass transition temperature can be improved.

[0026] In one embodiment, the structural unit (B) represented by the above general formula (2) is represented by the following general formula (5): When the polycarbonate resin has the structure of formula (5), it is preferable in that the solubility in non-halogen-based organic solvents is improved. [ka]

[0027] In the above formula (5), m represents an integer of 1 to 7.

[0028] In one embodiment, in formula (5), m is 1. That is, in a preferred embodiment, the structural unit (B) is represented by the following general formula (5A). [ka]

[0029] In the above formula (5) and formula (5A), R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 (Hereinafter referred to as “R 13 ~R 18 Each of R 1 and R 2 independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.13 ~R 18 are preferably each independently a hydrogen atom, methyl, ethyl or propyl.

[0030] In one embodiment, in the above formula (5), m is 2 to 7, and R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , and R 22 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0031] In one embodiment, in the above formula (5) and formula (5A), R 13 ~R 18 At least one of them (preferably 1 to 6, more preferably 1 to 3) is an alkyl group having 1 to 3 carbon atoms (for example, methyl, ethyl). In such a case, the glass transition temperature can be increased while maintaining the solvent solubility.

[0032] In one embodiment, in the above formula (5) and formula (5A), R 13 ~R 18 In one embodiment, in the above formula (5), m represents an integer of 2 to 7, R 13 ~R 18 are all hydrogen atoms.

[0033] In one embodiment, the structural unit (B) represented by the above general formula (2) is represented by the following general formula (4), R 11 and R 12 are each independently selected from a hydrogen atom and an aryl group having a carbon number of 6 to 12. Having such a structure is preferable in that a polycarbonate resin having a high glass transition temperature and capable of producing a film with low birefringence can be obtained.

[0034] The structural unit (B) represented by the above general formula (2) can use either a single type alone or a combination of two or more types.

[0035] In the polycarbonate resin of the present embodiment, the molar ratio (A / B) of the structural unit (A) represented by general formula (1) to the structural unit (B) represented by general formula (2) is 45 / 55 to 95 / 5. By setting the molar ratio at such a level, it is possible to achieve a high glass transition temperature while improving the solubility in a solvent (e.g., a non-halogen-based solvent). From the viewpoints of the glass transition temperature and the solubility in a solvent, the molar ratio (A / B) of the structural unit (A) to the structural unit (B) is preferably 45 / 55 to 80 / 20, more preferably 50 / 50 to 80 / 20.

[0036] The polycarbonate resin may contain a structural unit (C) other than the structural unit (A) and the structural unit (B) as long as the solvent solubility and high glass transition temperature are not impaired. The total proportion of the structural unit (A) and the structural unit (B) in the polycarbonate resin is preferably 70 to 100 mass %, and more preferably 80 to 100 mass %, with respect to the polycarbonate resin (total mass: 100 mass %). Examples of the structural unit (C) include structural units derived from synthetic resins such as polycarbonates other than the polycarbonate resin of the present invention, aromatic polyesters, aliphatic polyesters, polyamides, polystyrenes, polyolefins, acrylics, amorphous polyolefins, ABS and AS, biodegradable resins such as polylactic acid and polybutylene succinate, and rubbers. The polycarbonate resin may contain at least one additive, such as an antioxidant, a processing stabilizer, a light stabilizer, a polymerized metal deactivator, a flame retardant, a lubricant, an antistatic agent, a surfactant, an antibacterial agent, a release agent, an ultraviolet absorber, a plasticizer, or a compatibilizer, as long as the properties of the present invention are not impaired.

[0037] The method for producing the polycarbonate resin is not particularly limited, and the polycarbonate resin can be produced by a conventionally known method using a dihydroxy compound and a carbonate binder as raw materials. For example, the method of directly reacting a dihydroxy compound with phosgene or the like (interfacial polymerization method, phosgene method) and the method of transesterifying a dihydroxy compound with a carbonate diester in a molten state (transesterification method, melting method) can be mentioned.

[0038] As the dihydroxy compound, a dihydroxy compound corresponding to the structural unit (A) represented by the above general formula (1) and the structural unit (B) represented by the above general formula (2) may be used. Specifically, the compound represented by the following general formula (1)' (i.e., 4,4'-(4-methylpentane-2,2-diyl)diphenol; also referred to as "MIBK" in this specification) and the compound represented by general formula (2)' are used. If necessary, a dihydroxy compound corresponding to the other structural unit (C) is used in combination. [ka] In the above formula (2)', R1 to R8 and X are defined as in the above formula (2).

[0039] When the interfacial polymerization method is used, a dihydroxy compound is usually reacted with phosgene in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as pyridine, sodium hydroxide, or potassium hydroxide is used, and as the solvent, for example, methylene chloride or chloroform is used. In order to promote the condensation polymerization reaction, a tertiary amine catalyst such as triethylamine, or a quaternary ammonium salt such as benzyltriethylammonium chloride may be used.

[0040] In the above-mentioned production method, it is preferable to further add a monofunctional compound such as phenol, pt-butylphenol (PTBP), p-cumylphenol, long-chain alkyl-substituted phenol, alkoxy-substituted phenol, benzotriazole-substituted phenol, etc., to the reaction system as a molecular weight regulator (end terminator). The timing of adding the molecular weight regulator (end terminator) is not particularly limited, and it may be added during the reaction of the dihydroxy compound or after the reaction of the dihydroxy compound.

[0041] The amount of the molecular weight regulator used is usually 0.95 mol or more, preferably 1.5 mol or more, and usually 10 mol or less, preferably 5 mol or less, based on 100 mol of the dihydroxy compound.

[0042] By adding a molecular weight regulator, a terminal structure derived from the molecular weight regulator is introduced to the terminal of the polycarbonate resin (copolymer). In one embodiment, the terminal structure derived from the molecular weight regulator is usually 0.95 mol or more, preferably 1.5 mol or more, and usually 10 mol or less, preferably 5 mol or less, per 100 mol of the structural unit derived from the dihydroxy compound (for example, the total of the structural unit (A) represented by general formula (1) and the structural unit (B) represented by general formula (2)). In one embodiment of the present invention, the terminal structure of the polycarbonate resin (copolymer) is derived from a compound selected from phenol, pt-butylphenol (PTBP), p-cumylphenol, long-chain alkyl-substituted phenols, alkoxy-substituted phenols, and benzotriazole-substituted phenols. The addition of a molecular weight regulator is preferable in that it not only makes it possible to adjust the viscosity average molecular weight (Mv) of the polycarbonate resin to a desired range, but also makes it possible to impart unique physical properties to the polycarbonate resin that are derived from the structure of the molecular weight regulator.

[0043] An example of the alkoxy-substituted phenol is a compound represented by the following formula (T1)′. [ka] By using the compound of the above formula (T1)', a terminal structure represented by the following formula (T1) is introduced to the terminal of the main chain of the polycarbonate resin. [ka] In formula (T1)' and formula (T1), R A represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms, each of which may have a substituent; R B and R C each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, Z represents an ether bond, a carbonyl group, an ester bond, or a single bond; a is an integer from 1 to 3; * indicates the bonding position with the main chain of the polycarbonate resin. Examples of the compound represented by the above formula (T1)' include, but are not limited to, p-hydroxyphenethyl alcohol (PHEP), m-hydroxyphenethyl alcohol, o-hydroxyphenethyl alcohol, o-hydroxybenzyl alcohol (i.e., salicyl alcohol), p-hydroxybenzyl alcohol, m-hydroxybenzyl alcohol, vanillyl alcohol, homovanillyl alcohol, 3-(4-hydroxy-3-methoxyphenyl)-1-propanol, sinapyl alcohol, coniferyl alcohol, p-coumaryl alcohol, etc. Among these, from the viewpoint of reactivity, p-hydroxyphenethyl alcohol and p-hydroxybenzyl alcohol are preferred, and p-hydroxyphenethyl alcohol is even more preferred. These alkoxy-substituted phenols are excellent in that they can introduce a hydroxyl group into the end of the main chain of the resulting polycarbonate resin, thereby imparting reactivity to the polycarbonate resin.

[0044] Alternatively, the molecular weight regulator may be a compound represented by the following formula (T2)′: [ka] By using the compound of the above formula (T2)', a terminal structure represented by the following formula (T2) is introduced to the terminal of the main chain of the polycarbonate resin. [ka] In formula (T2)' and formula (T2), R D is hydrogen or an alkyl group having 1 to 6 carbon atoms; R E is an alkylene group having 1 to 6 carbon atoms, R F is a hydrogen atom or a methyl group, R G represents a hydrogen atom or a halogen, and * represents the bonding position with the main chain of the polycarbonate resin.

[0045] Among them, the compound represented by the above formula (T2)' is preferably the compound represented by the following formula (T3)'. By blending the compound of formula (T3)', a terminal structure represented by the following formula (T3) is introduced to the terminal of the main chain of the polycarbonate resin. [ka] In formula (T3)' and formula (T3), R D represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and * represents the bonding position with the main chain of the polycarbonate resin. These benzotriazole-substituted phenols are excellent in that they can impart reactivity derived from the methacryl group and ultraviolet absorbing performance derived from the benzotriazole group to the resulting polycarbonate resin.

[0046] Among these, in terms of reactivity during synthesis, availability, and cost, it is preferable to use, as the molecular weight regulator, a compound selected from the group consisting of pt-butylphenol (PTBP), the compound represented by the above formula (T1)' (particularly, p-hydroxyphenethyl alcohol (PHEP), and the compound represented by the above formula (T2)' (particularly, the compound represented by formula (T3)').

[0047] In one embodiment of the present invention, the polycarbonate resin comprises a terminal structure selected from the terminal structure represented by the above formula (T1) (particularly, a terminal structure derived from p-hydroxyphenethyl alcohol (PHEP)), the terminal structure represented by the above formula (T2) (particularly, a terminal structure represented by the above formula (T3)), and the terminal structure represented by the following formula (T4). [ka]

[0048] In one embodiment of the present invention, the polycarbonate resin contains a terminal structure represented by the above formula (T4).

[0049] In one embodiment of the present invention, the polycarbonate resin contains a terminal structure represented by the above formula (T1) (particularly, a terminal structure derived from p-hydroxyphenethyl alcohol (PHEP)).

[0050] In one embodiment of the present invention, the polycarbonate resin contains a terminal structure represented by the above formula (T2) (particularly, a terminal structure represented by formula (T3)).

[0051] If desired, small amounts of antioxidants such as sodium sulfite and hydrosulfite, and branching agents such as phloroglucin, isatin bisphenol and trisphenolethane may be added.

[0052] When the polycarbonate is produced by the transesterification method or the melting method, a dihydroxy compound is usually reacted with a carbonic acid diester in the presence of a transesterification catalyst. Specific examples of the carbonic acid diester include aromatic carbonic acid diesters such as diphenyl carbonate, ditolyl carbonate, bis(2-chlorophenyl) carbonate, dinaphthyl carbonate, bis(4-phenylphenyl) carbonate, etc. When a dicarboxylic acid, a dicarboxylic acid ester, etc. is used together with a carbonic acid diester, a polyester carbonate can be obtained. As the transesterification catalyst, at least one of an alkali metal compound and an alkaline earth metal compound can be used. It is also possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound in combination as an auxiliary. The transesterification catalyst may be used alone or in combination of multiple types.

[0053] (Physical properties of polycarbonate resin) The viscosity average molecular weight (Mv) of the polycarbonate resin is preferably 16,000 to 80,000, and more preferably 20,000 to 80,000, from the viewpoint of ease of handling of the resin solution, and is more preferably 26,000 to 80,000, still more preferably 26,000 to 60,000, still more preferably 26,000 to 50,000, and particularly preferably 26,000 to 40,000, from the viewpoint of strength (e.g., pencil strength) of the obtained film.

[0054] The viscosity average molecular weight (Mv) of the polycarbonate resin can be measured by the method described below. (Viscosity average molecular weight (Mv) measurement conditions) Measuring instrument: Ubbelohde capillary viscometer Solvent: Dichloromethane Resin solution concentration: 0.5 grams / dl Measurement temperature: 25℃ Measure under the above conditions, calculate the intrinsic viscosity [η] deciliters / gram with a Huggins constant of 0.45, and use the following formula to calculate.

number

[0055] The glass transition temperature (Tg) of the polycarbonate resin is preferably 150°C or higher. If it is 150°C or higher, the heat resistance is excellent. From the viewpoints of heat resistance and ease of molding, it is more preferably 155°C or higher, and even more preferably 157°C or higher. For example, the glass transition temperature (Tg) of the polycarbonate resin is preferably 150 to 200°C, more preferably 155 to 200°C, and even more preferably 157 to 200°C.

[0056] The glass transition temperature (Tg) of a polycarbonate resin can be measured by the method described below. (Glass transition temperature (Tg) measurement conditions) Measurement equipment: Differential scanning calorimeter (DSC) Heating rate: 10℃ / min Gas flow environment: Nitrogen 20ml / min Sample pretreatment: Heat melting at 300℃

[0057] Polycarbonate resins have excellent solvent solubility. From the viewpoint of improving efficiency when performing wet molding, it is preferable that the concentration (mass%) of the polycarbonate resin that can be dissolved in the solution (100 mass%) of the solvent is 20 mass% or more. In particular, it is desirable that the polycarbonate resin is dissolved in a non-halogen-based organic solvent (preferably at least one of a ketone-based solvent and an ester-based solvent described later) at a concentration of preferably 20 mass% or more, more preferably 25 mass% or more.

[0058] 2. Polycarbonate resin composition Additives such as antioxidants, processing stabilizers, light stabilizers, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, release agents, ultraviolet absorbers, plasticizers and compatibilizers may be added to the polycarbonate resin to form a polycarbonate resin composition, within the scope of not impairing the characteristics of the present invention. The polycarbonate resin can also be used as a polymer alloy by kneading it with one or more of polycarbonates other than the polycarbonate resin of the present invention, synthetic resins such as aromatic polyesters, aliphatic polyesters, polyamides, polystyrenes, polyolefins, acrylics, amorphous polyolefins, ABS and AS, biodegradable resins such as polylactic acid and polybutylene succinate, and rubber.

[0059] The method for blending the polycarbonate resin with the various additives is not particularly limited as long as it is a commonly used polymer blending method, and examples of the method include mixing using a tumbler, V-type blender, super mixer, Nauta mixer, Banbury mixer, kneading roll, extruder, etc., or a solution blending method in which the above-mentioned components are mixed in a state of being dissolved in a common good solvent such as methylene chloride.

[0060] Polycarbonate resins or polycarbonate resin compositions can be used as raw materials for various molded articles such as films, sheets, disks, lenses, and prisms.

[0061] 3. Molded body According to one embodiment, there is provided a molded article obtained by molding the polycarbonate resin or a resin composition containing the polycarbonate resin. For example, the polycarbonate resin of the embodiment or a resin composition containing the same can be suitably used as a film. One embodiment is a film containing a polycarbonate resin.

[0062] The polycarbonate resin of the embodiment or a resin composition containing the same can be molded by various methods, for example, dry molding such as compression molding, transfer molding, injection molding, blow molding, extrusion molding, lamination molding, and calendar molding; wet molding such as solution casting and casting. Among them, the polycarbonate resin of the embodiment has excellent solubility in a solvent and is therefore suitable for molding by wet molding, and is particularly suitable as a raw material for films such as optical films by wet molding.

[0063] Film molding by wet molding has the advantage that it is easy to obtain thin films and non-oriented films, and also that high-quality films can be obtained without discoloration or gel formation when melted at high temperatures. Therefore, it is used to manufacture films of materials with high glass transition temperatures. In wet molding, the resin is required to have good solubility in the solvent and solution stability. Conventionally, polycarbonates with high glass transition temperatures have low solubility in solvents, and most of them only dissolve in non-halogenated organic solvents (especially non-halogenated organic solvents with low boiling points) at low concentrations. Therefore, the molding efficiency of wet molding is low, and there are problems in terms of productivity. However, the polycarbonate resin of the present invention has the advantage that it exhibits high solubility in non-halogenated organic solvents with low boiling points and has high solution stability. This makes it possible to perform wet molding with high molding efficiency.

[0064] A solution of polycarbonate resin is used for wet molding. Any solvent can be used for preparing the solution as long as it dissolves the polycarbonate resin of the present invention and has moderate volatility. Among them, it is preferable to use a non-halogen organic solvent from the viewpoint of safety and hygiene during wet molding. One embodiment of the present invention is a resin solution containing a non-halogen organic solvent and a polycarbonate resin dissolved in the non-halogen solvent. One embodiment of the present invention is a film obtained by wet molding the resin solution. A further embodiment of the present invention is a method for producing a film, which includes wet molding the resin solution.

[0065] The resin concentration in the resin solution is usually 1 to 30% by weight. From the viewpoint of improving the efficiency of wet molding, the polycarbonate resin concentration in the resin solution is preferably 20% by mass or more. The polycarbonate resin concentration in the resin solution is preferably 20% by mass or more, more preferably 20 to 50% by mass.

[0066] The non-halogen-based organic solvent is not particularly limited, but from the viewpoint of improving the efficiency of wet molding, it is preferable to use one having a relatively low boiling point (for example, a boiling point of 100° C. or less, preferably 90° C. or less, more preferably 80° C. or less). Specific examples include ketone-based solvents, ester-based solvents, and ether-based solvents. In one embodiment, the non-halogenated organic solvent constituting the resin solution is at least one of a ketone solvent and an ester solvent. In one embodiment, the polycarbonate resin has a dissolution concentration of 20% by mass or more in one of a ketone solvent or an ester solvent. In a preferred embodiment, the polycarbonate resin has a dissolution concentration of 20% by mass or more in both a ketone solvent and an ester solvent.

[0067] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, etc. Among them, methyl ethyl ketone is preferred from the viewpoints of a low boiling point and the solubility of the polycarbonate resin in the solvent. Examples of ester-based solvents include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-ethoxyethyl acetate, 2-methoxy-1-methylethyl acetate, ethyl lactate, etc. Among these, ethyl acetate is preferred from the viewpoints of its low boiling point and the solubility of the polycarbonate resin in the solvent. In one embodiment, the non-halogenated organic solvent is at least one of methyl ethyl ketone and ethyl acetate.

[0068] The molded article of the present invention is a molded article containing a polycarbonate resin having the above-mentioned various preferred forms and configurations. There are no limitations on the shape, pattern, color, size, etc. of the molded article, and they may be arbitrarily set depending on the application. The molded article of the present invention can be used, for example, in electrical and electronic equipment, OA equipment, optical media, automobile parts, building materials, etc. Specifically, it can be preferably used in electrical and electronic equipment (for example, personal computers, game machines, television receivers, display devices such as liquid crystal displays and plasma displays, printers, copy machines, scanners, fax machines, electronic notebooks and PDAs, electronic desk calculators, electronic dictionaries, cameras, video cameras, mobile phones, smartphones, tablets, battery packs, drives and reading devices for recording media, mice, numeric keypads, CD players, MD players, portable radios and audio players, etc.). In particular, the film produced by wet molding has good heat resistance and transparency, and is preferably used as a laminate film by attaching a gas barrier film and a solvent-resistant film to both sides of the film, or as a film for liquid crystal displays such as a film for liquid crystal substrates (plastic cell substrates) or a retardation film together with a transparent conductive film or a polarizing plate, and specifically, it can be advantageously used in tablets, smartphones, handy terminals, various display elements, etc. Although the plastic substrate is used in an unstretched state, in order to use it as a retardation film, it is stretched and oriented in at least one axial direction to have optimal birefringence characteristics. A known method can be used for stretching the film, and vertical uniaxial, horizontal uniaxial, multi-stage simultaneous biaxial stretching, etc. may be used. EXAMPLES

[0069] The present invention will be described in detail below with reference to examples, but the technical scope of the present invention is not limited thereto. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0070] In the examples and comparative examples, the physical properties of the polycarbonate resin were measured by the following methods.

[0071] <Viscosity average molecular weight (Mv)> (Viscosity average molecular weight (Mv) measurement conditions) Measuring instrument: Ubbelohde capillary viscometer Solvent: Dichloromethane Resin solution concentration: 0.5 grams / dl Measurement temperature: 25℃ Measurement was performed under the above conditions, and the intrinsic viscosity [η] deciliters / gram was determined with a Huggins constant of 0.45, and calculated using the following formula.

number

[0072] <Glass transition temperature (Tg)> Measurement was performed under the following conditions. (Glass transition temperature (Tg) measurement conditions) Measurement equipment: Differential scanning calorimeter (DSC) (Shimadzu DSC-50) Heating rate: 10℃ / min Gas flow environment: Nitrogen 20ml / min Sample pretreatment: Heat melting at 300℃

[0073] <Solvent solubility> Polycarbonate resin was mixed with methyl ethyl ketone (MEK) or ethyl acetate (AcOEt) as a solvent, and the solubility of the polycarbonate resin in each solvent (concentration of polycarbonate resin dissolved in the solution, mass%) was judged to be good when it was 20 mass% or more, and poor when it was less than 20 mass%. Furthermore, the solubility in the two solvents (MEK, AcOEt) was evaluated according to the following criteria. A: Dissolved in any solvent at a concentration of 20% by mass or more B: Dissolved in only one of the solvents at a concentration of 20% by mass or more C: Not soluble in any solvent at a dissolution concentration of 20% by mass or more

[0074] <Synthesis of polycarbonate resin> [Example 1] 50.4 g (0.187 mol) of bisphenol MIBK (MIBK) manufactured by Honshu Chemical Industry Co., Ltd., 54.1 g (0.187 mol) of bisphenol AP (BPAP) manufactured by Honshu Chemical Industry Co., Ltd., and 0.5 g of hydrosulfite were added and dissolved in 500 ml of a 9% by mass aqueous solution of sodium hydroxide and 400 ml of pure water. 350 ml of dichloromethane was added thereto and stirred, and 51.0 g of phosgene was blown in over 40 minutes while maintaining the solution temperature in the range of 15 to 25°C. After the injection of phosgene was completed, 100 ml of a 9 w / w% aqueous solution of sodium hydroxide, 200 ml of dichloromethane, and 1.12 g (0.00746 mol) of p-tertiary butylphenol (PTBP) manufactured by Honshu Chemical Industry Co., Ltd. dissolved in 100 ml of dichloromethane were added and emulsified by vigorously stirring, after which 0.5 ml of triethylamine (TEA) was added as a polymerization catalyst and polymerization was carried out for approximately 40 minutes. The polymerization solution was separated into an aqueous phase and an organic phase, and the organic phase was neutralized with phosphoric acid and repeatedly washed with pure water until the pH of the washing liquid became neutral. The organic solvent was evaporated from the polycarbonate resin solution thus produced, to obtain a powdered polycarbonate resin. The obtained polycarbonate resin is a random copolymer composed of a structural unit derived from MIBK (i.e., structural unit (A)) and a structural unit derived from BPAP (structural unit (B), a unit of general formula (3B)), and both ends have a structure derived from PTBP.

[0075] [Example 2] A powdered polycarbonate resin was obtained in the same manner as in Example 1, except that BPAP was changed to 50.0 g (0.187 mol) of bisphenol Z (BPZ) manufactured by Honshu Chemical Industry Co., Ltd. The obtained polycarbonate resin has a constitutional unit derived from MIBK (i.e., constitutional unit (A)) and a constitutional unit derived from BPZ (constituent unit (B), R in general formula (5A) 13 ~R 22 is a hydrogen atom), and both ends have a structure derived from PTBP.

[0076] [Example 3] A powdered polycarbonate resin was obtained in the same manner as in Example 1, except that BPAP was changed to 70.7 g (0.187 mol) of bis-cresol fluorene (BCFL) manufactured by Honshu Chemical Industry Co., Ltd., and 0.056 g of benzyltriethylammonium chloride manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd. was added as a polymerization catalyst during the reaction before blowing in phosgene. The obtained polycarbonate resin was a polycarbonate resin having a structure derived from MIBK (i.e., the structure unit (A)) and a structure derived from BCFL (structure unit (B), in which X is represented by the general formula (2) and R1 to R8, R 11 , and R 12 is a hydrogen atom), and both ends have a structure derived from PTBP.

[0077] [Example 4] A powdered polycarbonate resin was obtained in the same manner as in Example 1, except that BPAP was changed to 52.7 g (0.187 mol) of bisphenol 3MZ (BP3MZ) manufactured by Honshu Chemical Industry Co., Ltd. The obtained polycarbonate resin has a structure in which a structural unit derived from MIBK (i.e., structural unit (A)) and a structural unit derived from BP3MZ (structural unit (B), R in general formula (5A) 15 is a methyl group, and R 13 , R 14 , R 16 ~R 22 is a hydrogen atom), and both ends have a structure derived from PTBP.

[0078] [Example 5] A powdered polycarbonate resin was obtained in the same manner as in Example 1, except that the amount of PTBP was changed to 1.87 g (0.0126 mol). The obtained polycarbonate resin is a random copolymer composed of a structural unit derived from MIBK (i.e., structural unit (A)) and a structural unit derived from BPAP (structural unit (B), units of general formula (3B)), and both ends have a structure derived from PTBP.

[0079] [Example 6] A powdered polycarbonate resin was obtained in the same manner as in Example 1, except that the amount of PTBP was changed to 0.56 g (0.00373 mol). The obtained polycarbonate resin is a random copolymer composed of a structural unit derived from MIBK (i.e., structural unit (A)) and a structural unit derived from BPAP (structural unit (B), units of general formula (3B)), and both ends have a structure derived from PTBP.

[0080] [Example 7] A powdered polycarbonate resin was obtained in the same manner as in Example 1, except that the amount of MIBK was changed to 60.5 g (0.224 mol) and the amount of BPAP was changed to 40.0 g (0.149 mol) of bisphenol Z (BPZ) manufactured by Honshu Chemical Industry Co., Ltd. The obtained polycarbonate resin was a polycarbonate resin having a structure composed of a structural unit derived from MIBK (i.e., structural unit (A)) and a structural unit derived from BPZ (structural unit (B), R 13 ~R 22 is a hydrogen atom), and both ends have a structure derived from PTBP.

[0081] [Example 8] A powdered polycarbonate resin was obtained in the same manner as in Example 1, except that the amount of MIBK was changed to 80.6 g (0.299 mol), BPAP was changed to 26.3 g (0.075 mol) of bisphenol cyclododecane (BPCD) manufactured by Honshu Chemical Industry Co., Ltd., and 0.020 g of benzyltriethylammonium chloride manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd. was added as a polymerization catalyst during the reaction before blowing in phosgene. The obtained polycarbonate resin was a polycarbonate resin having a structure derived from MIBK (i.e., structural unit (A)) and a structure derived from BPCD (structural unit (B), in general formula (5) where m is 6 and R 13 ~R 22 is a hydrogen atom), and both ends have a structure derived from PTBP.

[0082] [Example 9] A powdered polycarbonate resin was obtained in the same manner as in Example 1, except that the amount of 9 w / w% aqueous sodium hydroxide solution during the reaction was 540 ml, pure water was 170 ml, phosgene was 51.7 g, and PTBP was changed to 1.71 g (0.0124 mol) of p-hydroxyphenethyl alcohol (PHEP) manufactured by Otsuka Chemical Co., Ltd., which was added before blowing in phosgene. The obtained polycarbonate resin is a random copolymer composed of a structural unit derived from MIBK (i.e., structural unit (A)) and a structural unit derived from BPAP (structural unit (B), units of general formula (3B)), and both ends have a structure derived from PHEP.

[0083] [Example 10] A powdered polycarbonate resin was obtained in the same manner as in Example 1, except that the amount of 9 w / w% aqueous sodium hydroxide solution during the reaction was 540 ml, the pure water was 170 ml, the phosgene was 51.7 g, and the PTBP was changed to 4.01 g (0.0124 mol) of RUVA-93 manufactured by Otsuka Chemical Co., Ltd. The obtained polycarbonate resin was a random copolymer composed of a structural unit derived from MIBK (i.e., structural unit (A)) and a structural unit derived from BPAP (structural unit (B), units of general formula (3B)), and both ends have a structure derived from RUVA-93.

[0084] [Comparative Example 1] A powdered polycarbonate resin was obtained in the same manner as in Example 1, except that BPAP was changed to 46.2 g (0.187 mol) of bisphenol A (BPA) manufactured by Nippon Steel Chemical & Material Co., Ltd. The obtained polycarbonate resin was a random copolymer composed of a structural unit derived from MIBK (i.e., structural unit (A)) and a structural unit derived from BPA, and both ends had a structure derived from PTBP.

[0085] [Comparative Example 2] A powdered polycarbonate resin was obtained in the same manner as in Example 1, except that the amount of MIBK was changed to 40.3 g (0.149 mol) and the amount of BPAP was changed to 65.0 g (0.224 mol). The obtained polycarbonate resin is a random copolymer composed of a structural unit derived from MIBK (i.e., structural unit (A)) and a structural unit derived from BPAP (structural unit (B), units of general formula (3B)), and both ends have a structure derived from PTBP.

[0086] [Comparative Example 3] A powdered polycarbonate resin was obtained in the same manner as in Example 1, except that MIBK was changed to 45.3 g (0.187 mol) of bisphenol B (BPB) manufactured by Honshu Chemical Industry Co., Ltd. The obtained polycarbonate resin is a random copolymer composed of a structural unit derived from BPB and a structural unit derived from BPAP (structural unit (B), units of general formula (3B)), and both ends have a structure derived from PTBP.

[0087] [Comparative Example 4] A powdered polycarbonate resin was obtained in the same manner as in Example 1, except that MIBK was changed to 45.3 g (0.187 mol) of bisphenol C (BPC) manufactured by Honshu Chemical Industry Co., Ltd., and 0.056 g of benzyltriethylammonium chloride manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd. was added as a polymerization catalyst during the reaction before blowing in phosgene. The obtained polycarbonate resin is a random copolymer composed of a BPC-derived structural unit and a BPAP-derived structural unit (structural unit (B), units of general formula (3B)), and both ends have a structure derived from PTBP.

[0088] The abbreviations and structures of the raw material monomers used in the above examples are shown below. [Table A] The structures and abbreviations of the molecular weight regulators (terminal terminators) used in the above examples, as well as the terminal structures introduced into the copolymers, are shown below. [Table B]

[0089] The compositions, viscosity average molecular weights (Mv), glass transition temperatures (Tg), and solvent solubilities of the polycarbonate resins synthesized in the above Examples and Comparative Examples are summarized in the table below.

[0090] [Table 1]

[0091] As shown in Table 1 above, the polycarbonate resins of Examples 1 to 8, which contain a structural unit (A) represented by general formula (2) and a structural unit (B) represented by general formula (2) and have a molar ratio (A / B) of the structural unit (A) to the structural unit (B) of 45 / 55 to 95 / 5, are confirmed to have a high glass transition temperature (150°C or higher) and excellent solvent solubility.

[0092] In particular, when the structural unit (B) (M2) contained the structure (BPAP) of formula (3B) (Examples 1, 5, and 6), the polymer had a high glass transition temperature and excellent solvent solubility. It was confirmed that when the structural unit (B) (M2) contained cyclohexane substituted with an alkyl group (BP3MZ) (Example 4), the solvent solubility was superior and the glass transition temperature could be significantly increased compared to when the structural unit contained unsubstituted cyclohexane (BPZ) (Examples 2 and 7). The structural unit (B) (M2) containing cycloalkylene (BPCD) having 12 carbon atoms (Example 8) had excellent solvent solubility and a high glass transition temperature compared to the structural unit (B) (M2) containing cyclohexane (BPZ) having 6 carbon atoms (Examples 2 and 7). This suggests that increasing the number of carbon atoms in the cycloalkylene improves the solvent solubility and glass transition temperature. When the structural unit (B) (M2) had a fluorene structure (Example 3), a polycarbonate resin having a particularly high glass transition temperature was obtained.

[0093] On the other hand, when the structural unit (B) was not contained, the glass transition temperature was low (Comparative Example 1) or the solvent solubility was poor (Comparative Example 2). When the structural unit (A) was not included, the solvent solubility was also insufficient (Comparative Examples 3 and 4).

[0094] The scope of the present invention is not limited to the above description, and may be appropriately modified and implemented without departing from the spirit of the present invention, other than the above examples. All documents and publications described in this specification are incorporated herein by reference in their entirety, regardless of their purpose. This specification also includes the claims and disclosures of the specification of Japanese Patent Application No. 2019-108054 (filed on June 10, 2019), which is a Japanese patent application on which the priority claim of this application is based. [Industrial Applicability]

[0095] The polycarbonate resin of the present invention has a high glass transition temperature and excellent solvent solubility, and is suitable for wet molding. The film obtained by wet molding can be used in a wide range of applications, such as electric and electronic materials for electric and electronic equipment and office automation equipment, optical materials for optical media, automobile parts, and building materials.

Claims

1. A polycarbonate resin which is a copolymer of a structural unit (A) represented by general formula (1) and a structural unit (B) represented by general formula (3B), and which has, at an end of the copolymer, a terminal structure selected from a terminal structure represented by formula (T1) and a terminal structure represented by formula (T2), and in which the molar ratio (A / B) of the structural unit (A) to the structural unit (B) is 45 / 55 to 95 / 5. 【Chemistry 25】 [In formula (T1), R Ａ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms, each of which may have a substituent; R Ｂ and R Ｃ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, Z represents an ether bond, a carbonyl group, or an ester bond, or represents a single bond; a is an integer from 1 to 3; * indicates the bonding position with the main chain of the polycarbonate resin. 【Chemistry 26】 [In formula (T2), R Ｄ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R Ｅ represents an alkylene group having 1 to 6 carbon atoms, R Ｆ represents a hydrogen atom or a methyl group, R Ｇ represents a hydrogen atom or a halogen atom, * indicates the bonding position with the main chain of the polycarbonate resin.

2. The resin according to claim 1, having a viscosity average molecular weight (Mv) of 16,000 to 80,000.

3. The resin according to claim 1 or 2, having a viscosity average molecular weight (Mv) of 26,000 to 80,000.

4. The resin according to any one of claims 1 to 3, having a glass transition temperature (Tg) of 150°C or higher.

5. The polycarbonate resin according to any one of claims 1 to 4, wherein the copolymer has a terminal structure represented by formula (T2) at a terminal.

6. A polycarbonate resin comprising a structural unit (A) represented by general formula (1) and a structural unit (B) represented by general formula (2), and having at its terminal a terminal structure selected from a terminal structure represented by formula (T1) and a terminal structure represented by formula (T2), wherein the molar ratio (A / B) of the structural unit (A) to the structural unit (B) is 45 / 55 to 95 / 5. 【Chemical 27】 [In formula (2), R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and an aralkyl group having 7 to 17 carbon atoms, each of which may have a substituent; X is a divalent group represented by the following formula (4): 【Chemistry 28】 (In formula (4), R １１ and R １２ are each independently selected from a hydrogen atom and an aryl group having 6 to 12 carbon atoms. 【Chemical 29】 [In formula (T1), R A represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms, each of which may have a substituent; R B and R C each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; Z represents an ether bond, a carbonyl group, or an ester bond, or represents a single bond; a is an integer from 1 to 3; * indicates the bonding position with the main chain of the polycarbonate resin. 【Chemistry 30】 [In formula (T2), R D represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R E represents an alkylene group having 1 to 6 carbon atoms; R F represents a hydrogen atom or a methyl group; R G represents a hydrogen atom or a halogen atom; * indicates the bonding position with the main chain of the polycarbonate resin.

7. R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are each independently selected from a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

8. A film comprising the polycarbonate resin according to any one of claims 1 to 7.

9. A resin solution comprising a non-halogenated organic solvent and the polycarbonate resin according to any one of claims 1 to 7 dissolved in the non-halogenated solvent.

10. The resin solution according to claim 7, wherein a concentration of the polycarbonate resin in the resin solution is 20% by mass or more.

11. The resin solution according to claim 9 or 10, wherein the non-halogen-based organic solvent is at least one of a ketone-based solvent and an ester-based solvent.

12. A film obtained by wet molding the resin solution according to any one of claims 7 to 9.

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