Polycarbonate resin and resin composition containing same

Abstract

According to the present invention, it is possible to provide a polycarbonate resin that contains a constituent unit (A) derived from a monomer represented by general formula (1), a constituent unit (B) derived from a monomer represented by general formula (2) and a constituent unit (C) derived from a monomer represented by general formula (3). Relative to the total amount of constituent units (A), (B) and (C) that constitute the polycarbonate resin, the proportion of constituent unit (A) is 20-50 mol%, the proportion of constituent unit (B) is 5-20 mol%, and the proportion of constituent unit (C) is 30-75 mol%.

Description

Polycarbonate resin and resin composition containing same

[0001] The present invention relates to a polycarbonate resin that is easily soluble in a carbonate-based organic solvent such as propylene carbonate, and a resin composition that contains the resin and has a viscosity suitable for forming a coating film and high transmittance.

[0002] It is known that certain polycarbonate resins can be dissolved in organic solvents and used as inks, paints, and other applications, and various organic solvents are used. In recent years, there has been a shift away from halogenated organic solvents, toluene, 1,4-dioxane, and other solvents that pose safety concerns for humans, toward safer solvents (Patent Document 1). Meanwhile, carbonate-based solvents such as dimethyl carbonate and ethylene carbonate are relatively safe and have been widely used, particularly as electrolyte solvents for lithium-ion batteries. However, for use as polycarbonate electrolytes, the solubility of polycarbonate resins in carbonate-based solvents is low, making it difficult to obtain coating films, leaving room for improvement. To address this issue, various studies have been conducted, including the proposal of adding methylene chloride as a solvent and coating the resulting colloidal solution (Patent Document 2). However, methylene chloride is a halogenated solvent that poses a significant environmental burden, raising concerns about its safety for humans.

[0003] Furthermore, when polycarbonate resin is dissolved in a carbonate-based solvent, the solution viscosity of the resin composition (resin solution) is required to be appropriate for forming a coating film. For example, when forming a coating film, if the solution viscosity is low, there are limitations on the usable coating surface, such as the lack of inclination of the coated surface. Furthermore, advanced coating techniques are required, such as the need to control the flow of the resin solution during application. On the other hand, if the solution viscosity is high, the flow of the resin solution becomes poor, making it difficult to form a precise coating film. The polycarbonate resin described in Patent Document 3 is soluble in carbonate-based organic solvents such as dimethyl carbonate and diethyl carbonate, but is difficult to dissolve in carbonate-based organic solvents such as propylene carbonate. Even when dissolved in propylene carbonate, the solution viscosity is too high, leaving room for improvement. Furthermore, a resin solution with high transmittance is preferable because it makes it easier to check the molding state during coating film formation. Furthermore, good storage stability, i.e., maintaining high transmittance, after solution preparation is practically desirable.

[0004] Patent Document 1: WO2018 / 123282 Patent Document 2: JP2000-357533A Patent Document 3: WO2022 / 181460A

[0005] An object of the present invention is to provide a polycarbonate resin that is easily soluble in a carbonate-based organic solvent such as propylene carbonate, and a resin composition that contains the resin and has a viscosity suitable for forming a coating film and high transmittance.

[0006] As a result of extensive research aimed at solving the above problems, the present inventors have found that polycarbonate resins having specific structural units have excellent solubility in carbonate-based organic solvents such as propylene carbonate, and have thus completed the present invention.

[0007] That is, the present invention is as follows: <1> A polycarbonate resin containing a structural unit (A) derived from a monomer represented by the following general formula (1), a structural unit (B) derived from a monomer represented by the following general formula (2), and a structural unit (C) derived from a monomer represented by the following general formula (3), wherein, relative to the total of the structural units (A), (B), and (C) constituting the polycarbonate resin, the proportion of the structural unit (A) is 20 to 50 mol %, the proportion of the structural unit (B) is 5 to 20 mol %, and the proportion of the structural unit (C) is 30 to 75 mol %. (In general formula (1), R １１ ~R １４ and R １５ ~R １８ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, each of which may have a substituent. (In general formula (2), R ２１ ~R ２４ and R ２５ ~R ２８ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, each of which may have a substituent. (In general formula (3), R ３１ ~R ３４ and R ３５ ~R ３８ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, each of which may have a substituent; X is where R ５ and R ６each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; R ５ and R ６ represents a group that combines to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 atoms, provided that R ５ and R ６ and R are not both hydrogen or trifluoromethyl groups; ７ and R ８ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent.) <2> The polycarbonate resin according to <1> above, wherein, based on the total of the structural units (A), (B), and (C) constituting the polycarbonate resin, the proportion of the structural unit (A) is 20 to 30 mol %, the proportion of the structural unit (B) is 10 to 15 mol %, and the proportion of the structural unit (C) is 61 to 70 mol %. <3> The polycarbonate resin according to <1> or <2> above, wherein the monomer represented by general formula (1) is a mixture of the following formulae (1-1), (1-2), and (1-3): the monomer represented by general formula (2) is 2,2-bis(4-hydroxyphenyl)hexafluoropropane (BPAF), and the monomer represented by general formula (3) is 2,2-bis(4-hydroxyphenyl)propane (BPA): <4> A resin composition comprising the polycarbonate resin according to any one of <1> to <3> above and a carbonate-based organic solvent, wherein the content of the polycarbonate resin in the resin composition is 0.05 to 50 mass% and the content of the carbonate-based organic solvent in the resin composition is 50 to 99.5 mass%. <5> The resin composition according to <4> above, wherein the carbonate-based organic solvent contains propylene carbonate. <6> The resin composition according to <5> above, wherein when the content of the polycarbonate resin in the resin composition is 10 mass% and the content of the propylene carbonate in the resin composition is 90 mass%, the transmittance of the resin composition at 440 nm is 90% or more. <7> The resin composition according to <5> or <6> above, wherein when the content of the polycarbonate resin in the resin composition is 10% by mass and the content of the propylene carbonate in the resin composition is 90% by mass, the viscosity of the resin composition is 80 to 170 mPa·S. <8> A coating film obtained by drying the resin composition according to any one of <4> to <7> above. <9> An electrolyte solution in which 0.1 to 30% by mass of a lithium salt is dissolved in the resin composition according to any one of <4> to <7> above. <10> The lithium salt is LiPF ６ and C ２ F ６ LiNO ４ <11> A polymer gel electrolyte obtained by gelling the electrolyte solution according to <9> or <10> above. <12> The polymer gel electrolyte according to <11> above, having a conductivity of 1 to 30,000 μS / cm.

[0008] According to the present invention, it is possible to provide a polycarbonate resin that is easily soluble in a carbonate-based organic solvent such as propylene carbonate, and a resin composition that contains the resin and has a viscosity suitable for forming a coating film and high transmittance.

[0009] The present invention will be described in detail below by showing embodiments and examples, but the present invention is not limited to the embodiments and examples shown below, and can be modified and implemented as desired within the scope that does not deviate from the gist of the present invention.

[0010] [Polycarbonate Resin] The polycarbonate resin of the present invention contains a structural unit (A) derived from a monomer represented by the following general formula (1), a structural unit (B) derived from a monomer represented by the following general formula (2), and a structural unit (C) derived from a monomer represented by the following general formula (3). In general formula (1), R １１ ~R １４ and R １５ ~R １８ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, each of which may have a substituent, preferably a hydrogen, a methyl group, or an allyl group, more preferably a hydrogen. In this specification, examples of the "substituent" when referring to "optionally having a substituent" include "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 5 carbon atoms, and an aralkyl group having 7 to 17 carbon atoms" (the same applies hereinafter). In general formula (2), R ２１ ~R ２４ and R ２５ ~R ２８ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, each of which may have a substituent, and preferably represents hydrogen, a methyl group, or an allyl group, and more preferably represents hydrogen. In general formula (3), R ３１ ~R ３４ and R ３５ ~R ３８each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, each of which may have a substituent, and preferably represents hydrogen, a methyl group, or an allyl group, and more preferably represents hydrogen. where R ５ and R ６ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; R ５ and R ６ represents a group that combines to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 atoms, provided that R ５ and R ６ and R are not both hydrogen or trifluoromethyl groups; ７ and R ８ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent. X is preferably —C(CH ３ ) ２ represents —, —O—, or a cyclohexylidene group, and more preferably represents —C(CH ３ ) ２ - represents.

[0011] In the polycarbonate resin of the present invention, the proportion of the structural unit (A) is 20 to 50 mol%, preferably 20 to 40 mol%, and more preferably 20 to 30 mol%, based on the total of the structural units (A), (B), and (C) constituting the polycarbonate resin, the proportion of the structural unit (B) is 5 to 20 mol%, preferably 8 to 20 mol%, more preferably 8 to 16 mol%, and particularly preferably 10 to 15 mol%, and the proportion of the structural unit (C) is 30 to 75 mol%, preferably 40 to 72 mol%, more preferably 44 to 72 mol%, even more preferably 54 to 72 mol%, and particularly preferably 61 to 70 mol%. The polycarbonate resin of the present invention may contain structural units other than the structural units (A), (B), and (C), as long as the effects of the present invention are not impaired.

[0012] In one embodiment of the present invention, the monomer represented by general formula (1) is preferably a mixture of the following formulae (1-1), (1-2), and (1-3). The mixing ratio of these is not particularly limited, but is preferably formula (1-1):formula (1-2):formula (1-3)=27 to 33:48 to 52:17 to 20 (mass%), more preferably 29 to 33:48 to 51:17 to 20 (mass%), and particularly preferably 31 to 33:48 to 50:17.5 to 19.5 (mass%).

[0013] In one embodiment of the present invention, the monomer represented by general formula (1) preferably has a purity of 99.0% by mass or more, and more preferably 99.3% by mass or more, as determined by quantitative analysis in accordance with JIS K 0124. Furthermore, the monomer represented by general formula (1) preferably contains 0.1% by mass or less of phenol as an impurity, as determined by quantitative analysis in accordance with JIS K 0124. Furthermore, the monomer represented by general formula (1) preferably contains 0.6% by mass or less of a compound represented by the following formula as an impurity, as determined by quantitative analysis in accordance with JIS K 0124: L = 2 to 6

[0014] In one embodiment of the present invention, the monomer represented by general formula (1) preferably has an ash content of 0.1% by mass or less as determined by an ash content test based on JIS K4101-10. The monomer represented by general formula (1) also preferably has a melting point of 115 to 121°C as measured based on JIS K 0064. When the monomer represented by general formula (1) has such purity, impurity content, and ash content, the heat resistance and color of the resulting polycarbonate resin and coating film can be improved.

[0015] In one embodiment of the present invention, the monomer represented by the general formula (2) is preferably 2,2-bis(4-hydroxyphenyl)hexafluoropropane (BPAF), 2,2-bis(4-hydroxy-3-methylphenyl)hexafluoropropane, or 2,2-bis(4-hydroxy-3-allylphenyl)hexafluoropropane, and more preferably 2,2-bis(4-hydroxyphenyl)hexafluoropropane (BPAF) represented by the following structural formula:

[0016] In one embodiment of the present invention, the monomer represented by the general formula (3) is preferably 2,2-bis(4-hydroxyphenyl)propane (BPA), 2,2-bis(4-hydroxyphenyl)cyclohexane (BPZ), or bis(4-hydroxyphenyl)ether (DHDE), and more preferably 2,2-bis(4-hydroxyphenyl)propane (BPA) represented by the following structural formula:

[0017] In one embodiment of the present invention, it is preferable to contain all of the constitutional units represented below.

[0018] The polycarbonate resin of the present invention can be produced by reacting a monomer represented by the general formula (1), a monomer represented by the general formula (2), and a monomer represented by the general formula (3) with a carbonate ester-forming compound. Therefore, the polycarbonate resin can be produced by a known method used in producing a polycarbonate resin derived from bisphenol A, such as a direct reaction of a bisphenol with phosgene (phosgene method) or a transesterification reaction of a bisphenol with a bisarylcarbonate (transesterification method).

[0019] In the phosgene method, the monomer represented by the general formula (1), the monomer represented by the general formula (2), and the monomer represented by the general formula (3) are typically reacted with phosgene in the presence of an acid binder and a solvent. Examples of acid binders include pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and examples of solvents include methylene chloride and chloroform. Furthermore, to promote the condensation polymerization reaction, it is preferable to add a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt such as benzyltriethylammonium chloride. Furthermore, to adjust the degree of polymerization, it is preferable to add a monofunctional compound such as phenol, p-t-butylphenol, p-cumylphenol, p-hydroxyphenethyl alcohol, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, or a long-chain alkyl-substituted phenol as a molecular weight regulator. If desired, small amounts of antioxidants such as sodium sulfite and hydrosulfite, or branching agents such as phloroglucin and isatin bisphenol may also be added. The reaction temperature is usually 0 to 150°C, preferably 5 to 40°C. The reaction time varies depending on the reaction temperature, but is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. During the reaction, it is desirable to maintain the pH of the reaction system at 10 or higher.

[0020] On the other hand, in the transesterification method, the monomer represented by the general formula (1), the monomer represented by the general formula (2), and the monomer represented by the general formula (3) are mixed with a bisaryl carbonate and reacted at high temperature under reduced pressure. Examples of bisaryl carbonates include bisaryl carbonates such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Two or more of these compounds can also be used in combination. The reaction is typically carried out at a temperature ranging from 150 to 350°C, preferably from 200 to 300°C, and the final pressure reduction is preferably 1 mmHg or less, allowing phenols derived from the bisaryl carbonate produced by the transesterification reaction to be distilled out of the system. The reaction time varies depending on the reaction temperature and the degree of vacuum, but is typically about 1 to 24 hours. The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. If desired, the reaction may be carried out in the presence of a molecular weight regulator, an antioxidant, or a branching agent.

[0021] The polycarbonate resin of the present invention preferably maintains a good balance of the solvent solubility, coatability, peelability, scratch resistance, impact resistance, and other properties required for a coating film-forming resin. By setting the lower limit of the resin's intrinsic viscosity to a predetermined value or higher, scratch resistance and impact strength are improved, and by setting the upper limit of the intrinsic viscosity to a predetermined value or lower, a decrease in solvent solubility and an increase in solution viscosity are suppressed, thereby maintaining coatability. The intrinsic viscosity of the polycarbonate resin is preferably in the range of 0.3 to 2.0 dl / g, and more preferably in the range of 0.35 to 1.5 dl / g.

[0022] [Resin Composition] The resin composition of the present invention contains the polycarbonate resin described above and a carbonate-based organic solvent. The blending amount of the polycarbonate resin in the resin composition of the present invention is 0.05 to 50 mass%. For applications requiring coating, this blending amount is preferably 1 to 30 mass%, more preferably 1 to 20 mass%, depending on the intrinsic viscosity and solvent solubility. When the blending amount of the polycarbonate resin is within this range, a good balance between solvent solubility and coatability is achieved, improving workability and appearance.

[0023] <Carbonate-Based Organic Solvent> The resin composition of the present invention is a solution in which the above-mentioned polycarbonate resin is dissolved in a carbonate-based organic solvent, and in this state is equivalent to a paint generally known as a clear color. The resin composition of the present invention may be made into a colored paint composition by further dissolving or dispersing a desired dye and / or pigment in the resin composition.

[0024] The resin composition of the present invention uses at least a carbonate-based organic solvent as a solvent. The carbonate-based organic solvent preferably contains propylene carbonate. Propylene carbonate is an ester of propylene glycol and carbonic acid, and has the molecular formula C ４ H ６ O ３ and has a molar mass of 102.09 g / mol. The content of propylene carbonate in the carbonate organic solvent is preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 100% by mass. In one embodiment of the present invention, other carbonate organic solvents may be contained within a range that does not impair the effects of the present invention. Specific examples include linear carbonates such as dimethyl carbonate (hereinafter abbreviated as "DMC"), diethyl carbonate (hereinafter abbreviated as "DEC"), and methyl ethyl carbonate (hereinafter abbreviated as "MEC"), as well as cyclic carbonates such as ethylene carbonate (hereinafter abbreviated as "EC"), vinylene carbonate, and fluoroethylene carbonate. In the present invention, two or more of these can also be used in combination. Among these, DMC, DEC, and MEC, which have relatively high solubility in polycarbonate resins, are preferred.

[0025] In the present invention, the content of carbonate-based organic solvents in the resin composition is 50 to 99.95% by mass. It is preferably 70 to 99% by mass, more preferably 75 to 99% by mass, and particularly preferably 80 to 99% by mass. In the present invention, it is preferable to use a solvent composed solely of a combination of carbonate-based organic solvents. However, when a coating liquid is envisioned, organic solvents that are not toxic or deleterious substances as defined by Japan's Poisonous and Deleterious Substances Control Act or specific chemical substances as defined by the Industrial Safety and Health Act may be added within a range that does not impair the effects of the present invention. Specifically, the content of organic solvents other than carbonate-based organic solvents in the resin composition of the present invention can be approximately 0 to 30% by mass.

[0026] <Optional Additives> When the resin composition of the present invention is used by coating, pigments, dyes, colored particles, or particles having optical interference properties can be added to enhance the color effect. Examples of the pigments and dyes include organic pigments such as azo pigments and phthalocyanine pigments, and specific examples include Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 215, Red No. 220, Orange No. 203, Orange No. 204, Blue No. 1, Blue No. 404, Yellow No. 205, Yellow No. 401, and Yellow No. 405. In addition, to produce white, pearlescent, metallic, or glittery colors, titanium mica, titanium oxide, iron oxide, tin oxide, zirconium oxide, chromium oxide, bismuth oxychloride, silica, chromium, titanium nitride, titanium, magnesium fluoride, gold, silver, nickel, and the like can also be used. Particles with optical coherence are particles that enhance color effects by reflecting or scattering light, and examples include glass beads, tiny seashells, and mica. These are preferably added to the resin composition in an amount of 0.0001 to 10.0 mass% as desired. Furthermore, rust inhibitors, antioxidants, dispersants, ultraviolet absorbers, antifoaming agents, leveling agents, and the like may be added as needed.

[0027] The transmittance at 440 nm of the resin composition of the present invention is preferably 90% or more, more preferably 95% or more, and particularly preferably 96% or more, when the content of polycarbonate resin in the resin composition is 10% by mass and the content of propylene carbonate in the resin composition is 90% by mass. The transmittance can be measured by the method described in the Examples below.

[0028] The viscosity of the resin composition of the present invention can be set arbitrarily depending on the desired application, but when the content of polycarbonate resin in the resin composition is 10% by mass and the content of propylene carbonate in the resin composition is 90% by mass, the viscosity is preferably in the range of 80 to 170 mPa s, more preferably in the range of 90 to 170 mPa s, and particularly preferably in the range of 100 to 160 mPa s. Viscosity can be measured, for example, using a vibration viscometer (CJV5000) manufactured by A&D Co., Ltd. at a measurement temperature of 25°C.

[0029] The thickness of the coating film after applying and drying the resin composition of the present invention is preferably in the range of 1 to 200 μm, more preferably in the range of 5 to 120 μm, and particularly preferably in the range of 10 to 60 μm. A coating film thickness of 1 μm or more can ensure the surface protection strength of the coating film, and a coating film thickness of 200 μm or less is preferred because peeling due to shrinkage of the coating film can be suppressed.

[0030] [Electrolyte] When the resin composition of the present invention is used as an electrolyte, it is preferable to add 0.1 to 30 mass % of a Li salt. The Li salt is soluble in a carbonate-based organic solvent, and specifically, LiPF ６ , C ２ F ６ LiNO ４ , LiClO ４ , LiBF ４ , LiCoO ２ , LiBOB, LiBH ４、 Li(FSO ２ ) ２ N, Li(CF ３ SO ２ ) ２Among them, Li salts include LiPF ６ and C ２ F ６ LiNO ４ It is preferable that the electrode contains at least one of the following: A small amount of a stabilizer for stabilizing the electrode surface, an overcharge inhibitor, a flame retardant, etc. may also be added.

[0031] [Polymer Gel Electrolyte] A polymer gel electrolyte can be obtained by concentrating the electrolyte solution of the present invention and partially gelling it. The method for concentrating the electrolyte solution is not particularly limited, but examples include a method in which the solvent is partially removed by air drying to obtain a highly viscous liquid with a solidified surface. The polymer gel electrolyte of the present invention preferably has a conductivity at 20°C of 1 to 30,000 μS / cm, more preferably 10 to 20,000 μS / cm, and particularly preferably 100 to 10,000 μS / cm. The polymer gel electrolyte of the present invention can be preferably used as a material for Li-ion polymer batteries, electric double layer capacitors, electrolytic capacitors, and the like.

[0032] Examples of the present invention will be shown below together with comparative examples to explain the details of the invention, but the present invention is not limited to these examples.

[0033] (1) Solubility in propylene carbonate (10 mass% solution) 1 g of polycarbonate resin and 9 g of propylene carbonate were placed in a 20 ml vial and stirred. The appearance of the resulting resin composition (resin solution) was visually inspected and evaluated according to the following criteria: Resin composition (resin solution) transparent with no residual resin: "A" Resin composition (resin solution) with residual resin visible after standing: "B" Resin composition (resin solution) cloudy: "C" Resin not soluble at all: "D"

[0034] (2) Solubility in propylene carbonate (20% by mass solution) 2 g of polycarbonate resin and 8 g of propylene carbonate were placed in a 20 ml vial and stirred. The appearance of the resulting resin composition (resin solution) was visually inspected and evaluated using the same criteria as for the 10% by mass solution described above.

[0035] (3) Viscosity (mPa·S) of 10% by mass propylene carbonate solution The viscosity of the resin composition (resin solution) obtained in (1) above was measured using a vibration viscometer. Measuring device: vibration viscometer CJV5000 manufactured by A&D Co., Ltd. Measurement temperature: 25°C

[0036] (4) Transmittance at 440 nm of a 10% by mass solution of propylene carbonate upon preparation The transmittance of the resin composition (resin solution) obtained in (1) above was measured using a spectrophotometer. Measuring instrument: Shimadzu Corporation UV-1280 ultraviolet-visible spectrophotometer Cell: 1 cm quartz cell Measurement wavelength: 400 nm - 850 nm Measurement procedure: 1. Base correction was performed using propylene carbonate in spectrum mode. 2. The transmittance of the resin composition (resin solution) was measured at 400 nm - 850 nm. 3. The transmittance at 440 nm was extracted. Note that the "transmittance at 440 nm after standing for 3 days" is the value obtained by measuring the transmittance in the same manner after standing for 3 days after preparing the resin composition (resin solution).

[0037] Example 1 In 820 ml of a 6.8 wt % aqueous sodium hydroxide solution, 25 g (0.12 mol) of dihydroxydiphenylmethane (hereinafter abbreviated as "BPF-SG": manufactured by Gun-ei Chemical Industry Co., Ltd., isomer mixture, formula (1-1): formula (1-2): formula (1-3) = 31.9:49.2:18.5 (mass %), purity 99.6 mass %, phenol content 30 ppm), 60 g (0.26 mol) of 2,2-bis(4-hydroxyphenyl)propane (hereinafter abbreviated as "BPA": manufactured by Mitsubishi Chemical Corporation), and 15 g (0.04 mol) of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (hereinafter abbreviated as "BPAF": manufactured by Central Glass Co., Ltd.) were dissolved as raw material monomers (dihydroxy compounds), and further 0.5 g of hydrosulfite were dissolved. To this was added 300 ml of methylene chloride, and while stirring, 59.9 g of phosgene was then blown in over 40 minutes while maintaining the temperature at 15 to 25°C. After the phosgene blow-in was completed, 2.50 g of p-tert-butylphenol (hereinafter abbreviated as "PTBP"; manufactured by Dainippon Ink and Chemicals, Inc.) was added as a molecular weight modifier and stirred vigorously to emulsify the reaction solution. After emulsification, 0.5 ml of triethylamine was added, and the mixture was stirred at 20 to 30°C for approximately 1 hour to polymerize. After polymerization was completed, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and repeatedly washed with water until the conductivity of the initial solution (aqueous phase) reached 10 μS / cm or less. The resulting polymer solution was transferred onto an aluminum dish, and the solvent was evaporated and removed on a hot plate. The resulting solid was further dried at 120°C for 24 hours to obtain a polymer solid. The resulting polymer was analyzed by infrared absorption spectroscopy, revealing a peak at 1770 cm －１ Absorption due to carbonyl groups at a position near 1240 cm －１ Absorption due to ether bonds was observed near the position, confirming that the resin was a polycarbonate resin having carbonate bonds (hereinafter abbreviated as "PC-1"). The molecular weight (Mv), solubility in propylene carbonate, viscosity of a 10% by mass solution of propylene carbonate, and transmittance of the resulting resin (PC-1) are shown in Table 1.

[0038] (Examples 2 to 4, Comparative Examples 1 to 4) Polycarbonate resins were obtained in the same manner as in Example 1, except that the raw material monomer (dihydroxy compound) was changed to the monomer type and molar ratio (mol %) shown in Table 1. Table 1 shows the molecular weight (Mv), solubility in propylene carbonate, viscosity of a 10% by mass solution in propylene carbonate, and transmittance of the obtained resins.

[0039]

Claims

1. A polycarbonate resin comprising monomer-derived structural units (A) represented by the following general formula (1), monomer-derived structural units (B) represented by the following general formula (2), and monomer-derived structural units (C) represented by the following general formula (3), The polycarbonate resin wherein, with respect to the total of the constituent units (A), (B), and (C) constituting the polycarbonate resin, the proportion of constituent unit (A) is 20 to 50 mol%, the proportion of constituent unit (B) is 5 to 20 mol%, and the proportion of constituent unit (C) is 30 to 75 mol%. 【Chemistry 1】 (In general formula (1), R １１ ~R １４ and R １５ ~R １８ Each of these independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or a C1-C20 alkyl group, a C6-C12 aryl group, a C2-C12 alkenyl group, a C1-C5 alkoxy group, or a C7-C17 aralkyl group, each of which may have substituents. 【Chemistry 2】 (In general formula (2), R ２１ ~R ２４ and R ２５ ~R ２８ Each of these independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or a C1-C20 alkyl group, a C6-C12 aryl group, a C2-C12 alkenyl group, a C1-C5 alkoxy group, or a C7-C17 aralkyl group, each of which may have substituents. 【Transformation 3】 (In general formula (3), R ３１ to R ３４ and R ３５ to R ３８ each independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, each of which may have a substituent, X is, 【Chemistry 4】 And, Here R ５ and R ６ Each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or a C1-C20 alkyl group, a C1-C5 alkoxy group, or a C6-C12 aryl group, each of which may have substituents. ５ and R ６ R represents a group that bonds to form a carbon ring with 5 to 20 carbon atoms or a heterocycle with 5 to 12 elements, however, ５ and R ６ Both cannot be hydrogen or a trifluoromethyl group. R ７ and R ８ Each of these independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or a C1-C9 alkyl group, a C1-C5 alkoxy group, a C2-C12 alkenyl group, or a C6-C12 aryl group, each of which may have substituents.

2. The polycarbonate resin according to claim 1, wherein, with respect to the total of the constituent units (A), (B), and (C) constituting the polycarbonate resin, the proportion of constituent unit (A) is 20 to 30 mol%, the proportion of constituent unit (B) is 10 to 15 mol%, and the proportion of constituent unit (C) is 61 to 70 mol%.

3. The polycarbonate resin according to claim 1 or 2, wherein the monomer represented by the general formula (1) is a mixture of the following formulas (1-1), (1-2), and (1-3), the monomer represented by the general formula (2) is 2,2-bis(4-hydroxyphenyl)hexafluoropropane (BPAF), and the monomer represented by the general formula (3) is 2,2-bis(4-hydroxyphenyl)propane (BPA). 【Transformation 5】

4. A resin composition comprising the polycarbonate resin described in claim 1 and a carbonate-based organic solvent, The content of the polycarbonate resin in the resin composition is 0.05 to 50% by mass. The resin composition wherein the content of the carbonate-based organic solvent in the resin composition is 50 to 99.5% by mass.

5. The resin composition according to claim 4, wherein the carbonate-based organic solvent comprises propylene carbonate.

6. The content of the polycarbonate resin in the resin composition is 10% by mass. When the propylene carbonate content in the resin composition is 90% by mass, The resin composition according to claim 5, wherein the transmittance of the resin composition at 440 nm is 90% or more.

7. The content of the polycarbonate resin in the resin composition is 10% by mass. When the propylene carbonate content in the resin composition is 90% by mass, The resin composition according to claim 5, wherein the viscosity of the resin composition is 80 to 170 mPa·S.

8. A coating film obtained by drying the resin composition according to any one of claims 4 to 7.

9. An electrolyte in which 0.1 to 30% by mass of lithium salt is dissolved in the resin composition according to any one of claims 4 to 7.

10. The lithium salt is LiPF ６ and C ２ F ６ LiNO ４ The electrolyte according to claim 9, comprising at least one of the following.

11. A polymer gel electrolyte obtained by gelling the electrolyte according to claim 9.

12. The polymer gel electrolyte according to claim 11, wherein the conductivity is 1 to 30,000 μS / cm.

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