Resin composition, coating film using same, and electrolyte

Abstract

According to the present invention, it is possible to provide a resin composition including: a polycarbonate resin comprising a structural unit represented by general formula (1) (in the formula, R1-R4 and R11-R14 each independently represent hydrogen, fluorine, chlorine, bromine, iodine, etc., a is an integer of 1-1,000, and X represents –S-, etc.); and a carbonate-based organic solvent, wherein the content of the polycarbonate resin in the resin composition is 0.05-50 mass%, the content of the carbonate-based organic solvent in the resin composition is 50-99.5 mass%, and the molar ratio of the total of structural units represented by general formulae (2)-(4) to all the structural units represented by general formula (1) is 0-75%.

Description

[Technical Field]

[0001] The present invention relates to a resin composition that is low in toxicity and can be easily applied as an ink or paint, and to a coating film and an electrolyte solution that use the same. [Background technology]

[0002] It is known that certain polycarbonate resins are dissolved in organic solvents and used as inks, paints, etc., and various organic solvents are used for this purpose. In recent years, there has been a shift away from solvents that pose safety concerns for humans, such as halogenated organic solvents, toluene, and 1,4-dioxane, to solvents with higher safety (Patent Document 1). On the other hand, carbonate-based solvents such as dimethyl carbonate and ethylene carbonate are relatively safe and are widely used, particularly as electrolyte solvents for lithium-ion batteries. However, when used as a polycarbonate electrolyte, polycarbonate resin has low solubility in carbonate-based solvents, making it difficult to obtain a coating film, leaving room for improvement. To address this issue, various studies have been conducted, including a proposal to add methylene chloride as a solvent and coat it as a colloidal solution (Patent Document 2). However, methylene chloride is a halogen-based solvent that places a heavy burden on the environment, raising concerns about its safety to humans. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] WO2018 / 123282 publication [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-357533 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a resin composition that is low in toxicity and can be easily applied as an ink or paint, and a coating film and an electrolyte solution that use the same. The present inventors focused on low-toxicity carbonate-based organic solvents, but because carbonate-based organic solvents do not dissolve general bisphenol A-type polycarbonate resins, in order to dissolve polycarbonate resins, it was necessary to improve the solvent solubility of the polycarbonate resin itself and combine it with an optimal carbonate-based solvent. [Means for solving the problem]

[0005] As a result of extensive research aimed at solving the above problems, the present inventors have discovered that polycarbonate resins having specific structural units have excellent solubility in low-toxicity carbonate-based organic solvents, thereby completing the present invention.

[0006] That is, the present invention is as follows. <1> General formula (1): [ka] (In the formula, R1 to R4 and R 11 ~R 14 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; a is an integer from 1 to 1,000; X is [ka] and wherein R5 and R6 each independently represent 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; or R5 and R6 combine to form a carbocycle having 5 to 20 carbon atoms or a heterocycle having 5 to 12 elements; R7 and R8 each independently represent 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; b represents an integer of 0 to 20. A polycarbonate resin containing a structural unit represented by the formula: A resin composition comprising a carbonate-based organic solvent, the content of the polycarbonate resin in the resin composition is 0.05 to 50% by mass, the content of the carbonate-based organic solvent in the resin composition is 50 to 99.5% by mass, The following formulas (2) to (4) among all the structural units represented by the general formula (1): [ka] The resin composition is one in which the total proportion of structural units represented by the following formula is 0 to 75% by molar ratio. <2> The content of the carbonate-based organic solvent in the resin composition is 70 to 99 mass %. <1> The resin composition is as described in the above. <3> The carbonate-based organic solvent contains at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate. <1> or <2> The resin composition is as described in the above. <4> The carbonate-based organic solvent further contains ethylene carbonate. <3> The resin composition is as described in the above. <5> The structural unit represented by the general formula (1) includes one or more structural units selected from the group consisting of structural units represented by the following formulas (5) to (9): <1> ~ <4> The resin composition according to any one of the above items. [ka] <6> The structural unit represented by the general formula (1) includes one or more structural units selected from the group consisting of structural units represented by the formulas (5), (6), and (8). <5> The resin composition is as described in the above. <7> The polycarbonate resin has an intrinsic viscosity of 0.3 to 2.0 dl / g. <1> ~ <6> The resin composition according to any one of the above items. <8> The resin composition does not contain any organic solvent other than the carbonate-based organic solvent. <1> ~ <7> The resin composition according to any one of the above items. <9> the above <1> ~ <8> 1. A coating film obtained by drying the resin composition according to any one of the above items. <10> the above <1> ~ <8> The electrolytic solution is obtained by dissolving 0.1 to 30 mass % of a lithium salt in the resin composition according to any one of the above items. <11> The lithium salt includes at least one of LiPF6 and C2F6LiNO4. <10> The electrolyte solution is as described in <12> the above <10> or <11> 1. A polymer gel electrolyte obtained by gelling the electrolyte solution described in 1. <13> The above has a conductivity of 1 to 30,000 μS / cm. <12> The polymer gel electrolyte is described in [Effects of the Invention]

[0007] The resin composition of the present invention is not only less toxic than conventional polycarbonate resin solutions, but also can be easily applied as an ink or paint, and is suitable for, for example, coating various substrates to form coating layers. Furthermore, it has good compatibility with lithium salts, and exhibits conductivity even when the polycarbonate resin is dissolved, thereby having the advantage of functioning as an electrolyte. DETAILED DESCRIPTION OF THE INVENTION

[0008] 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.

[0009] [Resin composition] The resin composition of the present invention is a resin having the general formula (1): [ka] A polycarbonate resin containing a structural unit represented by the formula: A resin composition comprising a carbonate-based organic solvent, the content of the polycarbonate resin in the resin composition is 0.05 to 50% by mass, the content of the carbonate-based organic solvent in the resin composition is 50 to 99.5% by mass, The following formulas (2) to (4) among all the structural units represented by the general formula (1): [ka] The resin composition is one in which the total proportion of structural units represented by the following formula is 0 to 75% by molar ratio.

[0010] In the above general formula (1), R1 to R4 and R 11 ~R 14 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 this specification, examples of the "substituent" when referring to "may have 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). a is an integer of 1 to 1,000, preferably an integer of 10 to 900, and more preferably an integer of 30 to 600. X is [ka] and wherein R5 and R6 each independently represent 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; or R5 and R6 combine to form a carbocycle having 5 to 20 carbon atoms or a heterocycle having 5 to 12 elements; R7 and R8 each independently represent 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; b represents an integer of 0 to 20, preferably an integer of 1 to 15, and more preferably an integer of 1 to 10.

[0011] In the present invention, the constitutional unit represented by the general formula (1) preferably includes one or more types selected from the group consisting of constitutional units represented by the following formulas (5) to (9). [ka] In particular, in the present invention, it is preferable that the structural unit represented by the general formula (1) includes one or more types selected from the group consisting of structural units represented by the formulae (5), (6), and (8).

[0012] In the present invention, the total proportion of the structural units represented by the above formulas (2) to (4) in all structural units represented by general formula (1) is 0 to 75% by molar ratio, preferably 0 to 70%, and more preferably 0 to 60%. Since the lower limit of the structural units represented by the above formulas (2) to (4) is 0%, these structural units are optional structural units that do not need to be included in the structural units represented by general formula (1). Here, the structural unit represented by the above formula (2) is a structural unit derived from 2,2-bis(4-hydroxyphenyl)propane (BPA), the structural unit represented by the above formula (3) is a structural unit derived from 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), and the structural unit represented by the above formula (4) is a structural unit derived from 1,1-bis(4-hydroxyphenyl)-1-phenylethane (BPAP).

[0013] When the structural units represented by general formula (1) consist solely of structural units derived from 2,2-bis(4-hydroxyphenyl)propane (BPA), 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), or 1,1-bis(4-hydroxyphenyl)-1-phenylethane (BPAP) (i.e., 100% by molar ratio), or when the proportion of these structural units is high (i.e., greater than 75% by molar ratio), the solubility in carbonate-based organic solvents decreases. The molar ratio of each structural unit can be determined based on the molar ratio of the monomers used in synthesizing the polycarbonate resin. Alternatively, the molar ratio can be calculated by analysis such as nuclear magnetic resonance spectroscopy.

[0014] <Polycarbonate resin> The polycarbonate resin used in the resin composition of the present invention can be produced by reacting a bisphenol, which derives the structural unit represented by the general formula (1), with a carbonate-forming compound. Therefore, it can be produced using 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).

[0015] The bisphenols that serve as raw material monomers for the polycarbonate resin used in the resin composition of the present invention are represented by the following general formula (11).

[0016] [ka] (In the formula, R1~R4, R 11 ~R 14 and X are the same as those in general formula (1). Specific examples of the monomer represented by the general formula (11) include 4,4'-biphenyldiol, bis(4-hydroxyphenyl)methane, bis(2-hydroxyphenyl)methane, 2,4'-dihydroxydiphenylmethane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(2-hydroxyphenyl)sulfone, bis(4-hydroxy-3-methylphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)ethane, bis(4-hydroxy-3-methylphenyl)methane, 2,2-bis(4-hydroxy-3-t-butylphenyl)propane , 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cycloundecane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 2,2-bis(4-hydroxy-3-allylphenyl)propane, 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane, 9,9- Bis(4-hydroxy-3-ethylphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisphenol, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenol, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 2,Examples include 2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)decane, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane. Two or more of these can also be used in combination.

[0017] Among these, bis(4-hydroxyphenyl)methane (BPF), 2,2-bis(4-hydroxyphenyl)propane (BPA), 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC), 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 1,1-bis(4-hydroxyphenyl)-1-phenylethane (BPAP), 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane (TMC), 2,2-bis(4-hydroxyphenyl)-4-methylpentane (MIBK), and 2,2-bis(4-hydroxyphenyl)hexafluoropropane (BPAF) are particularly preferred.

[0018] In addition, using 2,2-bis(4-hydroxyphenyl)propane (BPA), 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), and 1,1-bis(4-hydroxyphenyl)-1-phenylethane (BPAP) alone is not preferred because of their low solubility in dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate, which are common carbonate-based organic solvents. Therefore, when 2,2-bis(4-hydroxyphenyl)propane (BPA), 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), or 1,1-bis(4-hydroxyphenyl)-1-phenylethane (BPAP) is used as the monomer represented by the above general formula (11), the amount of 2,2-bis(4-hydroxyphenyl)propane (BPA), 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), or 1,1-bis(4-hydroxyphenyl)-1-phenylethane (BPAP) in the monomer represented by the above general formula (11) is, in molar ratio, 0 to 75%, preferably 0 to 70%, and more preferably 0 to 60%. Furthermore, when solubility in the electrolyte is important, it is more preferable to select from 2,2-bis(4-hydroxyphenyl)propane (BPA), 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane (MIBK), and 2,2-bis(4-hydroxyphenyl)hexafluoropropane (BPAF).

[0019] In the phosgene process, the monomer represented by the general formula (11) is 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. Examples of solvents include methylene chloride and chloroform. To promote the condensation polymerization reaction, it is preferable to add a catalyst such as a tertiary amine (e.g., triethylamine) or a quaternary ammonium salt (e.g., benzyltriethylammonium chloride). To control the degree of polymerization, it is preferable to add a monofunctional compound such as phenol, pt-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 is generally carried out at a temperature in the range of 0 to 150°C, preferably 5 to 40°C. The reaction time varies depending on the reaction temperature, but is generally 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, a monomer represented by the general formula (11) is 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, a molecular weight modifier, antioxidant, or branching agent may be added during the reaction.

[0021] The polycarbonate resin used in the resin composition 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, while 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] The blending amount of polycarbonate resin in the resin composition of the present invention is 0.05 to 50% by mass. In the case of coating applications, this blending amount is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, depending on the intrinsic viscosity and solvent solubility. When the blending amount of polycarbonate resin is within this range, the solvent solubility and coatability are well balanced, improving workability and appearance. On the other hand, when the resin composition of the present invention is used as an electrolyte, the blending amount of polycarbonate resin is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass. Although it depends on the concentration of the lithium salt, precipitation of the polycarbonate resin may occur if the blending amount exceeds 10% by mass.

[0023] <Carbonate-based organic solvent> The resin composition of the present invention is a solution of the polycarbonate resin 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 further converted into a colored paint composition by dissolving or dispersing a desired dye and / or pigment therein.

[0024] The resin composition of the present invention uses at least a carbonate-based organic solvent as a solvent. Specific examples of carbonate-based organic solvents 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"), propylene carbonate, vinylene carbonate, and fluoroethylene carbonate. In the present invention, two or more of these can also be used in combination. Among these, it is preferable to use one or more of DMC, DEC, and MEC, which have relatively high solubility for polycarbonate resins. Furthermore, it is preferable that the carbonate-based organic solvent used in the present invention further contains ethylene carbonate in addition to at least one selected from DMC, DEC, and MEC. In this case, taking into consideration that the polycarbonate resin tends to precipitate, the content of ethylene carbonate in the carbonate-based organic solvent is preferably less than 50% by mass.

[0025] In the present invention, the content of the carbonate-based organic solvent in the resin composition is 50 to 99.95% by mass, 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 only of a combination of carbonate-based organic solvents, but when a coating liquid is envisioned, organic solvents that are not poisonous or hazardous substances as defined in Japan's Poisonous and Deleterious Substances Control Act or specific chemical substances as defined in 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 about 0 to 30 mass%. Furthermore, when the resin composition of the present invention is intended for use as an electrolyte, an organic solvent that has little effect on the electrolyte, such as acetonitrile, tetraglyme, or sulfolane, may be added to adjust solubility or viscosity, as long as the effect of the present invention is not impaired. Specifically, the content of organic solvents other than carbonate-based organic solvents in the resin composition of the present invention can be about 0 to 30 mass%.

[0026] <Optional additives> When the resin composition of the present invention is applied, pigments, dyes, colored particles, and particles with optical coherence can be added to enhance the color effect. Examples of pigments and dyes include organic pigments such as azo pigments and phthalocyanine pigments. 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. Furthermore, titanium dioxide, titanium oxide, iron oxide, tin oxide, zirconium oxide, chromium oxide, bismuth oxychloride, silica, chromium, titanium nitride, titanium, magnesium fluoride, gold, silver, and nickel can also be used to create white, pearlescent, metallic, and glitter colors. Optical coherence particles are particles that enhance the color effect by reflecting or scattering light, and examples include glass beads, tiny shells, and mica. These are preferably added to the resin composition in an amount of 0.0001 to 10.0% by mass, as desired. Furthermore, if necessary, a rust inhibitor, an antioxidant, a dispersant, an ultraviolet absorber, an antifoaming agent, a leveling agent, or the like may be added.

[0027] The viscosity of the resin composition of the present invention can be set arbitrarily depending on the desired application, but is preferably in the range of 1 to 20,000 mPa·s, more preferably 5 to 10,000 mPa·s. When the resin composition of the present invention is used as an electrolyte, its viscosity is preferably in the range of 1 to 10,000 mPa·s, more preferably 10 to 5,000 mPa·s. The viscosity can be measured, for example, using a vibration viscometer (CJV5000) manufactured by A&D Co., Ltd. at a measurement temperature of 25°C.

[0028] 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.

[0029] [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 specific examples thereof include LiPF6, C2F6LiNO4, LiClO4, LiBF4, LiCoO2, LiBOB, and LiBH 4、 Examples include Li(FSO2)2N and Li(CF3SO2)2N. Among these, the Li salt preferably contains at least one of LiPF6 and C2F6LiNO4. Small amounts of a stabilizer for stabilizing the electrode surface, an overcharge inhibitor, a flame retardant, etc. may also be added.

[0030] [Polymer gel electrolyte] The 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 S / 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. [Example]

[0031] 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.

[0032] Example 1 102.4 g (0.4 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter abbreviated as "BPC": manufactured by Honshu Chemical Industry Co., Ltd.) and 0.1 g of hydrosulfite were dissolved in 1100 ml of a 5 w / w % aqueous sodium hydroxide solution. 500 ml of methylene chloride was added to the mixture, and while stirring, 0.5 g of benzyltriethylammonium chloride (hereinafter abbreviated as "TEBAC") was added. While maintaining the temperature at 15°C, 60 g of phosgene was then blown in over 60 minutes. After the phosgene injection was completed, 1.5 g of pt-butylphenol (hereinafter abbreviated as "PTBP": manufactured by Dainippon Ink and Chemicals, Inc.) was added as a molecular weight regulator and stirred vigorously to emulsify the reaction liquid. After emulsification, 0.4 ml of triethylamine was added, and the mixture was stirred at 20 to 25°C for approximately 1 hour to allow polymerization. After polymerization was completed, the reaction mixture 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 electrical conductivity of the aqueous phase reached 10 μS / cm or less. The resulting polymer solution was added dropwise to warm water maintained at 45°C, and the solvent was evaporated to obtain a white powdery precipitate. The resulting precipitate was filtered and dried at 105°C for 24 hours to obtain a polymer powder. The obtained polymer was analyzed by infrared absorption spectroscopy, and found to be -1 Absorption due to carbonyl groups at a position near 1240 cm -1 Absorption due to ether bonds was observed in the vicinity, and it was confirmed that the resin was a polycarbonate resin having carbonate bonds (hereinafter abbreviated as "PC-1"). The intrinsic viscosity of the obtained polycarbonate resin was measured by the method described below. Furthermore, as described below, resin compositions containing the obtained polycarbonate resin and each carbonate-based organic solvent were prepared, and solvent solubility tests and film thickness measurements were performed for each. Furthermore, the obtained polycarbonate resin was used to prepare electrolytic solution A and electrolytic solution B described below, and the electrical conductivity of each was measured. The results are shown in Table 1.

[0033] <Intrinsic viscosity (η) of polycarbonate resin> The specific viscosity of a 0.5 g / dL solution of polycarbonate resin in methylene chloride was measured at 25°C using an Ubbelohde capillary viscometer, and the intrinsic viscosity was calculated using the following formula (I) with a Huggins constant of 0.45. The measurement conditions are as follows: Measurement equipment: Ubbelohde capillary viscometer Solvent: Dichloromethane Resin solution concentration: 0.5 grams / dL (=C) ·Measurement temperature: 25℃ ·Specific viscosity:η sp The intrinsic viscosity [η] deciliters / gram was calculated using the following formula with the Huggins constant set at 0.45 (k'). η sp / C=[η]+k'[η] 2 C (I)

[0034] <Solvent solubility test> The resulting polycarbonate resin was added to various carbonate organic solvents (dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC)) to concentrations of 1 mass %, 10 mass %, and 20 mass % to prepare resin compositions, which were then placed in sealed glass containers and shaken for 24 hours using a shaker, after which the presence or absence of residual dissolved material was visually confirmed. The evaluation criteria were as follows: A: 20% by mass completely dissolved B: 10% by mass was completely dissolved, but 20% by mass remained undissolved C: 1% by mass completely dissolved, and 10% by mass remained undissolved D: 0.05% by mass completely dissolved, and 1% by mass remained undissolved E: 0.05% by mass of undissolved material

[0035] <Coating properties> The obtained polycarbonate resin was added to dimethyl carbonate (DMC) to a concentration of 10% by mass to prepare a resin composition, which was then coated using a 200 μm gap coater (400 μm gap coater was used for Example 7 only), air-dried for 1 day, and then dried at 120°C for 1 hour, and the thickness of the resulting coating film was measured.

[0036] <Conductivity measurement> A 0.5 mol / L dimethyl carbonate (DMC) solution was prepared using commercially available C2F6LiNO4 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and designated as Solution A. Five parts by mass of polycarbonate resin and 85 parts by mass of DMC were dissolved in a sealed container, and 10 parts by mass of the above Solution A were added and stirred to obtain Electrolyte Solution A. A commercially available 1.0 mol / L (EC:DEC = 1:1 volume ratio) solution containing LiPF (LBG-96533 electrolyte (1 mol / L LiPF EC:DEC 1:1 v / v%) manufactured by Kishida Chemical Co., Ltd.) was used as solution B. EC stands for ethylene carbonate. Five parts by mass of polycarbonate resin and 90 parts by mass of DMC were dissolved in a sealed container, and 5 parts by mass of the above solution B were added and stirred to obtain electrolyte B. The electrical conductivities of the resulting electrolytes A and B were measured. Measuring device: Conductivity meter (AS ONE Corporation waterproof conductivity meter AS650)

[0037] Example 2 Polymerization was carried out in the same manner as in Example 1, except that the amount of BPC was changed to 60.4 g, the amount of PTBP was changed to 1.8 g, and 40.1 g of 2,2-bis(4-hydroxyphenyl)propane (hereinafter abbreviated as "BPA": manufactured by Mitsubishi Chemical Corporation) was also used, to obtain a polycarbonate resin (hereinafter abbreviated as "PC-2"). The intrinsic viscosity of the obtained polycarbonate resin was measured in the same manner as in Example 1. Furthermore, a resin composition and an electrolyte solution were prepared using the obtained polycarbonate resin in the same manner as in Example 1, and a solvent solubility test and measurements of film thickness and conductivity were carried out. The results are shown in Table 1.

[0038] Example 3 Polymerization was carried out in the same manner as in Example 1, except that 54 g of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (hereinafter abbreviated as "MIBK": manufactured by Honshu Chemical Industry Co., Ltd.) and 58 g of 1,1-bis(4-hydroxyphenyl)-1-phenylethane (hereinafter abbreviated as "BPAP": manufactured by Honshu Chemical Industry Co., Ltd.) were used instead of BPC, the amount of PTBP was changed to 2.0 g, and TEBAC was not used, to obtain a polycarbonate resin (hereinafter abbreviated as "PC-3"). The intrinsic viscosity of the obtained polycarbonate resin was measured in the same manner as in Example 1. Furthermore, a resin composition and an electrolyte solution were prepared using the obtained polycarbonate resin in the same manner as in Example 1, and a solvent solubility test and measurements of film thickness and conductivity were carried out. The results are shown in Table 1. Note that for electrolyte solutions A and B, the polycarbonate resin precipitated, so the measurement of conductivity was discontinued.

[0039] Example 4 Polymerization was carried out in the same manner as in Example 1, except that 108 g of MIBK was used instead of BPC, 4.3 g of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (hereinafter abbreviated as "BTAZ": manufactured by Otsuka Chemical Co., Ltd.) was used instead of PTBP, and TEBAC was not used, to obtain a polycarbonate resin (hereinafter abbreviated as "PC-4"). The intrinsic viscosity of the obtained polycarbonate resin was measured in the same manner as in Example 1. Furthermore, a resin composition and an electrolyte solution were prepared using the obtained polycarbonate resin in the same manner as in Example 1, and a solvent solubility test and measurements of film thickness and conductivity were carried out. The results are shown in Table 1.

[0040] Example 5 Polymerization was carried out in the same manner as in Example 1, except that 36.0 g of bis(4-hydroxyphenyl)methane (hereinafter abbreviated as "BPF": manufactured by Sanko Co., Ltd.) and 50.2 g of BPA were used instead of BPC, the amount of PTBP was changed to 0.93 g, and TEBAC was not used, to obtain a polycarbonate resin (hereinafter abbreviated as "PC-5"). The intrinsic viscosity of the obtained polycarbonate resin was measured in the same manner as in Example 1. Furthermore, a resin composition and an electrolyte solution were prepared using the obtained polycarbonate resin in the same manner as in Example 1, and a solvent solubility test and measurements of film thickness and conductivity were carried out. The results are shown in Table 1. Note that for electrolyte solutions A and B, the polycarbonate resin precipitated, so the measurement of conductivity was discontinued.

[0041] Example 6 Polymerization was carried out in the same manner as in Example 1, except that the amount of BPC was changed to 60.4 g, 40.1 g of BPA and 1.92 g of p-hydroxyphenethyl alcohol (hereinafter abbreviated as "PHEP": manufactured by Otsuka Chemical Co., Ltd.) were used at the same time, and PTBP and TEBAC were not used, to obtain a polycarbonate resin (hereinafter abbreviated as "PC-6"). The intrinsic viscosity of the obtained polycarbonate resin was measured in the same manner as in Example 1. Furthermore, a resin composition and an electrolyte solution were prepared using the obtained polycarbonate resin in the same manner as in Example 1, and a solvent solubility test and measurements of film thickness and conductivity were carried out. The results are shown in Table 1.

[0042] Example 7 Polymerization was carried out in the same manner as in Example 1, except that 124.0 g of 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter abbreviated as "TMC": manufactured by Sanko Co., Ltd.) was used instead of BPC, the amount of PTBP was changed to 1.62 g, and TEBAC was not used, to obtain a polycarbonate resin (hereinafter abbreviated as "PC-7"). The intrinsic viscosity of the obtained polycarbonate resin was measured in the same manner as in Example 1. Furthermore, a resin composition and an electrolyte solution were prepared using the obtained polycarbonate resin in the same manner as in Example 1, and a solvent solubility test and measurements of film thickness and conductivity were carried out. The results are shown in Table 1. Note that for electrolyte solutions A and B, the polycarbonate resin precipitated, so the measurement of conductivity was discontinued.

[0043] Example 8 Polymerization was carried out in the same manner as in Example 1, except that 94.1 g of BPAF, 27.4 g of BPA, and 1.10 g of PHEP were used instead of BPC, and PTBP was not used, to obtain a polycarbonate resin (hereinafter abbreviated as "PC-8"). The intrinsic viscosity of the obtained polycarbonate resin was measured in the same manner as in Example 1. Furthermore, a resin composition and an electrolyte solution were prepared using the obtained polycarbonate resin in the same manner as in Example 1, and a solvent solubility test and measurements of film thickness and conductivity were carried out. The results are shown in Table 1.

[0044] Example 9 2.0 g of PC-1 obtained in Example 1 and 8.0 g of diethyl carbonate (DEC) were placed in a 100 ml beaker and dissolved by stirring using a Teflon stirrer. After dissolution, 1.0 ml of the aforementioned Solution B (LBG-96533 electrolyte (1 mol / l LiPF6EC:DEC 1:1 v / v%) manufactured by Kishida Chemical Co., Ltd.) was added dropwise while stirring. Once Solution B was mixed, stirring was stopped and the mass was measured (11.2 g, excluding the beaker and stir bar, before concentration). The beaker was then left in a draft chamber for 24 hours, and the solvent was partially removed by air drying, leaving a highly viscous solution with a solidified surface. The mass of the solution (after concentration) was 8.1 g. A conductivity meter was inserted into this partially gelled (solvent-containing) polymer gel electrolyte to measure its conductivity. The results are shown in Table 2. The conductivity was measured as follows. Measuring device: Conductivity meter (AS ONE Corporation waterproof conductivity meter AS650)

[0045] Example 10 2.0 g of PC-8 obtained in Example 8 and 8.0 g of DEC were placed in a 100 ml beaker and stirred and dissolved using a Teflon stirrer. After dissolution, 2.5 ml of the above-mentioned Solution B was added dropwise while stirring. Once Solution B was mixed, stirring was stopped and the mass was measured (13.0 g, excluding the beaker and stir bar, before concentration). The beaker was then left in a draft chamber for 24 hours, and the solvent was partially removed by air drying, leaving a highly viscous liquid with a solidified surface. The mass of the solution (after concentration) was 7.1 g. A conductivity meter was inserted into this partially gelled (solvent-containing) polymer gel electrolyte, and the conductivity was measured in the same manner as in Example 9. The results are shown in Table 2.

[0046] (Comparative Example 1) Polymerization was carried out in the same manner as in Example 1, except that 91.2 g of BPA was used instead of BPC, 2.00 g of PTBP was used, and no TEBAC was used, to obtain a polycarbonate resin (hereinafter abbreviated as "PC-9"). The intrinsic viscosity of the obtained polycarbonate resin was measured in the same manner as in Example 1. Furthermore, a resin composition was prepared using the obtained polycarbonate resin in the same manner as in Example 1, and a solvent solubility test was performed. An attempt was made to form a coating film using the resin composition prepared in the same manner as in Example 1, but the coating film could not be formed. Furthermore, electrolyte solutions A and B were prepared in the same manner as in Example 1, but the polycarbonate resin precipitated, so the conductivity measurement was discontinued. The results are shown in Table 1.

[0047] (Comparative Example 2) Polymerization was carried out in the same manner as in Example 1, except that 107.2 g of BPZ was used instead of BPC, the amount of PTBP was changed to 2.00 g, and TEBAC was not used, to obtain a polycarbonate resin (hereinafter abbreviated as "PC-10"). The intrinsic viscosity of the obtained polycarbonate resin was measured in the same manner as in Example 1. Furthermore, a resin composition was prepared using the obtained polycarbonate resin in the same manner as in Example 1, and a solvent solubility test was performed. An attempt was made to form a coating film using the resin composition prepared in the same manner as in Example 1, but the coating film could not be formed. Furthermore, electrolyte solutions A and B were prepared in the same manner as in Example 1, but the polycarbonate resin precipitated, so the conductivity measurement was discontinued. The results are shown in Table 1.

[0048] (Comparative Example 3) Polymerization was carried out in the same manner as in Example 1, except that 116.0 g of BPAP was used instead of BPC, the amount of PTBP was changed to 2.00 g, and TEBAC was not used, to obtain a polycarbonate resin (hereinafter abbreviated as "PC-11"). The intrinsic viscosity of the obtained polycarbonate resin was measured in the same manner as in Example 1. Furthermore, a resin composition was prepared using the obtained polycarbonate resin in the same manner as in Example 1, and a solvent solubility test was performed. An attempt was made to form a coating film using the resin composition prepared in the same manner as in Example 1, but the coating film could not be formed. Furthermore, electrolyte solutions A and B were prepared in the same manner as in Example 1, but the polycarbonate resin precipitated, so the conductivity measurement was discontinued. The results are shown in Table 1.

[0049] Comparative Example 4 Polymerization was carried out in the same manner as in Example 1, except that 14.8 g of 4,4'-biphenyldiol (hereinafter abbreviated as "BP": manufactured by Honshu Chemical Industry Co., Ltd.) and 73.0 g of BPA were used instead of BPC, the amount of PTBP was changed to 1.30 g, and TEBAC was not used, to obtain a polycarbonate resin (hereinafter abbreviated as "PC-12"). The intrinsic viscosity of the obtained polycarbonate resin was measured in the same manner as in Example 1. Furthermore, a resin composition was prepared using the obtained polycarbonate resin in the same manner as in Example 1, and a solvent solubility test was performed. An attempt was made to form a coating film using the resin composition prepared in the same manner as in Example 1, but the coating film could not be formed. Furthermore, electrolyte solutions A and B were prepared in the same manner as in Example 1, but the polycarbonate resin precipitated, so the conductivity measurement was discontinued. The results are shown in Table 1.

[0050] (Comparative Example 5) A composition was prepared in the same manner as in Example 1, except that no polycarbonate resin was used and the mass equivalent of the polycarbonate resin was replaced with dimethyl carbonate (DMC). An attempt was made to form a coating film using the obtained composition, but no coating film could be formed. Furthermore, electrolytic solutions A and B were prepared in the same manner as in Example 1, except that no polycarbonate resin was used and the mass equivalent of the polycarbonate resin was replaced with dimethyl carbonate (DMC), and the conductivity was measured. The results are shown in Table 1.

[0051] [Table 1] [Table 2] [ka] [Industrial Applicability]

[0052] The resin composition of the present invention is a resin composition in which a polycarbonate resin highly soluble in carbonate-based organic solvents is dissolved, and is low in toxicity, making it suitable as a coating material (paint or ink) for various substrates. Furthermore, it has good compatibility with Li salts, and maintains high conductivity even when the polycarbonate resin is dissolved, making it useful as an electrolyte. It is particularly useful for modifying the SEI (Solid Electrolyte Interphase) layer of the electrolyte of Li-ion batteries and Li-ion polymer batteries, and can impart flame retardancy and other properties to Li-ion batteries and Li-ion polymer batteries. Furthermore, the concentrated electrolyte of the present invention can be gelled, making it applicable as a polymer gel electrolyte for Li-ion polymer batteries.

Claims

1. General formula (1): 【Chemistry 1】 (In the formula, R １ ~R ４ and R １１ ~R １４ 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; a is an integer from 1 to 1,000; X is 【Chemistry 2】 and Here, 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 are bonded to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 atoms, R 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; b represents an integer of 0 to 20. A polycarbonate resin containing a structural unit represented by the formula: A resin composition comprising a carbonate-based organic solvent, the content of the polycarbonate resin in the resin composition is 0.05 to 50% by mass, the content of the carbonate-based organic solvent in the resin composition is 50 to 99.5% by mass, The following formulas (2) to (4) among all the structural units represented by the general formula (1): 【Transformation 3】 The total proportion of the structural units represented by the formula (I) is 0 to 75% by molar ratio, A resin composition, wherein the structural unit represented by the general formula (1) includes one or more structural units selected from the group consisting of structural units represented by the following formulas (6) to (9): 【Chemistry 4】

2. The resin composition according to claim 1, wherein the content of the carbonate-based organic solvent in the resin composition is 70 to 99 mass%.

3. The resin composition according to claim 1 or 2, wherein the carbonate-based organic solvent comprises at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate.

4. The resin composition according to claim 3 , wherein the carbonate-based organic solvent further contains ethylene carbonate.

5. The structural unit represented by the general formula (1) comprises one or more selected from the group consisting of structural units represented by the formulas (6) and (8). The resin composition according to any one of claims 1 to 4.

6. The resin composition according to any one of claims 1 to 5, wherein the polycarbonate resin has an intrinsic viscosity of 0.3 to 2.0 dl / g.

7. The resin composition according to any one of claims 1 to 6, wherein the resin composition does not contain any organic solvent other than the carbonate-based organic solvent.

8. A coating film obtained by drying the resin composition according to any one of claims 1 to 7.

9. An electrolytic solution comprising the resin composition according to any one of claims 1 to 7, and 0.1 to 30 mass % of a lithium salt dissolved therein.

10. The electrolyte of claim 9 wherein the lithium salt comprises LiPF 6 .

11. A polymer gel electrolyte obtained by gelling the electrolytic solution according to claim 9 or 10.

12. The polymer gel electrolyte according to claim 11, having a conductivity of 1 to 30,000 μS / cm.

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