Polycarbonate copolymer and molded article composed of same

Abstract

The present invention provides: a polycarbonate copolymer which has a small dimensional change caused by heat or water absorption and excellent heat resistance; and a molded article composed of the same. A polycarbonate copolymer according to the present invention includes, with respect to all constitutional units, at least 70 mol% of a constitutional unit (A) represented by formula (1) (in formula (1), R1, R2, and R3 each independently represent a hydrogen atom, a halogen atom, or a C1-C3 alkyl group, R4 represents a C1-C12 alkyl group, a C6-C12 aryl group, or a C7-C13 aryl-substituted alkyl group, and n and m each independently represent an integer of 1-4) and a constitutional unit (B) represented by formula (2) (in formula (2), X represents a group that is bonded to a carbon atom to form a C6-C12 alicyclic hydrocarbon which may have a substituent), and is characterized in that the proportion of the constitutional unit (A) in all the constitutional units is 10-90 mol%.

Description

Polycarbonate copolymer and molded article made thereof

[0001] The present invention relates to a polycarbonate copolymer that exhibits little dimensional change due to heat or water absorption and has excellent heat resistance, and to a molded article made thereof.

[0002] Polycarbonate resin is an engineering plastic that is used in a wide range of fields, including housings for electrical and electronic devices, interior and exterior parts for automobiles, building materials, furniture, musical instruments, and miscellaneous goods, due to its excellent transparency and impact resistance.

[0003] Some of these applications require extremely high heat resistance and excellent dimensional stability. Polycarbonate resins containing 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane as a structural unit are known to have excellent heat resistance (see, for example, Patent Documents 1 and 2). While these polycarbonate resins have excellent heat resistance, they have a problem in that their linear expansion coefficient is high, resulting in large dimensional changes due to heat.

[0004] It is also known that polycarbonate resins containing 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine as a structural unit exhibit excellent heat resistance and a low coefficient of linear expansion (see, for example, Patent Documents 3 to 5). Although these polycarbonate resins exhibit excellent heat resistance and a low coefficient of linear expansion, they have a problem in that they have a high water absorption rate and therefore undergo significant dimensional change due to water absorption.

[0005] Japanese Patent Laid-Open No. 2-88634, Special Publication No. 2011-521024, U.S. Patent No. 5,344,910, Special Publication No. 2009-517537, Special Publication No. 2016-536418

[0006] As described above, there is a demand for polycarbonate resins that exhibit little dimensional change due to heat or water absorption and have excellent heat resistance. Therefore, an object of the present invention is to provide polycarbonate resins that exhibit little dimensional change due to heat or water absorption and have excellent heat resistance, and molded articles made from such polycarbonate resins.

[0007] As a result of extensive research to achieve the above object, the present inventors discovered that a polycarbonate copolymer having a specific structural unit can solve the above problems, and thus arrived at the present invention. That is, the present invention provides the following items 1 to 8.

[0008] 1. A structural unit (A) represented by the following formula (1), and (In formula (1), R １ , R ２ and R ３ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms; R ４ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl-substituted alkyl group having 7 to 13 carbon atoms, and n and m each independently represent an integer of 1 to 4.) A structural unit (B) represented by the following formula (2): (In formula (2), X represents a group which bonds to a carbon atom to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent.) A polycarbonate copolymer comprising 70 mol % or more of all structural units, characterized in that the proportion of structural unit (A) in all structural units is 10 to 90 mol %.

[0009] 2. The polycarbonate copolymer according to item 1 above, wherein the proportion of the structural unit (B) in all structural units is 10 to 90 mol %. 3. The polycarbonate copolymer according to item 1 or 2 above, wherein the glass transition temperature is 200 to 280°C. 4. The polycarbonate copolymer according to any one of items 1 to 3 above, wherein the linear expansion coefficient is 40 to 60 ppm / °C. 5. The polycarbonate copolymer according to any one of items 1 to 4 above, wherein the saturated water absorption is 2.40% or less. 6. A molded article obtained by injection molding the polycarbonate copolymer according to any one of items 1 to 5 above. 7. A sheet or film obtained by extrusion molding the polycarbonate copolymer according to any one of items 1 to 5 above. 8. An electric or electronic part using the molded article according to item 6 above or the sheet or film according to item 7 above.

[0010] The polycarbonate copolymer of the present invention and molded articles made thereof exhibit small dimensional changes due to heat or water absorption and excellent heat resistance, and are therefore particularly suitable for use in electrical and electronic parts, and therefore have exceptional industrial effects.

[0011] <Polycarbonate Copolymer> The polycarbonate copolymer of the present invention is a polycarbonate copolymer containing a structural unit (A) represented by the following formula (1) and a structural unit (B) represented by the following formula (2): The polycarbonate copolymer contains 70 mol % or more of the structural unit (A) and the structural unit (B) relative to all structural units, preferably 80 mol % or more, and more preferably 90 mol % or more.

[0012] (In formula (1), R １ , R ２ and R ３ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms; R ４ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl-substituted alkyl group having 7 to 13 carbon atoms, and n and m each independently represent an integer of 1 to 4.

[0013] (In formula (2), X represents a group that bonds with a carbon atom to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent.)

[0014] In the structural unit (A) represented by the formula (1), R １ , R ２ and R ３ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom. ４ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl-substituted alkyl group having 7 to 13 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and most preferably a phenyl group.

[0015] The content (molar fraction) of the structural unit (A) is 10 to 90 mol%, preferably 20 to 90 mol%, more preferably 30 to 90 mol%, and even more preferably 30 to 80% of all structural units of the polycarbonate copolymer. If it is less than the lower limit, the glass transition temperature may be low or the linear expansion coefficient may be high. If it exceeds the upper limit, the water absorption may be high.

[0016] Furthermore, in the structural unit (B) represented by the formula (2) above, X is a group that bonds to a carbon atom to form an alicyclic hydrocarbon having 6 to 12 carbon atoms (including the carbon atoms in formula (2)), which may have a substituent, and is preferably a cyclohexyl group substituted with a methyl group, and most preferably a 3,3,5-trimethylcyclohexyl group.

[0017] The content (molar fraction) of the structural unit (B) is preferably 10 to 90 mol%, more preferably 10 to 80 mol%, even more preferably 10 to 70 mol%, and particularly preferably 20 to 70 mol%. If it is below the lower limit, the water absorption rate may be high. If it exceeds the upper limit, the glass transition temperature may be low or the linear expansion coefficient may be high.

[0018] In the present invention, by containing both the structural unit (A) represented by the formula (1) above and the structural unit (B) represented by the formula (2) above in a predetermined proportion, it is possible to solve the problems that arise when only the structural unit (A) or the structural unit (B) is contained, and to obtain a polycarbonate copolymer that has an excellent balance of heat resistance and dimensional change due to heat or water absorption.

[0019] The polycarbonate copolymer of the present invention may further contain a structural unit (C) represented by the following formula (3) or other copolymerization units in an amount of 30 mol % or less, preferably 20 mol % or less, and more preferably 10 mol % or less, of all structural units.

[0020] (In formula (3), Y is a single bond or at least one group selected from the group consisting of the following formula (4):)

[0021] (In formula (4), R５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ each independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R １３ and R １４ each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; when there are a plurality of groups, they may be the same or different, a is an integer from 1 to 10, and b is an integer from 4 to 7.

[0022] <Method for Producing Polycarbonate Copolymer> The raw material monomers used for the polycarbonate copolymer of the present invention include dihydric phenols represented by the following formula (5) and formula (6).

[0023] (In formula (5), R １ , R ２ and R ３ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms; R ４ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl-substituted alkyl group having 7 to 13 carbon atoms, and n and m each independently represent an integer of 1 to 4.

[0024] (In formula (6), X represents a group that bonds with a carbon atom to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent.)

[0025] As the dihydric phenol represented by the above formula (5), for example, 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine (hereinafter sometimes abbreviated as PPPBP) is suitable.

[0026] As the dihydric phenol represented by the above formula (6), for example, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as TMC) is suitable.

[0027] The raw material monomers used for the polycarbonate copolymer of the present invention include those represented by the above formula (5) and formula (6), and may further include a monomer represented by the following formula (7) other than the monomers represented by formula (5) and formula (6).

[0028] (In formula (7), Y is a single bond or at least one group selected from the group consisting of the following formula (4):)

[0029] (In formula (4), R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ each independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R １３ and R １４ each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; when there are a plurality of groups, they may be the same or different, a is an integer from 1 to 10, and b is an integer from 4 to 7.

[0030] Among these, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, or α,α'-bis(4-hydroxyphenyl)-1,3-diisopropylbenzene is preferred, and 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes abbreviated as BPA) is more preferred.

[0031] The polycarbonate copolymer of the present invention may be further copolymerized with other dihydroxy compounds or diol compounds to the extent that the properties of the polycarbonate copolymer are not impaired.

[0032] Other dihydroxy compounds include hydroquinone, resorcinol, orcinol, 2,2-bis(4-hydroxyphenyl)norbornene, 1,3-bis(4-hydroxyphenyl)adamantane; 2,2-bis(4-hydroxyphenyl)adamantane; 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 10,10-bis(4-hydroxyphenyl)-9-anthrone, 1,5-bis(4-hydroxyphenylthio)-2,3-dioxapentaenebisphenoxyethanolfluorene, and the like.

[0033] Other diol compounds include isosorbide:1,4:3,6-dianhydro-D-sorbitol, tricyclodecane dimethanol (TCDDM), 4,8-bis(hydroxymethyl)tricyclodecane, tetramethylcyclobutanediol (TMCBD), 2,2,4,4-tetramethylcyclobutane-1,3-diol, mixed isomers, cis / trans-1,4-cyclohexanedimethanol (CHDM), cis / trans-1,4-bis(hydroxymethyl)cyclohexane, cyclohex-1,4-ylenedimethanol, Examples of such cyclohexanedimethanol include 1,1'-bi(cyclohexyl)-4,4'-diol, spiroglycol, dicyclohexyl-4,4'-diol, 4,4'-dihydroxybicyclohexyl, and poly(ethylene glycol).

[0034] The polycarbonate copolymer of the present invention is obtained by reacting the dihydric phenol compound with a carbonate precursor. Reaction methods include interfacial polycondensation, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds. In the case of interfacial polycondensation, a monohydric phenol-based end-stopper is usually used.

[0035] The polycarbonate copolymer includes a polyester carbonate copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. The aliphatic bifunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Examples of preferred aliphatic bifunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosane dicarboxylic acid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These carboxylic acids may be copolymerized to the extent that the objective is not impaired. Furthermore, the polycarbonate copolymer can also be copolymerized with a structural unit containing a polyorganosiloxane unit, if necessary.

[0036] The polycarbonate copolymer can also be made into a branched polycarbonate by copolymerizing a structural unit containing a trifunctional or higher polyfunctional aromatic compound, if necessary.

[0037] Suitable examples of trifunctional or higher polyfunctional aromatic compounds used in branched polycarbonates include 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and trisphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol. Of these, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred. The content of the structural units derived from such polyfunctional aromatic compounds is preferably 0.03 to 1.5 mol %, more preferably 0.1 to 1.2 mol %, and particularly preferably 0.2 to 1.0 mol %, of the total of 100 mol % including the structural units derived from other dihydric phenol components.

[0038] The branched structural units may be derived not only from polyfunctional aromatic compounds but also from side reactions occurring during polymerization by melt transesterification without using polyfunctional aromatic compounds. １ It can be calculated by H-NMR measurement.

[0039] In reactions using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine. Examples of solvents that can be used include halogenated hydrocarbons such as methylene chloride and chlorobenzene. To promote the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. The reaction temperature is usually 0 to 40°C, and the reaction time is usually several minutes to 5 hours.

[0040] Transesterification reactions using, for example, a carbonate diester as a carbonate precursor are carried out by heating and stirring a predetermined proportion of aromatic dihydroxy components with the carbonate diester under an inert gas atmosphere, and distilling off the resulting alcohol or phenol. The reaction temperature varies depending on the boiling point of the resulting alcohol or phenol, but is typically in the range of 120 to 300°C. The reaction is completed by reducing the pressure from the beginning of the reaction to distill off the resulting alcohol or phenol. A catalyst typically used in transesterification reactions can also be used to promote the reaction. Examples of carbonate diesters used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

[0041] Monofunctional phenols that are commonly used as end terminators can be used. In particular, in reactions using phosgene as a carbonate precursor, monofunctional phenols are commonly used as end terminators to control molecular weight, and the resulting polycarbonate copolymers have excellent thermal stability compared to those that are not, since their ends are blocked with groups based on the monofunctional phenol. Specific examples of the monofunctional phenols include phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, and p-long-chain alkylphenols.

[0042] (Other Components) The polycarbonate copolymer of the present invention may contain various additives to provide various properties to the resin composition, provided that the object of the present invention is not impaired. Examples of additives that can be used include mold release agents, heat stabilizers, ultraviolet absorbers, bluing agents, antistatic agents, flame retardants, heat-shielding agents, fluorescent dyes (including fluorescent brighteners), pigments, light diffusing agents, reinforcing fillers, other resins, and elastomers.

[0043] Preferably, the release agent is one that is composed of 90% by weight or more of an ester of alcohol and fatty acid. Specific examples of the ester of alcohol and fatty acid include ester of monohydric alcohol and fatty acid, and partial or complete ester of polyhydric alcohol and fatty acid. Specific examples of the ester of monohydric alcohol and saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate. Stearyl stearate is preferred. Examples of partial or full esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, and full or partial esters of dipentaerythritol such as dipentaerythritol hexastearate. Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and mixtures of stearic acid triglyceride and stearyl stearate are preferred, with stearic acid monoglyceride and pentaerythritol tetrastearate being more preferred.

[0044] The amount of the release agent to be added is preferably in the range of 0.05 to 0.5 parts by weight, more preferably 0.1 to 0.4 parts by weight, and even more preferably 0.12 to 0.3 parts by weight, per 100 parts by weight of the polycarbonate copolymer.

[0045] Examples of the heat stabilizer include phosphorus-based heat stabilizers, sulfur-based heat stabilizers, and hindered phenol-based heat stabilizers. Examples of the phosphorus-based heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples include bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, [1,1-biphenyl]-4,4-diylbis[bis(2,4-di-tert-butylphenoxy)phosphine], 3,9-bis(2,6-di-tert-butylphenyl)propionate ...

[0033] Preferred are tris(2,4-di-tert-butylphenyl)phosphite, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.

[0046] The amount of the heat stabilizer to be added is preferably in the range of 0.001 to 0.5 parts by weight, more preferably 0.005 to 0.4 parts by weight, and even more preferably 0.01 to 0.3 parts by weight, per 100 parts by weight of the polycarbonate copolymer.

[0047] (Viscosity Average Molecular Weight) The viscosity average molecular weight of the polycarbonate copolymer in the present invention is preferably 6,000 to 30,000, more preferably 7,000 to 28,000, and even more preferably 8,000 to 25,000. A viscosity average molecular weight within the above range is preferred because it provides excellent mechanical properties, productivity, and processability.

[0048] The viscosity average molecular weight of the polycarbonate copolymer in the present invention can be calculated by the following formula: ０ ) / t ０ [t ０is the number of seconds it takes for methylene chloride to fall, and t is the number of seconds it takes for the sample solution to fall], the specific viscosity (ηSP) was measured using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of resin in 100 ml of methylene chloride at 20°C, and the viscosity average molecular weight Mv was calculated from the measured specific viscosity (ηSP) using the following formula: ηSP / c=[η]+0.45×[η] ２ c (where [η] is the intrinsic viscosity) [η] = 1.23 × 10 －４ Mv ０．８３ c=0.7

[0049] (Glass transition temperature: Tg) The glass transition temperature (Tg) of the polycarbonate copolymer of the present invention is preferably in the range of 200 to 280°C, more preferably 220 to 280°C, and even more preferably 240 to 275°C. A Tg within the above range is preferred because it provides excellent heat resistance. The glass transition temperature (Tg) is measured using a Model 2910 DSC manufactured by TA Instruments Japan Ltd. at a heating rate of 20°C / min.

[0050] (Coefficient of Linear Expansion: CTE) The coefficient of linear expansion (CTE) of the polycarbonate copolymer in the present invention is preferably in the range of 40 to 60 ppm / °C, more preferably 43 to 58 ppm / °C, and even more preferably 45 to 56 ppm / °C. A CTE within the above range is preferred because dimensional change due to heat is small. The coefficient of linear expansion (CTE) is measured three times using a thermomechanical analyzer (SS6100 manufactured by SII Nano Technology Co., Ltd.) on a sample having a length of 4 mm and a width of 20 mm at a heating rate of 10°C / min and a cooling rate of 50°C / min, and the linear expansion coefficient in the measurement temperature range of 50 to 90°C is calculated and the average value is obtained.

[0051] (Saturated Water Absorption) The saturated water absorption of the polycarbonate copolymer in the present invention is measured in accordance with JIS K7209:2000 and is preferably 2.40% or less, more preferably 2.38% or less, and even more preferably 2.35% or less. If the saturated water absorption is within the above range, dimensional change due to water absorption is small, which is preferable. The lower limit of the saturated water absorption is not particularly limited, but 0.10% or more is sufficient.

[0052] (Molding method and molded article) As a method for molding the polycarbonate copolymer in the present invention, general molding methods for polycarbonate copolymers can be used, such as injection molding, extrusion molding, compression molding, solution casting, etc. In particular, a method for molding a molded article by injection molding or a method for molding a sheet or film by extrusion molding are preferably used.

[0053] The polycarbonate copolymer of the present invention has excellent transparency, dimensional stability, and heat resistance, and can be used for various molded articles, and is particularly suitable for electrical and electronic parts such as connectors, switches, sockets, sensor cases, and flexible films that are used in high-temperature environments.

[0054] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. Evaluation was performed according to the following methods.

[0055] (1) Composition Ratio 40 mg of a sample was dissolved in 0.6 mL of deuterated chloroform, and the polymer composition ratio (molar ratio) was calculated from the integral ratio of each structural unit using proton NMR on a JEOL JNM-AL400.

[0056] (2) Viscosity average molecular weight Specific viscosity (ηSP) = (t-t ０ ) / t ０ [t ０ is the number of seconds for methylene chloride to fall, and t is the number of seconds for the sample solution to fall], the specific viscosity (ηSP) was measured using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of sample in 100 ml of methylene chloride at 20°C, and the viscosity average molecular weight Mv was calculated from the measured specific viscosity (ηSP) using the following formula: ηSP / c = [η] + 0.45 × [η] ２ c (where [η] is the intrinsic viscosity) [η] = 1.23 × 10 －４ Mv ０．８３ c=0.7

[0057] (3) Glass transition temperature (Tg) Using 8 mg of a sample, a thermal analysis system DSC-2910 manufactured by TA Instruments Co., Ltd. was used to measure the glass transition temperature (Tg) in accordance with JIS K7121 under the conditions of a nitrogen atmosphere (nitrogen flow rate: 40 ml / min) and a temperature rise rate of 20°C / min.

[0058] (4) Coefficient of Linear Expansion (CTE) 3 mg of a sample was dissolved in methylene chloride, and then the methylene chloride was evaporated to obtain a cast film. Using a thermomechanical analyzer (SS6100 manufactured by SII Nano Technology Co., Ltd.), a sample having a length of 4 mm, a width of 20 mm, was measured three times at a heating rate of 10°C / min and a cooling rate of 50°C / min to calculate the coefficient of linear expansion in the measurement temperature range of 50 to 90°C, and the average value was calculated.

[0059] (5) Saturated Water Absorption According to JIS K7209:2000, 3 mg of a sample was dissolved in methylene chloride, and then the methylene chloride was evaporated to obtain a cast film. The film was dried at 50°C for 24 hours, and then immersed in water at 25°C. The weight was measured and the water absorption was calculated using the following formula: Water absorption (%) = {(resin weight after water absorption - resin weight before water absorption) / resin weight before water absorption} x 100 The water absorption was measured over time, and the water absorption when it reached an equilibrium value was calculated as the saturated water absorption.

[0060] Example 1 A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 98.69 parts by weight of ion-exchanged water and 59.04 parts by weight of a 25% aqueous sodium hydroxide solution under a nitrogen atmosphere, and 33.15 parts by weight of 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine (manufactured by Shanxi Liuqing Pharmaceutical Co., Ltd., hereinafter referred to as PPPBP) as a dihydric phenol, 6.54 parts by weight of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (manufactured by Honshu Chemical Industry Co., Ltd., hereinafter referred to as TMC), and 0.079 parts by weight of hydrosulfite (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved therein. 116.5 parts by weight of methylene chloride was then added, and 13.57 parts by weight of phosgene was blown in over 60 minutes at 18 to 20°C with stirring. Thereafter, 8.435 parts by weight of a 25% aqueous sodium hydroxide solution and 0.506 parts by weight of p-tert-butylphenol were added and stirred. During the reaction, 0.027 parts by weight of triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and the reaction was terminated after stirring for 1.5 hours at 25-30°C. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, the organic phase was washed with acidic hydrochloric acid water. The aqueous phase was then repeatedly washed with ion-exchanged water until its conductivity became nearly the same as that of the ion-exchanged water. The aqueous phase was then added dropwise to warm water maintained at 50-80°C, and the solvent was evaporated to remove the solid, yielding a flaky solid. The resulting solid was filtered and dried at 120°C for 24 hours to yield a white flaky polycarbonate copolymer. The resulting polycarbonate copolymer was subjected to various evaluations using the methods described above, and the results are shown in Table 1.

[0061] Example 2: 94.80 parts by weight of ion-exchanged water and 56.70 parts by weight of 25% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser under a nitrogen atmosphere, and 7.96 parts by weight of PPPBP as a dihydric phenol, 25.11 parts by weight of TMC, and 0.066 parts by weight of hydrosulfite were dissolved therein. 116.5 parts by weight of methylene chloride was then added, and 13.03 parts by weight of phosgene was blown in over 60 minutes at 18 to 20°C with stirring. Subsequently, 56.7 parts by weight of 25% aqueous sodium hydroxide solution and 0.486 parts by weight of p-tert-butylphenol were added and stirred. During the reaction, 0.026 parts by weight of triethylamine was added, and stirring was continued for 1.5 hours at 25 to 30°C, at which point the reaction was terminated. After completion of the reaction, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, the mixture was washed with acidic water containing hydrochloric acid. The mixture was then repeatedly washed with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, it was dropped into warm water maintained at 50 to 80°C to evaporate and remove the solvent, yielding a flaky solid. The resulting solid was filtered and dried at 120°C for 24 hours to yield a white flaky polycarbonate copolymer. The resulting polycarbonate copolymer was subjected to various evaluations using the methods described above, and the results are shown in Table 1.

[0062] Example 3: 94.76 parts by weight of ion-exchanged water and 56.70 parts by weight of 25% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser under a nitrogen atmosphere, and 19.89 parts by weight of PPPBP as a dihydric phenol, 15.71 parts by weight of TMC, and 0.071 parts by weight of hydrosulfite were dissolved therein. 111.9 parts by weight of methylene chloride was then added, and 13.03 parts by weight of phosgene was blown in over 60 minutes at 18 to 20°C with stirring. Subsequently, 8.100 parts by weight of 25% aqueous sodium hydroxide solution and 0.486 parts by weight of p-tert-butylphenol were added and stirred. During the reaction, 0.026 parts by weight of triethylamine was added, and stirring was continued for 1.5 hours at 25 to 30°C, whereupon the reaction was terminated. After completion of the reaction, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, the mixture was washed with acidic water containing hydrochloric acid. The mixture was then repeatedly washed with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, it was dropped into warm water maintained at 50 to 80°C to evaporate and remove the solvent, yielding a flaky solid. The resulting solid was filtered and dried at 120°C for 24 hours to yield a white flaky polycarbonate copolymer. The resulting polycarbonate copolymer was subjected to various evaluations using the methods described above, and the results are shown in Table 1.

[0063] Example 4: A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 94.76 parts by weight of ion-exchanged water and 56.70 parts by weight of 25% aqueous sodium hydroxide solution under a nitrogen atmosphere, and 15.92 parts by weight of PPPBP (dihydric phenol), 15.71 parts by weight of TMC, 2.31 parts by weight of 2,2-bis(4-hydroxyphenyl)propane (manufactured by Nippon Steel Chemical & Materials, hereinafter referred to as BPA), and 0.063 parts by weight of hydrosulfite were dissolved therein. 111.87 parts by weight of methylene chloride was then added, and 13.03 parts by weight of phosgene was bubbled in over 60 minutes at 18-20°C with stirring. Subsequently, 8.10 parts by weight of 25% aqueous sodium hydroxide solution and 0.486 parts by weight of p-tert-butylphenol were added and stirred. During the reaction, 0.026 parts by weight of triethylamine was added, and the mixture was stirred at 25-30°C for 1.5 hours, at which point the reaction was terminated. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, the organic phase was washed with hydrochloric acid-acidified water. After that, the organic phase was repeatedly washed with ion-exchanged water. When the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, the aqueous phase was dropped into warm water maintained at 50-80°C, and the solvent was evaporated to obtain a flaky solid. The obtained solid was filtered and dried at 120°C for 24 hours to obtain a white flaky polycarbonate copolymer. The obtained polycarbonate copolymer was subjected to various evaluations using the methods described above, and the results are shown in Table 1.

[0064] Example 5: 109.45 parts by weight of ion-exchanged water and 65.49 parts by weight of 25% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser under a nitrogen atmosphere, and 41.36 parts by weight of PPPBP as a dihydric phenol, 3.63 parts by weight of TMC, and 0.090 parts by weight of hydrosulfite were dissolved therein. 129.22 parts by weight of methylene chloride was then added, and 15.05 parts by weight of phosgene was blown in over 60 minutes at 18 to 20°C with stirring. Subsequently, 9.36 parts by weight of 25% aqueous sodium hydroxide solution and 0.561 parts by weight of p-tert-butylphenol were added and stirred. During the reaction, 0.030 parts by weight of triethylamine was added, and stirring was continued for 1.5 hours at 25 to 30°C, at which point the reaction was terminated. After completion of the reaction, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, the mixture was washed with acidic water containing hydrochloric acid. The mixture was then repeatedly washed with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, it was dropped into warm water maintained at 50 to 80°C to evaporate and remove the solvent, yielding a flaky solid. The resulting solid was filtered and dried at 120°C for 24 hours to yield a white flaky polycarbonate copolymer. The resulting polycarbonate copolymer was subjected to various evaluations using the methods described above, and the results are shown in Table 1.

[0065] Comparative Example 1: 91.57 parts by weight of ion-exchanged water and 54.78 parts by weight of 25% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser under a nitrogen atmosphere, and 38.46 parts by weight of PPPBP as a dihydric phenol and 0.077 parts by weight of hydrosulfite were dissolved therein. Then, 108.09 parts by weight of methylene chloride was added, and 12.59 parts by weight of phosgene was blown in over 60 minutes at 18 to 20°C with stirring. Subsequently, 7.83 parts by weight of 25% aqueous sodium hydroxide solution and 0.469 parts by weight of p-tert-butylphenol were added and stirred. During the reaction, 0.025 parts by weight of triethylamine was added, and stirring was continued for 1.5 hours at 25 to 30°C, whereupon the reaction was terminated. After completion of the reaction, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, the mixture was washed with acidic water containing hydrochloric acid. The mixture was then repeatedly washed with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, it was dropped into warm water maintained at 50 to 80°C to evaporate and remove the solvent, yielding a flaky solid. The resulting solid was filtered and dried at 120°C for 24 hours to yield a white flaky polycarbonate resin. The resulting polycarbonate resin was subjected to various evaluations using the methods described above, and the results are shown in Table 1.

[0066] Comparative Example 2: 304.07 parts by weight of ion-exchanged water and 181.92 parts by weight of 25% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser under a nitrogen atmosphere, and 44.69 parts by weight of PPPBP as a dihydric phenol, 54.06 parts by weight of 2,2-bis(4-hydroxy-3-methylphenyl)propane (manufactured by Honshu Chemical Industry, hereinafter referred to as BPC), and 0.197 parts by weight of hydrosulfite were dissolved therein. 358.97 parts by weight of methylene chloride was then added, and 41.81 parts by weight of phosgene was blown in over 60 minutes at 18-20°C with stirring. Subsequently, 25.99 parts by weight of 25% aqueous sodium hydroxide solution and 1.559 parts by weight of p-tert-butylphenol were added and stirred. During the reaction, 0.082 parts by weight of triethylamine was added, and the mixture was stirred at 25-30°C for 1.5 hours, at which point the reaction was terminated. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, the organic phase was washed with hydrochloric acid-acidified water. After that, the organic phase was repeatedly washed with ion-exchanged water. When the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, the aqueous phase was dropped into warm water maintained at 50-80°C, and the solvent was evaporated to obtain a flaky solid. The obtained solid was filtered and dried at 120°C for 24 hours to obtain a white flaky polycarbonate copolymer. The obtained polycarbonate copolymer was subjected to various evaluations using the methods described above, and the results are shown in Table 1.

[0067] [Comparative Example 3] 94.76 parts by weight of ion-exchanged water and 56.70 parts by weight of 25% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser under a nitrogen atmosphere, and 7.96 parts by weight of PPPBP as a dihydric phenol, 18.47 parts by weight of BPA, and 0.016 parts by weight of hydrosulfite were dissolved therein. 111.87 parts by weight of methylene chloride was then added, and 13.03 parts by weight of phosgene was blown in over 60 minutes at 18 to 20 ° C. with stirring. 8.10 parts by weight of 25% aqueous sodium hydroxide solution and 0.486 parts by weight of p-tert-butylphenol were then added and stirred. During the reaction, 0.026 parts by weight of triethylamine was added, and the reaction was terminated after stirring at 25 to 30 ° C. for 1.5 hours. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, the mixture was washed with acidic water containing hydrochloric acid. The mixture was then repeatedly washed with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, it was dropped into warm water maintained at 50 to 80°C to evaporate and remove the solvent, yielding a flaky solid. The resulting solid was filtered and dried at 120°C for 24 hours to yield a white flaky polycarbonate copolymer. The resulting polycarbonate copolymer was subjected to various evaluations using the methods described above, and the results are shown in Table 1.

[0068] Comparative Example 4: 94.76 parts by weight of ion-exchanged water and 56.70 parts by weight of 25% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser under a nitrogen atmosphere, and 31.43 parts by weight of TMC as a dihydric phenol and 0.063 parts by weight of hydrosulfite were dissolved therein. Then, 111.87 parts by weight of methylene chloride was added, and 13.03 parts by weight of phosgene was blown in over 60 minutes at 18 to 20°C with stirring. Subsequently, 8.10 parts by weight of 25% aqueous sodium hydroxide solution and 0.486 parts by weight of p-tert-butylphenol were added and stirred. During the reaction, 0.026 parts by weight of triethylamine was added, and stirring was continued for 1.5 hours at 25 to 30°C, whereupon the reaction was terminated. After completion of the reaction, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, the mixture was washed with acidic water containing hydrochloric acid. The mixture was then repeatedly washed with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, it was dropped into warm water maintained at 50 to 80°C to evaporate and remove the solvent, yielding a flaky solid. The resulting solid was filtered and dried at 120°C for 24 hours to yield a white flaky polycarbonate resin. The resulting polycarbonate resin was subjected to various evaluations using the methods described above, and the results are shown in Table 1.

[0069] Comparative Example 5: 94.76 parts by weight of ion-exchanged water and 56.70 parts by weight of 25% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser under a nitrogen atmosphere. 11.00 parts by weight of TMC as a dihydric phenol, 15.00 parts by weight of BPA, and 0.022 parts by weight of hydrosulfite were dissolved therein. 111.87 parts by weight of methylene chloride was then added, and 13.03 parts by weight of phosgene was blown in over 60 minutes at 18-20°C with stirring. Subsequently, 8.10 parts by weight of 25% aqueous sodium hydroxide solution and 0.486 parts by weight of p-tert-butylphenol were added and stirred. During the reaction, 0.026 parts by weight of triethylamine was added, and the reaction was terminated after stirring at 25-30°C for 1.5 hours. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, the mixture was washed with acidic water containing hydrochloric acid. The mixture was then repeatedly washed with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, it was dropped into warm water maintained at 50 to 80°C to evaporate and remove the solvent, yielding a flaky solid. The resulting solid was filtered and dried at 120°C for 24 hours to yield a white flaky polycarbonate copolymer. The resulting polycarbonate copolymer was subjected to various evaluations using the methods described above, and the results are shown in Table 1.

[0070]

[0071] The polycarbonate copolymer of the present invention exhibits little dimensional change due to heat or water absorption and has excellent heat resistance, and therefore can be used in electrical and electronic parts such as connectors, switches, sockets, sensor cases, and flexible films that are used in high-temperature environments.

Claims

1. A structural unit (A) represented by the following formula (1), and 【Chemistry 1】 (In formula (1), R １ , R ２ and R ３ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms; R ４ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl-substituted alkyl group having 7 to 13 carbon atoms, and n and m each independently represent an integer of 1 to 4. Structural unit (B) represented by the following formula (2): 【Chemistry 2】 (In formula (2), X represents a group that bonds with a carbon atom to form an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have a substituent.) A polycarbonate copolymer containing 70 mol % or more of the above structural units relative to all structural units, wherein the proportion of structural units (A) in all structural units is 10 to 90 mol %.

2. 2. The polycarbonate copolymer according to claim 1, wherein the proportion of the structural unit (B) in all structural units is 10 to 90 mol %.

3. The polycarbonate copolymer according to claim 1, which has a glass transition temperature of 200 to 280°C.

4. 2. The polycarbonate copolymer according to claim 1, which has a linear expansion coefficient of 40 to 60 ppm / °C.

5. 2. The polycarbonate copolymer according to claim 1, which has a saturated water absorption of 2.40% or less.

6. A molded article obtained by injection molding the polycarbonate copolymer according to any one of claims 1 to 5.

7. A sheet or film obtained by extrusion molding the polycarbonate copolymer according to any one of claims 1 to 5.

8. An electric / electronic part using the molded product according to claim 6.

9. An electrical or electronic component using the sheet or film described in claim 7.

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