Polycarbonate resin and molded articles made therefrom

Abstract

To provide a polycarbonate resin that has superior optical properties and heat resistance as well as high hardness, and to provide a molded article composed of the same.SOLUTION: A polycarbonate resin includes a constitutional unit represented by a following formula (1) (where R1 is an optionally substituted alicyclic group or an optionally substituted aliphatic group, and L1 and L2 independently represent a divalent linking group).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polycarbonate resin and a molded product made therefrom.

Background Art

[0002] Polycarbonate resins are excellent in transparency, impact resistance, heat resistance, and dimensional stability, and are used as engineering plastics in a wide range of fields such as casings for electrical and electronic equipment, automotive interior and exterior parts, building materials, furniture, musical instruments, and sundries. Further, compared with inorganic glass, it has a low specific gravity and can be lightweight, and has excellent productivity, so it is used for window applications such as automobiles.

[0003] In recent years, due to the movement to reduce environmental impact, resins with a large amount of aliphatic components have been studied in all fields such as optical resins, and polycarbonates having a spiro ring structure such as spiroglycol and the diols described in Patent Document 1 have been proposed.

[0004] However, resins with a large amount of aliphatic components generally have problems in heat resistance with a low glass transition temperature compared to aromatic resins, and also have problems in optical properties such as a decrease in refractive index. Further, the hardness decreases compared to aromatic resins. Therefore, it has been desired to develop a resin with a large amount of aliphatic components that has a higher glass transition temperature and heat resistance than conventional aliphatic resins and realizes a high refractive index and high hardness.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] The problem that this invention aims to solve is to provide a polycarbonate resin and molded articles made therefrom that have excellent optical properties and heat resistance, as well as high hardness. [Means for solving the problem]

[0007] The inventors of this invention conducted extensive research to achieve this objective and, as a result, discovered that a polycarbonate resin having a specific structure can solve the aforementioned problem, leading to the present invention. That is, the present invention is as follows.

[0008] <<Aspect 1>> A polycarbonate resin containing the constituent units represented by the following formula (1). [ka] (In the formula, R 1 L represents an optionally substituted alicyclic group or an optionally substituted aliphatic group. 1 and L 2 Each of these independently represents a divalent linking group.

[0009] <<Aspect 2>> The polycarbonate resin according to embodiment 1, wherein the constituent unit represented by formula (1) accounts for 5 mol% to 100 mol% of the total constituent units that make up the polycarbonate resin. <<Aspect 3>> In the above equation (1), R 1 A polycarbonate resin according to embodiment 1 or 2, wherein the polycarbonate resin comprises a cyclohexane skeleton. <<Aspect 4>> A polycarbonate resin according to any one of embodiments 1 to 3, wherein the constituent unit represented by formula (1) is at least one constituent unit selected from the constituent units represented by the following formulas (2) and (3). [ka] (L 1 and L 2 Each of these independently represents a divalent linking group. [ka] (L 1 and L 2 each independently represents a divalent linking group.)

[0010] ≪Aspect 5≫ The polycarbonate resin according to any one of Aspects 1 to 4, further comprising a structural unit represented by the following formula (4). [Chemical formula] (In formula (4), R 2 and R 3 are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and L 3 and L 4 each independently represents a divalent linking group, and m and n each independently represent 0 or 1.)

[0011] ≪Aspect 6≫ The polycarbonate resin according to any one of Aspects 1 to 5, having an indentation hardness measured in accordance with ISO / TS 19278 of 200 to 450 (N / mm 2 ). ≪Aspect 7≫ The polycarbonate resin according to any one of Aspects 1 to 6, having a refractive index of 1.450 to 1.650. ≪Aspect 8≫ The polycarbonate resin according to any one of Aspects 1 to 7, having an Abbe number of 20 to 65. ≪Aspect 9≫ The polycarbonate resin according to any one of Aspects 1 to 8, having a glass transition temperature of 120 to 180 °C. ≪Aspect 10≫ The polycarbonate resin according to any one of Aspects 1 to 9, having a specific viscosity of 0.12 to 0.45. ≪Aspect 11≫ A molded article obtained by injection molding the polycarbonate resin according to any one of Aspects 1 to 10. ≪Aspect 12≫ A sheet or film obtained by extrusion molding the polycarbonate resin according to any one of Aspects 1 to 10. <<Aspect 13>> An optical component formed by injection molding a polycarbonate resin according to any one of embodiments 1 to 10. <<Aspect 14>> An optical component as described in embodiment 13, which is an optical lens. [Effects of the Invention]

[0012] The polycarbonate resin of the present invention is a polycarbonate resin having imide bonds, and it is now possible to provide a novel polycarbonate resin with beneficial properties. In particular, by successfully introducing imide bonds into the repeating aliphatic units, it became possible to improve optical properties such as refractive index, as well as hardness and heat resistance. [Brief explanation of the drawing]

[0013] [Figure 1] This is the 1H NMR spectrum of 2,2'-bis(2-hydroxyethyl)dodecahydro-1H,1'H-[5,5'-biisoindole]-1,1',3,3'(2H,2'H)-tetraone obtained in Reference Example 1. [Figure 2] This is the 1H NMR spectrum of 2,6-bis(2-hydroxyethyl)hexahydropyrrolo[3,4-f]isoindole-1,3,5,7(2H,6H)-tetraone obtained in Reference Example 2. [Figure 3] This is the 1H NMR spectrum of the polycarbonate resin obtained in Example 1. [Figure 4] This is the 1H NMR spectrum of the polycarbonate resin obtained in Example 2. [Figure 5] This is the 1H NMR spectrum of the polycarbonate resin obtained in Example 3. [Figure 6] This is a test force-depth graph of the polycarbonate resins of Example 3 and Comparative Examples 2-3. [Modes for carrying out the invention]

[0014] The present invention will be described in more detail.

[0015] <Polycarbonate resin> The polycarbonate resin of the present invention is a polycarbonate resin that includes a constituent unit represented by the following formula (1).

[0016] [ka] (In the formula, R 1 L represents an optionally substituted alicyclic group or an optionally substituted aliphatic group. 1 and L 2 Each of these independently represents a divalent linking group.

[0017] In the above equation (1), R 1 represents an optionally substituted alicyclic group or an optionally substituted aliphatic group, and examples of structures preferably include those represented by (1-a) below, R 1 The four internal bonding positions can be joined at any position.

[0018] [ka]

[0019] Of these, it is preferable that the constituent unit contains a cyclohexane skeleton from the viewpoint of stability, and it is even more preferable that it has at least one constituent unit selected from a constituent unit containing a bicyclohexyl skeleton (formula (2) below) and a constituent unit containing a cyclohexane skeleton (formula (3) below).

[0020] [ka] (L 1 and L 2 Each of these independently represents a divalent linking group. [ka] (L 1 and L 2 Each of these independently represents a divalent linking group.

[0021] In the above formula (1), L 1 , L 2 Each of these independently represents a divalent linking group, preferably a linear or branched alkylene group having 2 to 12 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms (ethylene group, n-propylene group, isopropylene group, n-butylene group), and even more preferably an ethylene group. 1 , L 2 The glass transition temperature (Tg) of polycarbonate resin can be adjusted by adjusting the length of the linking group.

[0022] The polycarbonate resin of the present invention is obtained by reacting a dihydroxy compound with a carbonate precursor.

[0023] Transesterification reactions using, for example, diester carbonate as a carbonate precursor are carried out by heating and stirring a predetermined proportion of aromatic dihydroxy components with the diester carbonate 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 usually in the range of 120 to 300°C. The reaction is completed by reducing the pressure from the beginning and distilling off the resulting alcohol or phenol. A catalyst commonly used in transesterification reactions can also be used to accelerate the reaction. Examples of diester carbonates 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.

[0024] The polycarbonate resin of the present invention comprises a polyester carbonate copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. The aliphatic difunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Examples of preferred aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanediic acid), dodecanediic acid, tetradecanediic acid, octadecanediic acid, and eicosanedioic acid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These carboxylic acids may be copolymerized to the extent that they do not impede the objective.

[0025] In the polycarbonate resin of the present invention, which contains a constituent unit represented by formula (1), the constituent unit represented by formula (1) may be contained in an amount of 5 mol% or more, 10 mol% or more, 15 mol% or more, 20 mol% or more, or 100 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, or 40 mol% or less among all the constituent units constituting the polycarbonate resin. In the polycarbonate resin of the present invention, the constituent unit represented by formula (1) may be contained in an amount of preferably 5 mol% or more to 100 mol%, more preferably 10 mol% or more to 80 mol%, even more preferably 15 mol% or more to 60 mol%, and particularly preferably 20 mol% or more to 50 mol% among all the constituent units constituting the polycarbonate resin. It is preferable that the proportion of the constituent unit represented by formula (1) be within the above range because it provides an excellent balance of optical properties, high hardness, heat resistance, and moldability.

[0026] The polycarbonate resin of the present invention may further contain a constituent unit represented by the following formula (4).

[0027] [ka] (In formula (4), R 2 and R 3 L represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, either identical or different. 3 and L 4Each of these independently represents a divalent linking group, and m and n independently represent either 0 or 1.

[0028] In equation (4) above, R 2 and R 3 Each of these independently represents a hydrocarbon group having 1 to 10 carbon atoms, which may contain a hydrogen atom or an aromatic group. Hydrogen atoms, methyl groups, phenyl groups, and naphthyl groups are preferred, hydrogen atoms, methyl groups, and phenyl groups are more preferred, and hydrogen atoms and methyl groups are even more preferred.

[0029] In the above formula (4), L 3 , L 4 Each of these independently represents a divalent linking group, which is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and even more preferably an ethylene group. 3 , L 4 The glass transition temperature (Tg) of the resin can be adjusted by adjusting the length of the linking group.

[0030] Furthermore, the polycarbonate resin of the present invention may contain additives such as heat stabilizers, plasticizers, light stabilizers, polymerization metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, antioxidants, ultraviolet absorbers, and mold release agents, as needed.

[0031] <Physical properties of polycarbonate resin> The polycarbonate resin of the present invention has an indentation hardness of 200-450 (N / mm²) as measured in accordance with ISO / TS 19278. 2 Preferably, it is 210-440 (N / mm²). 2 It is more preferable that the value is 220-430 (N / mm²). 2 It is even more preferable that the value is 230-420 (N / mm²). 2 It is even more preferable that the temperature is 235-410 (N / mm²). 2 It is particularly preferable that the value be 240-400 (N / mm²). 2 ) is most preferable. If the indentation hardness is within the above range, the molded product will have excellent scratch resistance.

[0032] The refractive index of the polycarbonate resin of the present invention, when measured at a temperature of 20°C and a wavelength of 587.56 nm, may be 1.450 or higher, 1.460 or higher, 1.470 or higher, 1.480 or higher, 1.490 or higher, or 1.500 or higher, and may also be 1.650 or lower, 1.640 or lower, 1.630 or lower, 1.620 or lower, 1.610 or lower, or 1.600 or lower.

[0033] The refractive index of the polycarbonate resin of the present invention is preferably 1.450 to 1.650, more preferably 1.460 to 1.645, even more preferably 1.470 to 1.640, particularly preferably 1.480 to 1.635, and most preferably 1.490 to 1.630.

[0034] The Abbe number of the polycarbonate resin of the present invention may be 20 or more, 21 or more, 22 or more, 23 or more, 24 or more, or 25 or more, and may be 65 or less, 64 or less, 63 or less, 62 or less, 61 or less, 60 or less, or 59 or less. The Abbe number (νd) is preferably 20 to 65, more preferably 22 to 60, and even more preferably 23 to 50.

[0035] Here, the Abbe number is calculated using the following formula based on the refractive index at a temperature of 20°C and wavelengths of 486.13 nm, 587.56 nm, and 656.27 nm. νd=(nd-1) / (nF-nC) nd: refractive index at a wavelength of 587.56 nm, nF: Refractive index at a wavelength of 486.13 nm. nC: This refers to the refractive index at a wavelength of 656.27 nm.

[0036] The polycarbonate resin of the present invention may have a glass transition temperature (Tg) of 120°C or higher, 125°C or higher, 130°C or higher, 135°C or higher, or 140°C or higher, and may also have a glass transition temperature (Tg) of 180°C or lower, 175°C or lower, 170°C or lower, 165°C or lower, or 160°C or lower. A Tg of 120-180°C is preferred, 125-170°C is more preferred, 130-165°C is even more preferred, and 135-160°C is particularly preferred. A glass transition temperature within the above range is preferable because it provides an excellent balance between heat resistance and moldability.

[0037] The specific viscosity of the polycarbonate resin of the present invention is preferably 0.12 to 0.45, more preferably 0.14 to 0.42, and even more preferably 0.16 to 0.40. A specific viscosity within the above range is preferable because it provides an excellent balance between moldability and mechanical strength.

[0038] The specific viscosity is measured by the specific viscosity (η) of a solution prepared by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20°C. SP The viscometer is used to measure the viscometer and calculate the value from the following formula. Specific viscosity (η SP ) = (t-t0) / t0 [t0 is the number of seconds for the methylene chloride to fall, and t is the number of seconds for the sample solution to fall.]

[0039] <Raw materials for polycarbonate resin> (The diol component of formula (1)) The diol component that forms the raw material for formula (1) is mainly the diol component represented by the following formula (a), and may be used alone or in combination of two or more types.

[0040] [ka]

[0041] In equation (a), R 1 , L 1 and L 2 R in equation (1) 1 , L1 and L 2 This is synonymous with the same thing, and the preferred range is also similar. The diol represented by formula (a) is obtained by reacting an amino alcohol represented by the general formula: H2N-L-OH (wherein L represents a chain-like or branched alkylene group having 2 to 12 carbon atoms) with a tetracarboxylic dianhydride represented by the following formula (5).

[0042] [ka] (In formula (5), R 4 (This indicates an optionally substituted alicyclic group or an optionally substituted aliphatic group.) R in formula (5) 4 For example, R in equation (1) above. 1 This is synonymous with the same thing, and the preferred range is also similar.

[0043] In the above formula (a), L 1 , L 2 is an amino alcohol residue used in the synthesis of formula (a) above. Among them, L 1 , L 2 It is preferable that the residue is an amino alcohol residue represented by the general formula: H2N-L-OH (wherein L represents a linear or branched alkylene group having 2 to 12 carbon atoms) (i.e., a linear or branched alkylene group having 2 to 12 carbon atoms) from the viewpoint of ease of synthesis of the diol compound, toughness of the final diol compound and economic efficiency, and it is more preferable that it is an alkylene group having 2 to 4 carbon atoms (ethylene group, n-propylene group, isopropylene group, n-butylene group).

[0044] (Components of formula (4) above) The polycarbonate resin of the present invention may further have the constituent units of formula (4), and the dihydroxy compound components that serve as raw materials for formula (4) are shown below. These may be used individually or in combination of two or more.

[0045] The dihydroxy compound component that serves as a raw material for formula (4) of the present invention is 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9 Examples include bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene, and 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, with 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene being particularly preferred. These may be used individually or in combination of two or more.

[0046] <Manufacturing method> (Method of manufacturing polycarbonate resin) The polycarbonate resin of the present invention is obtained by a known reaction method, for example, by reacting a dihydroxy compound component with a carbonate precursor by melt polymerization. When producing the polycarbonate resin, catalysts, end-terminating agents, antioxidants, etc., may be used as needed.

[0047] (Method for manufacturing polyester carbonate resin) When the polycarbonate resin of the present invention is a polyester carbonate resin, it can be produced by reacting a dihydroxy compound component and a dicarboxylic acid or its ester-forming derivative with a carbonate precursor such as a carbonate ester. The polymerization method can be the same as that for the polycarbonate resin described above.

[0048] <Polycarbonate resin molded products, sheets, or films> The polycarbonate resin of the present invention can be used to obtain the desired molded product by methods such as injection molding, injection compression molding, injection blow molding, two-color molding, extrusion molding, or blow molding.

[0049] The polycarbonate resin of the present invention is not particularly limited in its manufacturing method. For example, molded products of various shapes can be obtained by injection molding, and sheet-like and film-like molded products can also be obtained by methods such as molten extrusion and solution casting (casting method). A specific method of molten extrusion involves, for example, supplying a fixed amount of polycarbonate resin to an extruder, heating and melting it, extruding the molten resin in a sheet-like form onto a mirror-polished roll from the tip of a T-die, taking it up while cooling it with multiple rolls, and cutting or winding it to an appropriate size once it has solidified. A specific method of solution casting involves, for example, casting a solution (concentration 5% to 40%) of polycarbonate resin dissolved in methylene chloride from a T-die onto a mirror-polished stainless steel plate, peeling the sheet while passing it through an oven with gradually controlled temperatures, removing the solvent, and then cooling and winding it up.

[0050] Sheets and films extruded from polycarbonate resin can also be formed into laminates. Any method can be used to manufacture the laminates, but the thermocompression method or co-extrusion method is particularly preferred. Any method can be used for thermocompression, but for example, a method of thermocompressing polycarbonate resin sheets with a laminating machine or press machine, or a method of thermocompression immediately after extrusion is preferred, and a method of continuously thermocompressing the polycarbonate resin sheets immediately after extrusion is particularly industrially advantageous.

[0051] Furthermore, the sheets and films extruded from the polycarbonate resin of the present invention have excellent scratch resistance, heat resistance, and moldability, and therefore do not require coating treatment and can be used for various display devices such as interior lighting lamp lenses, display meter covers, meter dials, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, head-up displays, protective parts, and light-transmitting parts.

[0052] <Optical components> The optical component of the present invention is preferably formed from the above-mentioned polycarbonate resin by injection molding. Such optical components are not particularly limited as long as they are for optical applications in which the above-mentioned polycarbonate resin is useful, but examples include optical lenses, optical discs, transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, optical films, substrates, optical filters, hard coat films, and the like. [Examples]

[0053] The present invention will be described in more detail by the following examples, but the present invention is not limited thereto.

[0054] ≪Evaluation Method≫ <Compounds containing imide bonds> <nmr> The obtained diol compound was processed using JEOL Ltd.'s JNM-ECZ400S. 1 The structure was identified by 1H NMR measurement. DMSO-d6 was used as the solvent.

[0055] <Purity> Measurements were performed using an Agilent Technologies single quadrupole GC / MS 5977B under the following conditions. In the examples, unless otherwise specified, purity (%) is the area percentage value corrected for excluding the solvent in the GC / MS. (GC) Column: DB-1 (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm) Injection volume: 1μl Injection method: Split ratio 40:1 Inlet temperature: 280℃ Oven: 60°C - 10°C / minute - 280°C (28 minutes) Carrier gas: He, linear velocity 36.6 cm / s (MS) Ion source temperature: 230℃ Ionization mode: EI 70eV Measurement range: m / z 33-700

[0056] <Polycarbonate resin> <Copolymerization ratio> The obtained polycarbonate resin was processed using JEOL Ltd.'s JNM-ECZ400S. 1 The composition ratio of the polycarbonate resin was calculated by 1H NMR measurement. CDCl3 was used as the solvent.

[0057] <Specific viscosity> (Specific viscosity (η SP )) The specific viscosity (η) is calculated using the following formula. SP The viscosity was determined using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of the sample in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP ) = (t-t0) / t0 [t0 is the number of seconds for the methylene chloride to fall, and t is the number of seconds for the sample solution to fall.]

[0058] <Hardness characteristics> (Hit level) Based on ISO / TS 19278, a dynamic ultra-micro hardness tester (Shimadzu Corporation, model DUH-210S) was used to measure the relationship between load and indentation depth in real time on the surface of a resin plate, and the indentation hardness (N / mm²) was determined. 2 ) was measured. (Measurement conditions) Measuring indenter: Berkovich indenter (made of diamond) Test force: 500mN Minimum test force: 4.9 mN Loading / unloading time: 30sec Load holding time: 40sec Unloading holding time: 0sec Number of tests: 5 (Method for calculating indentation hardness) Indentation hardness (Hit) measures the resistance to semi-permanent deformation or damage. Indentation hardness is calculated using the following formula: Hit = F max / Ap F max : Maximum test force Ap: Projected area where the indenter and the test specimen are in contact. Ap = 23.96 × hc 2 (In the case of a triangular pyramidal indenter (115°)) hc=h max -ε(h max -hr) ε = 3 / 4 (in the case of a triangular pyramid) hr: F of the force-depth curve max The intercept where the tangent line to the unloading curve intersects the depth axis.

[0059] <Optical properties> (Refractive index) A 3mm thick polycarbonate resin test specimen was prepared by compression molding, polished, and then the refractive index nd (587.56nm) at 20°C was measured using a Shimadzu KPR-2000 precision refractometer. (Abbe number) The measurement wavelengths for the Abbe number are 486.13 nm, 587.56 nm, and 656.27 nm. The calculation was performed using the following formula based on the folding rate. νd=(nd-1) / (nF-nC) nd: refractive index at a wavelength of 587.56 nm, nF: Refractive index at a wavelength of 486.13 nm. nC: This refers to the refractive index at a wavelength of 656.27 nm.

[0060] <Thermal properties> (Glass transition temperature (Tg)) The obtained polycarbonate resin was measured using a TA Instruments Discovery SDT650 differential thermal and thermogravimetric analyzer at a heating rate of 20°C / min. Approximately 5 mg of sample was used for the measurement.

[0061] [Reference Example 1] Synthesis of IM-1 Under a nitrogen atmosphere, 12.50 g of dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride (hereinafter sometimes abbreviated as HBPDA) and 200 ml of DMF (super-dehydrated) were charged into a flask equipped with a stirrer, condenser, and thermometer. The mixture was stirred at 90°C under a nitrogen atmosphere to completely dissolve the HBPDA in the DMF. Then, 5.98 ml of 2-aminoethanol was added to a dropping funnel and added dropwise over 30 minutes. After the addition was complete, the temperature was raised to 130°C and the reaction was carried out at 130°C for 8 hours. After the reaction was complete, the DMF was removed by distillation using an evaporator, and then recrystallized with methanol to obtain 4.44 g of crystals of 2,2'-bis(2-hydroxyethyl)dodecahydro-1H,1'H-[5,5'-biisoindole]-1,1',3,3'(2H,2'H)-tetraone (hereinafter sometimes abbreviated as IM-1) (yield 28%). The purity was 99.53%.

[0062] [Reference Example 2] Synthesis of IM-2 Under a nitrogen atmosphere, 5.00 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (hereinafter sometimes abbreviated as HPMDA) and 50 ml of DMF (super-dehydrated) were charged into a flask equipped with a stirrer, condenser, and thermometer. The mixture was stirred at 30°C under a nitrogen atmosphere to completely dissolve the HPMDA in the DMF. Then, 3.27 ml of 2-aminoethanol was added dropwise to a dropping funnel and added over 30 minutes. After the addition was complete, the temperature was raised to 110°C and the reaction was carried out at 110°C for 2 hours. After the reaction was complete, the DMF was removed by distillation using an evaporator, and then recrystallization was performed using acetone as a good solvent and hexane as a poor solvent to obtain 6.55 g of crystals of 2,6-bis(2-hydroxyethyl)hexahydropyrrolo[3,4-f]isoindole-1,3,5,7(2H,6H)-tetraone (hereinafter sometimes abbreviated as IM-2) (yield 95%). The purity was 99.42%.

[0063] [Example 1] 3.9 parts by mass (20 ml%) of IM-1 obtained in Reference Example 1, 17.54 parts by mass (80 ml%) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter sometimes abbreviated as BPEF), 10.82 parts by mass (101 ml%) of diphenyl carbonate (hereinafter sometimes abbreviated as DPC), and 8.51 × 10¹⁶ of tetrabutoxytitanium at a concentration of 100 mmol / L as a catalyst. ―4 Part of mass (5.00×10 ―3 %) was added and heated to 200°C under a nitrogen atmosphere to melt. Then, the pressure was adjusted to 20kPa over 5 minutes. The temperature was raised to 250°C at a heating rate of 60°C / hr, and after the phenol leaching rate reached 70%, the pressure was reduced to 60kPa / hr and the polymerization reaction was carried out until the predetermined power was reached. After the reaction was complete, the resin was removed from the flask. The obtained polycarbonate resin was then processed. 1 Analysis by 1H NMR confirmed that the IM-1 component was introduced at a concentration of 20 ml relative to the total monomers, and the BPEF component at a concentration of 80 ml relative to the total monomers. The copolymerization ratio, specific viscosity, refractive index, Abbe number, Tg, and indentation hardness were evaluated using this polycarbonate resin, and the results are shown in Table 1.

[0064] [ka]

[0065] [Example 2] A polycarbonate resin was manufactured in the same manner as in Example 1, except that IM-2 obtained in Reference Example 2 was used instead of IM-1. The copolymerization ratio, specific viscosity, refractive index, Abbe number, Tg, and indentation hardness of this polycarbonate resin were evaluated, and the results are shown in Table 1. IM-2 has the following chemical structure.

[0066] [ka]

[0067] [Comparative Example 1] The use of spiroglycol (hereinafter sometimes abbreviated as SPG) instead of IM-1, and the use of 4.20 × 10¹⁶ sodium bicarbonate at a concentration of 60 mmol / L as a catalyst, were significant factors. -4 Part of mass (5.00×10 -3 %), tetramethylammonium hydroxide at a concentration of 274 mmol / L: 2.72 × 10 -3 Part of mass (2.99×10 -2 A polycarbonate resin was manufactured in the same manner as in Example 1, except that a %) was used. The copolymerization ratio, specific viscosity, refractive index, Abbe number, Tg, and indentation hardness of the polycarbonate resin were evaluated, and the results are shown in Table 1. The SPG has the following structure.

[0068] [ka]

[0069] [Example 3] A polycarbonate resin was produced in the same manner as in Example 2, except that the copolymerization ratio was changed. The copolymerization ratio, specific viscosity, refractive index, Abbe number, Tg, and indentation hardness of this polycarbonate resin were evaluated, and the results are shown in Table 1.

[0070] [Comparative Example 2] A polycarbonate resin was manufactured in the same manner as in Comparative Example 1, except that the copolymerization ratio was changed. The copolymerization ratio, specific viscosity, refractive index, Abbe number, Tg, and indentation hardness of this polycarbonate resin were evaluated, and the results are shown in Table 1.

[0071] [Comparative Example 3] A polycarbonate resin was produced in the same manner as in Comparative Example 2, except that (3,12-diethyl-1,5,10,14-tetraoxadispiro[5.2.59.26]hexadecane-3,12-diyl)dimethanol (hereinafter sometimes abbreviated as DESM) was used instead of SPG. The copolymerization ratio, specific viscosity, refractive index, Abbe number, Tg, and indentation hardness were evaluated using this polycarbonate resin, and the results are shown in Table 1. DESM has the following structure.

[0072] [ka]

[0073] [Table 1]

[0074] The polycarbonate resins obtained in Examples 1 and 2 have a higher refractive index (nd) and higher indentation hardness than Comparative Example 1, which uses the conventional aliphatic diol compound spiroglycol. This indicates that they have superior not only optical properties but also scratch resistance. Furthermore, they have a high Tg of 140°C or higher, demonstrating excellent heat resistance.

[0075] The polycarbonate resin obtained in Example 3 has a higher refractive index and indentation hardness compared to Comparative Examples 2 and 3. This indicates that, due to the presence of imide bonds, it exhibits superior not only optical properties but also scratch resistance compared to conventional aliphatic diol compounds. Furthermore, its high Tg of 140°C or higher demonstrates excellent heat resistance. [Industrial applicability]

[0076] The polycarbonate resin of the present invention has a high refractive index despite having a high aliphatic component content, and also exhibits excellent heat resistance, making it suitable for use as an optical material. Specifically, it can be used as an optical component such as optical lenses, prisms, optical discs, transparent conductive substrates, optical cards, sheets, films, optical fibers, optical films, optical filters, and hard coat films, and is particularly useful as an optical lens material.

[0077] Furthermore, because the polycarbonate resin of the present invention has excellent scratch resistance, heat resistance, and moldability, it does not require coating treatment and can be used for various display devices such as interior lighting lamp lenses, display meter covers, meter dials, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, head-up displays, protective parts, and light-transmitting parts.< / nmr>

Claims

1. A polycarbonate resin comprising a constituent unit represented by the following formula (1) and a constituent unit represented by the following formula (4). 【Chemistry 1】 (In the formula, R １ L represents an optionally substituted alicyclic group or an optionally substituted aliphatic group. １ and L ２ Each of these independently represents a divalent linking group. 【Chemistry 2】 (In formula (4), R2 and R3 are the same or different, representing a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; L3 and L4 each independently represent a divalent linking group; and m and n each independently represent 0 or 1.)

2. The polycarbonate resin according to claim 1, wherein the constituent unit represented by formula (1) accounts for 5 mol% to 100 mol% of the total constituent units that make up the polycarbonate resin.

3. In the above formula (1), R １ The polycarbonate resin according to claim 1, wherein the cyclohexane skeleton is included.

4. The polycarbonate resin according to claim 1, wherein the constituent unit represented by formula (1) is at least one constituent unit selected from the constituent units represented by the following formulas (2) and (3). 【Transformation 3】 (L １ and L ２ Each of these independently represents a divalent linking group. 【Chemistry 4】 (L １ and L ２ Each of these independently represents a divalent linking group.

5. The polycarbonate resin according to claim 1, having an indentation hardness measured in accordance with ISO / TS 19278 of 200 to 450 (N / mm ２ ).

6. The polycarbonate resin according to claim 1, wherein the refractive index is 1.450 to 1.

650.

7. The polycarbonate resin according to claim 1, wherein the Abbe number is 20 to 65.

8. The polycarbonate resin according to claim 1, wherein the glass transition temperature is 120 to 180°C.

9. The polycarbonate resin according to claim 1, wherein the specific viscosity is 0.12 to 0.

45.

10. A molded article obtained by injection molding a polycarbonate resin according to any one of claims 1 to 9.

11. A sheet or film obtained by extruding a polycarbonate resin according to any one of claims 1 to 9.

12. An optical component formed by injection molding of a polycarbonate resin according to any one of claims 1 to 9.

13. The optical component according to claim 12, which is an optical lens.

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