Polycarbonate resin and its manufacturing method

Abstract

The present specification relates to a polycarbonate resin having a relaxation time of 2 to 15 seconds at 250° C. and a residual phenol content of 3000 ppm or less.

Description

[Technical Field]

[0001] This application claims the benefit of the filing date of Korean Patent Application No. 10-2022-0127150 filed with the Korean Intellectual Property Office on October 5, 2022, and Korean Patent Application No. 10-2022-0141544 filed with the Korean Intellectual Property Office on October 28, 2022, the entire contents of which are incorporated herein by reference.

[0002] The present specification relates to a polycarbonate resin and a method for producing the same. [Background technology]

[0003] Optical glass or optical resin is used as an optical material for plastic optical products such as various lenses, prisms, optical disk substrates, optical fibers, and optical films. Optical glass has excellent heat resistance, transparency, dimensional stability, and chemical resistance, but has problems such as high material costs, poor moldability, and low productivity.

[0004] On the other hand, optical materials containing optical resins can be mass-produced by injection molding. Examples of optical resins that are used include polycarbonate resins, polyester resins, and polyester-carbonate resins.

[0005] However, the optical resins have drawbacks such as insufficient fluidity and poor processability. Therefore, it may be difficult to apply them to injection molding of articles that require the aforementioned precision. In order to apply the resins to injection molding, the molding temperature and mold temperature must be increased, which lengthens the molding cycle, increases molding costs, or causes deterioration of the resin and color during molding.

[0006] To solve this problem, methods for improving the fluidity of resins during molding of optical materials include lowering the viscosity or weight average molecular weight, adding low molecular weight oligomers, and broadening the molecular weight distribution, but these methods tend to reduce the excellent physical properties that resins inherently possess, such as heat resistance and impact resistance.

[0007] Therefore, efforts are ongoing to improve processability while retaining the advantages of resins. Summary of the Invention [Problem to be solved by the invention]

[0008] An object of one embodiment of the present specification is to provide a polycarbonate resin and a method for producing the same.

[0009] Another embodiment of the present specification aims to provide a polycarbonate resin composition containing the above-mentioned polycarbonate resin, and a molded article produced from the polycarbonate resin composition. [Means for solving the problem]

[0010] One embodiment of the present specification provides a polycarbonate resin having a relaxation time of 2 to 15 seconds at 250° C. and a residual phenol content of 3000 ppm or less.

[0011] One embodiment of the present specification provides a polycarbonate resin having a relaxation time of 1 to 15 seconds at 250°C and a residual phenol content of 3000 ppm or less, the polycarbonate resin comprising a first unit of the following Chemical Formula 1; a second unit of the following Chemical Formula 2; and a third unit of the following Chemical Formula 3: [Chemical formula 1] [ka] In the above Chemical Formula 1, X1 to X4 are the same or different and each independently represents O or S; R1 to R4 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted heteroaryl group; Z1 and Z2 are the same or different and each independently represent a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; R and R are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or are bonded to each other to form a substituted or unsubstituted hydrocarbon ring; R101 and R102 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; r101 is 1 or 2, and when r101 is 2, the two R101 are the same or different from each other; r102 is 1 or 2, and when r102 is 2, the two R102 are the same or different from each other; m and n are each an integer of 0 to 6, p is an integer from 1 to 6; When m, n, and p are each 2 or more, the structures in the parentheses are the same or different from each other, * indicates the site connected to the main chain of the resin. [Chemical formula 2] [ka] In the above Chemical Formula 2, X5 to X8 are the same or different and each independently represents O or S; L1 and L2 are the same or different and each independently represent a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group; R13 and R14 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or are bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; Z3 and Z4 are the same or different and each independently represent a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; m' and n' are each an integer of 0 to 6, p' is an integer from 1 to 6, r13 and r14 are each an integer of 1 to 4, When r13, r14, m', n', and p' are each 2 or more, the structures in the 2 or more brackets are the same or different from each other, * indicates the site connected to the main chain of the resin. [Chemical formula 3] [ka] In the above Chemical Formula 3, X9 to X12 are the same or different and each independently represents O or S; Z5 and Z6 are the same or different and each independently represent a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; R15 and R16 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or are bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; m'' and n'' are each an integer from 0 to 6; p'' is an integer from 1 to 6; r15 and r16 are each an integer of 1 to 6, When r15, r16, m'', n'', and p'' are each 2 or more, the structures in the 2 or more brackets are the same or different from each other, * indicates the site connected to the main chain of the resin.

[0012] Furthermore, one embodiment of the present specification provides a method for producing the aforementioned polycarbonate resin, comprising polymerizing a composition for producing a polycarbonate resin, the composition including: a compound represented by the following Chemical Formula 1a; a compound represented by the following Chemical Formula 2a; a compound represented by the following Chemical Formula 3a; and a polycarbonate precursor. [Chemical formula 1a] [ka] In the above chemical formula 1a, X1 to X4 are the same or different and each independently represents O or S; R1 to R4 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted heteroaryl group; Z1 and Z2 are the same or different and each independently represent a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; R and R are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or are bonded to each other to form a substituted or unsubstituted hydrocarbon ring; R101 and R102 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; r101 is 1 or 2, and when r101 is 2, the two R101 are the same or different from each other; r102 is 1 or 2, and when r102 is 2, the two R102 are the same or different from each other; m and n are each an integer of 0 to 6, When m and n are each 2 or more, the structures in the two or more parentheses may be the same or different from each other, [Chemical formula 2a] [ka] [Chemical formula 3a] [ka] In the above chemical formulas 2a and 3a, X5 to X12 are the same or different and each independently represents O or S; L1 and L2 are the same or different and each independently represent a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group; Z3 to Z6 are the same or different and each independently represent a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; R13 to R16 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or are bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; r13 and r14 are each an integer of 1 to 4, r15 and r16 are each an integer of 1 to 6, m', m'', n', and n'' are each an integer from 0 to 6; When each of r13 to r16, m', m'', n', and n'' is 2 or more, the structures in the 2 or more brackets are the same or different.

[0013] Another embodiment of the present invention provides a polycarbonate resin composition comprising a polycarbonate resin according to the above-described embodiment.

[0014] Another embodiment of the present specification provides a molded article comprising the polycarbonate resin composition according to the above-described embodiment. [Effects of the Invention]

[0015] The polycarbonate resin according to one embodiment of the present specification has a shorter molecular relaxation time than conventional polycarbonate resins, and therefore has a faster cooling time in an injection mold and excellent processability. Furthermore, the polycarbonate resin undergoes less molecular weight reduction during processing and has excellent processing stability.

[0016] By using the polycarbonate resin according to one embodiment of the present specification, it is possible to obtain an excellent optical lens, optical film, optical thin film, optical resin, optical fiber, or LED encap with a small thickness. DETAILED DESCRIPTION OF THE INVENTION

[0017] The present specification will be explained in more detail below.

[0018] The polycarbonate resin according to one embodiment of the present specification has a relaxation time of 2 to 15 seconds at 250° C. and a residual phenol content of 3000 ppm or less.

[0019] One embodiment of the present specification provides a polycarbonate resin having a relaxation time of 1 to 15 seconds at 250°C and a residual phenol content of 3000 ppm or less, the polycarbonate resin comprising a first unit of Chemical Formula 1; a second unit of Chemical Formula 2; and a third unit of Chemical Formula 3.

[0020] According to one embodiment of the present specification, the relaxation time of the polycarbonate resin is 1 to 15 seconds at 250° C. Or, 2 to 15 seconds at 250° C. Specifically, it is 2.5 to 14.5 seconds at 250° C., and more specifically, it is 3.39 to 14.2 seconds.

[0021] When the polycarbonate resin satisfies the relaxation time at the above temperature, the molecular relaxation time is relatively short, resulting in a fast cooling time in the mold during injection molding, a reduced processing load, a shorter time between filling cycles, and a shorter relaxation time, which reduces phenomena such as weld lines, cracks, warpage, birefringence, and undermolding during injection molding.

[0022] The relaxation time according to one embodiment of the present specification can be measured by any method commonly used in the art, and specifically, using a hybrid rheometer (discovery (HR-2)) at 250°C and 0.1 Hz to 100 Hz. A shear force was applied at 250°C until a deformation rate of 30% was reached, and then the force was removed. When the applied shear force reached 1 Pa (=1 N / m 2 The viscoelastic behavior of polymers that occurs at high temperatures (250°C) is measured by measuring the rate at which the shear force returns to 100 Pa. The shear force is maximized and applied to the extent that the molten polymer moves, at which point the stress reaches 100 Pa or more. The stress is then quickly removed and the time it takes for the stress to return to 1 Pa is measured; the time it takes for the stress to return to 1 Pa is the relaxation time.

[0023] In one embodiment of the present specification, the relaxation time is important because, if the resin cools in a mold while retaining residual stress during injection, it can cause problems such as physical damage due to a weak external force. Therefore, when the relaxation time according to one embodiment of the present specification is set, the residual stress is reduced, significantly reducing problems during resin injection molding. However, the longer the relaxation time, the greater the residual stress, making physical damage more likely to occur even with a weak external force.

[0024] When the residual phenol content of the polycarbonate resin according to one embodiment of the present invention is 3,000 ppm or less, the polycarbonate resin undergoes little molecular weight loss during processing and exhibits excellent processing stability. However, if the residual phenol content exceeds the aforementioned range, the molecular weight loss of the polycarbonate resin can cause various problems, such as reduced strength and physical properties, leading to cracking of the injection molded article during processing. Therefore, it is preferable that the residual phenol content be 3,000 ppm or less.

[0025] According to one embodiment of the present specification, the polycarbonate resin has a residual phenol content of 3,000 ppm or less, specifically 10 ppm to 3,000 ppm, 50 ppm to 3,000 ppm, or 100 ppm to 3,000 ppm, more specifically 200 ppm to 2,000 ppm, 200 ppm to 1,200 ppm, or 470 ppm to 720 ppm.

[0026] In this specification, the content (concentration) of residual phenol can be calculated as follows: First, 1.0 g of pellets is dried, and 1 g of resin solids is dissolved in 12 ml of methylene chloride (MC) and 18 ml of methanol (MeOH). The solution is then filtered through a 0.2 μm pore filter and subjected to HPLC / UV analysis to calculate the content of residual phenol (measurement wavelength: 200 μm HPLC, mobile phase A: acetonitrile, mobile phase B: HO, column: Capcellpak C18 (4.6 mm ID × 50 mm, 5 μm), column temperature: 40°C, flow rate: 1 ml / min, injection volume: 5 μl, run time: 10 min).

[0027] In this specification, when a part "comprises" a certain component, this does not mean that it excludes other components, but that it may further include other components, unless otherwise specified.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0029] Although methods and materials similar or equivalent to those described herein may be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, and in the event of a conflict, the present invention, including definitions, will prevail unless a specific passage is recited. It should be noted that the materials, methods, and examples are merely illustrative and not limiting.

[0030] According to one embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa·s to 200 Pa·s at 250° C. When the polycarbonate resin has the high shear viscosity at the above temperature, the processing load is reduced, thereby reducing phenomena such as weld lines, cracks, warpage, birefringence, and unmolded portions during injection molding.

[0031] According to one embodiment of the present specification, the high shear viscosity of the polycarbonate resin is 10 Pa·s to 200 Pa·s at 250°C, preferably 30 Pa·s to 200 Pa·s, more preferably 50 Pa·s to 190 Pa·s, and even more preferably 60.7 Pa·s to 146 Pa·s.

[0032] According to one embodiment of the present specification, the high shear viscosity of the polycarbonate resin is 10 Pa·s to 200 Pa·s at 10 Hz or 63 Hz.

[0033] According to one embodiment of the present specification, the high shear viscosity of the polycarbonate resin is 10 Pa·s to 200 Pa·s at 10 Hz.

[0034] According to one embodiment of the present specification, the high shear viscosity of the polycarbonate resin is 10 Pa·s to 200 Pa·s at 63 Hz.

[0035] According to one embodiment of the present specification, the high shear viscosity of the polycarbonate resin is 10 Pa·s to 200 Pa·s at one or more of 250°C, 10 Hz and 250°C, 63 Hz.

[0036] According to one embodiment of the present specification, the high shear viscosity of the polycarbonate resin is 10 Pa·s to 200 Pa·s at 250°C, 10 Hz and / or 250°C, 63 Hz.

[0037] According to one embodiment of the present specification, the high shear viscosity of the polycarbonate resin is 10 Pa·s to 200 Pa·s at 250°C, 10 Hz and at 250°C, 63 Hz.

[0038] According to one embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa·s to 200 Pa·s at 250°C, 10 Hz or 250°C, 63 Hz.

[0039] According to one embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa·s to 200 Pa·s at 250° C. and 10 Hz.

[0040] According to one embodiment of the present specification, the high shear viscosity of the polycarbonate resin is 10 Pa·s to 200 Pa·s at 250° C. and 63 Hz.

[0041] In this specification, when the polycarbonate resin has the high shear viscosity described above at the above frequency, it has the advantage of being easy to process due to excellent fluidity when processing a thermoplastic polymer using extrusion / injection.

[0042] According to one embodiment of the present specification, the high shear viscosity of the polycarbonate resin is 10 Pa·s to 200 Pa·s at one or more of 250°C, 10 Hz and 250°C, 63 Hz, preferably 30 Pa·s to 200 Pa·s, more preferably 50 Pa·s to 190 Pa·s, and even more preferably 60.7 Pa·s to 146 Pa·s.

[0043] According to one embodiment of the present specification, the high shear viscosity of the polycarbonate resin is 10 Pa·s to 200 Pa·s at 250°C, 10 Hz and / or 250°C, 63 Hz, preferably 30 Pa·s to 200 Pa·s, more preferably 50 Pa·s to 190 Pa·s, and even more preferably 60.7 Pa·s to 146 Pa·s.

[0044] According to one embodiment of the present specification, the high shear viscosity of the polycarbonate resin is 10 Pa·s to 200 Pa·s at 250°C and 10 Hz, preferably 30 Pa·s to 200 Pa·s, more preferably 50 Pa·s to 190 Pa·s, and even more preferably 76.3 Pa·s to 146 Pa·s.

[0045] According to one embodiment of the present specification, the high shear viscosity of the polycarbonate resin is 10 Pa·s to 200 Pa·s at 250°C and 63 Hz, preferably 30 Pa·s to 200 Pa·s, more preferably 50 Pa·s to 190 Pa·s, and even more preferably 60.7 Pa·s to 99.4 Pa·s.

[0046] According to one embodiment of the present specification, the polycarbonate resin includes a first unit of the following Chemical Formula 1; a second unit of the following Chemical Formula 2; and a third unit of the following Chemical Formula 3. [Chemical formula 1] [ka] In the above Chemical Formula 1, X1 to X4 are the same or different and each independently represents O or S; R1 to R4 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted heteroaryl group; Z1 and Z2 are the same or different and each independently represent a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; R and R are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or are bonded to each other to form a substituted or unsubstituted hydrocarbon ring; R101 and R102 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; r101 is 1 or 2, and when r101 is 2, the two R101 are the same or different from each other; r102 is 1 or 2, and when r102 is 2, the two R102 are the same or different from each other; m and n are each an integer of 0 to 6, p is an integer from 1 to 6; When m, n, and p are each 2 or more, the structures in the parentheses are the same or different from each other, * indicates the site connected to the main chain of the resin. [Chemical formula 2] [ka] In the above Chemical Formula 2, X5 to X8 are the same or different and each independently represents O or S; L1 and L2 are the same or different and each independently represent a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group; R13 and R14 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or are bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; Z3 and Z4 are the same or different and each independently represent a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; m' and n' are each an integer of 0 to 6, p' is an integer from 1 to 6, r13 and r14 are each an integer of 1 to 4, When r13, r14, m', n', and p' are each 2 or more, the structures in the 2 or more brackets are the same or different from each other, * indicates the site connected to the main chain of the resin. [Chemical formula 3] [ka] In the above Chemical Formula 3, X9 to X12 are the same or different and each independently represents O or S; Z5 and Z6 are the same or different and each independently represent a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; R15 and R16 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or are bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; m'' and n'' are each an integer from 0 to 6; p'' is an integer from 1 to 6; r15 and r16 are each an integer of 1 to 6, When r15, r16, m'', n'', and p'' are each 2 or more, the structures in the 2 or more brackets are the same or different from each other, * indicates the site connected to the main chain of the resin.

[0047] When the polycarbonate resin contains the first unit of Formula 1, it contains an isopropylidene group, which is relatively small compared to larger substituents such as fluorene. This shortens the relaxation time of the polycarbonate resin, shortens the cooling time in the mold during injection, and provides excellent processability, economical processes, and a reduced probability of processing defects.

[0048] According to one embodiment of the present specification, the polycarbonate resin comprises two or more second units of Chemical Formula 2.

[0049] According to one embodiment of the present specification, the polycarbonate resin contains two or more second units of Chemical Formula 2.

[0050] According to one embodiment of the present specification, there is provided a polycarbonate resin comprising a first unit of Chemical Formula 1; two or more second units of Chemical Formula 2; and a third unit of Chemical Formula 3.

[0051] According to one embodiment of the present specification, in the polycarbonate resin, the Chemical Formula 2 and the Chemical Formula 3 can complement the glass transition temperature (Tg) of the first unit of the Chemical Formula 1 or can make the chain behavior of the first unit of the Chemical Formula 1 flexible, which has a technical effect advantageous for injection processing of molded articles.

[0052] In one embodiment of the present specification, the weight-average molecular weight of the polycarbonate resin is 3,000 g / mol to 500,000 g / mol, preferably 5,000 g / mol to 300,000 g / mol, 7,000 g / mol to 250,000 g / mol, or 8,000 g / mol to 200,000 g / mol, and more preferably 9,000 g / mol to 150,000 g / mol, 10,000 g / mol to 100,000 g / mol, 12,000 g / mol to 80,000 g / mol, or 13,000 g / mol to 60,000 g / mol.

[0053] In one embodiment of the present invention, the number average molecular weight of the polycarbonate resin is 2,000 g / mol to 300,000 g / mol, 3,000 g / mol to 200,000 g / mol, 4,000 g / mol to 150,000 g / mol, or 4,500 g / mol to 100,000 g / mol, preferably 5,000 g / mol to 80,000 g / mol.

[0054] When the polycarbonate resin satisfies the above-mentioned ranges of weight average molecular weight and number average molecular weight, the polycarbonate resin can have optimal fluidity and processability.

[0055] The weight-average molecular weight (Mw) of polycarbonate resins and oligomers used in their production can be measured by gel permeation chromatography (GPC) using an Agilent 1200 series instrument with a polystyrene standard (PS standard). Specifically, measurements can be performed using an Agilent 1200 series instrument with a Polymer Laboratories PLgel MIX-B 300 mm column at a measurement temperature of 40°C, tetrahydrofuran (THF) as the solvent, and a flow rate of 1 mL / min. Polycarbonate resin or oligomer samples are prepared to a concentration of 10 mg / 10 mL and then added in 10 μL amounts. The weight-average molecular weight (Mw) values ​​are derived using a calibration curve formed using polystyrene standards. In this case, nine types of polystyrene standards with molecular weights (g / mol) of 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000 are used.

[0056] According to one embodiment of the present specification, the refractive index of the polycarbonate resin is 1.6 to 1.8 at 587 nm. The refractive index may be preferably 1.6 to 1.75, more preferably 1.6 to 1.72, and even more preferably 1.660 to 1.669. When the resin satisfies the above-mentioned refractive index, when it is applied to a molded product such as an optical lens, it is possible to produce a thin and lightweight optical lens.

[0057] In one embodiment of the present specification, the Abbe number of the polycarbonate resin measured and calculated at wavelengths of 486, 587, and 656 nm may be 5 to 45, preferably 10 to 25.

[0058] When the polycarbonate resin satisfies the above-mentioned Abbe number range, when the resin is applied to a molded product such as an optical lens, dispersion is reduced and clarity is improved.

[0059] Specifically, the Abbe number can be calculated by measuring the refractive indexes (nD, nF, nC) at wavelengths D (587 nm), F (486 nm), and C (656 nm) at 25°C and using the following formula: Abbe number = (nD-1) / (nF-nC)

[0060] The refractive index can be measured by a prism coupler method, for example, SPA-3DR manufactured by SAIRON Technology, but is not limited to this.

[0061] Using a prism coupler, the resin is placed on a glass slide placed on a heating plate at 200°C, and the change in the amount of light reflected from the flat sample is measured to calculate the refractive index. When the sample is placed in contact with the prism and a laser is incident on the prism, almost total reflection occurs. However, if certain incident angles and conditions are met, an evanescent field is generated at the interface, and light coupling occurs. By measuring the angle at which coupling occurs and the intensity of the light detected by the detector drops sharply, the prism coupler can automatically calculate the refractive index of the film from parameters related to the light polarization mode and the refractive indices of the prism and substrate.

[0062] In one embodiment of the present specification, the glass transition temperature (Tg) of the polycarbonate resin may be 90°C to 200°C, preferably 100°C to 190°C, 120°C to 170°C, or 130°C to 160°C, and more preferably 141°C to 142°C.

[0063] When the polycarbonate resin satisfies the above-mentioned glass transition temperature range, it has excellent heat resistance and injectability, and when it is mixed with a resin having a glass transition temperature different from the above-mentioned range to prepare a polycarbonate resin composition, it is easy to control the glass transition temperature, and the physical properties targeted in this specification can be satisfied.

[0064] The glass transition temperature (Tg) can be measured using a differential scanning calorimeter (DSC). Specifically, the glass transition temperature can be measured from a graph obtained by heating 5.5 mg to 8.5 mg of the polycarbonate resin sample to 270°C in a nitrogen atmosphere, cooling it, and then heating it for the second time at a heating rate of 10°C / min while scanning.

[0065] According to one embodiment of the present specification, the polycarbonate resin has an MI (melt index) of 5 to 150, specifically 10 to 100, and more specifically 20 to 80, or 41 to 53. The MI can be measured by a method commonly used in the art, specifically using a Goettfert Melt Indexer (Mi2.2). A sample is dried in an oven at 120°C for at least 5 hours, and the dried sample is placed in the instrument at the measurement temperature (260°C) and melted for 5 minutes. The weight of the sample passing through the nozzle for 5 seconds when a pressure of 2.16 kg is applied is measured, and the weight is converted to g / 10 min to calculate the melt index (MI).

[0066] When the polycarbonate resin has the above-mentioned melt index, it maintains appropriate fluidity and exhibits properties suitable for injection molding.

[0067] In this specification, examples of the substituents are described below, but are not limited to these.

[0068] In this specification, [ka] means the site to be linked.

[0069] The term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position of the substitution is not limited as long as it is a position at which a hydrogen atom is substituted, i.e., a position at which a substituent can be substituted, and when two or more substituents are substituted, the two or more substituents may be the same or different.

[0070] As used herein, the term "substituted or unsubstituted" means substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a hydroxy group, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryloxy group, an arylthio group, an alkylthio group, a silyl group, an aryl group, and a heteroaryl group, or substituted with a substituent in which two or more of the above-exemplified substituents are linked, or has no substituents.

[0071] In this specification, "two or more substituents are linked" means that a hydrogen atom of any one of the substituents is linked to another substituent. For example, "two substituents are linked" means that a phenyl group and a naphthyl group are linked, [ka] In addition, the linking of three substituents includes not only the linking of (substituent 1)-(substituent 2)-(substituent 3) consecutively, but also the linking of (substituent 1) to (substituent 2) and (substituent 3). For example, a phenyl group, a naphthyl group, and an isopropyl group can be linked together, [ka] The above definitions also apply to the case where four or more substituents are connected.

[0072] As used herein, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

[0073] In this specification, the alkyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like.

[0074] In this specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and adamantyl groups, but are not limited to these.

[0075] In this specification, the alkoxy group may be linear, branched, or cyclic. The number of carbon atoms in the alkoxy group is not particularly limited, but preferably has 1 to 30 carbon atoms. Specific examples include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, and p-methylbenzyloxy.

[0076] In this specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but preferably is 2 to 30. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, a stilbenyl group, and a styrenyl group, but are not limited to these.

[0077] In this specification, the aryl group is not particularly limited, but preferably has 6 to 50 carbon atoms, and the aryl group may be monocyclic or polycyclic.

[0078] When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably is 6 to 30. Specific examples of the monocyclic aryl group include, but are not limited to, a phenyl group, a biphenyl group, and a terphenyl group.

[0079] When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited, but preferably is 10 to 50. Specific examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a phenalene group, a perylene group, a chrysene group, and a fluorene group.

[0080] In this specification, the fluorene group may be substituted, and adjacent groups may be bonded to each other to form a ring.

[0081] Examples of the fluorene group include: [ka] These include, but are not limited to:

[0082] As used herein, the term "adjacent" groups may refer to a substituent substituted on an atom directly linked to the atom on which the substituent is substituted, a substituent sterically closest to the substituent, or another substituent substituted on the atom on which the substituent is substituted. For example, two substituents substituted at ortho positions on a benzene ring and two substituents substituted on the same carbon atom on an aliphatic ring can be interpreted as groups "adjacent" to each other.

[0083] In this specification, a heteroaryl group includes one or more non-carbon atoms, i.e., heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but is preferably 2 to 30, and the heteroaryl group may be monocyclic or polycyclic. Examples of heteroaryl groups include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a pyridine group, a bipyridine group, a pyrimidine group, a triazine group, an acridine group, a pyridazine group, a pyrazine group, a quinoline group, a quinazoline group, a quinoxaline group, a phthalazine group, a pyridopyrimidine group, a pyridopyrazine group, a pyrazinopyrazine group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuran group, and a phenanthridine group. Examples of such an alkyl group include, but are not limited to, phenanthridine, phenanthroline, isoxazole, thiadiazole, dibenzofuran, dibenzosilole, phenoxathiine, phenoxazine, phenothiazine, dihydroindenocarbazole, spirofluorenexanthene, spirofluorenethioxanthene, tetrahydronaphthothiophene, tetrahydronaphthofuran, tetrahydrobenzothiophene, and tetrahydrobenzofuran groups.

[0084] In this specification, the silyl group may be an alkylsilyl group, an arylsilyl group, an alkylarylsilyl group, a heteroarylsilyl group, etc. The alkyl group in the alkylsilyl group may be the same as the alkyl group exemplified above, the aryl group in the arylsilyl group may be the same as the aryl group exemplified above, the alkyl group and aryl group in the alkylarylsilyl group may be the same as the alkyl group exemplified above, and the heteroaryl group in the heteroarylsilyl group may be the same as the heteroaryl group exemplified above.

[0085] In this specification, an aryloxy group may be represented by -ORo, and the above description of the aryl group applies to Ro.

[0086] In this specification, an arylthio group may be represented by -SRs1, and the above description of the aryl group applies to Rs1.

[0087] In this specification, an alkylthio group may be represented by -SRs2, and the above description of the alkyl group applies to Rs2.

[0088] In this specification, the alkylene group refers to an alkyl group having two bonding positions, i.e., a divalent group. The above description of the alkyl group may be applied, except that each of these is a divalent group.

[0089] In this specification, a cycloalkylene group refers to a cycloalkyl group having two bonding positions, i.e., a divalent group. The above description of the cycloalkyl group may be applied, except that each of these is a divalent group.

[0090] One embodiment of the present specification provides a method for producing the polycarbonate resin, comprising polymerizing a composition for producing the polycarbonate resin, the composition comprising: a compound represented by the following Chemical Formula 1a; a compound represented by the following Chemical Formula 2a; a compound represented by the following Chemical Formula 3a; and a polycarbonate precursor: [Chemical formula 1a] [ka] In the above chemical formula 1a, X1 to X4 are the same or different and each independently represents O or S; R1 to R4 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted heteroaryl group; Z1 and Z2 are the same or different and each independently represent a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; R and R are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or are bonded to each other to form a substituted or unsubstituted hydrocarbon ring; R101 and R102 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; r101 is 1 or 2, and when r101 is 2, the two R101 are the same or different from each other; r102 is 1 or 2, and when r102 is 2, the two R102 are the same or different from each other; m and n are each an integer of 0 to 6, When m and n are each 2 or more, the structures in the two or more parentheses may be the same or different from each other, [Chemical formula 2a] [ka] [Chemical formula 3a] [ka] In the above chemical formulas 2a and 3a, X5 to X12 are the same or different and each independently represents O or S; L1 and L2 are the same or different and each independently represent a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group; Z3 to Z6 are the same or different and each independently represent a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; R13 to R16 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or are bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; r13 and r14 are each an integer of 1 to 4, r15 and r16 are each an integer of 1 to 6, m', m'', n', and n'' are each an integer from 0 to 6; When each of r13 to r16, m', m'', n', and n'' is 2 or more, the structures in the 2 or more brackets are the same or different.

[0091] One embodiment of the present specification provides a method for producing the polycarbonate resin, comprising polymerizing a composition for producing a polycarbonate resin, the composition comprising: the compound of Chemical Formula 1a; the compound of Chemical Formula 2a; the compound of Chemical Formula 3a; and a polycarbonate precursor.

[0092] One embodiment of the present specification provides a method for producing the polycarbonate resin, comprising polymerizing a composition for producing a polycarbonate resin, the composition comprising: the compound of Formula 1a; the two or more compounds of Formula 2a; the compound of Formula 3a; and a polycarbonate precursor.

[0093] The relaxation time and residual phenol content of the polycarbonate resin are as described above.

[0094] According to one embodiment of the present specification, X1 is O.

[0095] According to one embodiment of the present specification, X2 is O.

[0096] According to one embodiment of the present specification, X3 is O.

[0097] According to one embodiment of the present specification, X4 is O.

[0098] According to one embodiment of the present specification, X5 is O.

[0099] According to one embodiment of the present specification, X6 is O.

[0100] According to one embodiment of the present specification, X7 is O.

[0101] According to one embodiment of the present specification, X8 is O.

[0102] According to one embodiment of the present specification, X9 is O.

[0103] According to one embodiment of the present specification, X10 is O.

[0104] According to one embodiment of the present specification, X11 is O.

[0105] According to one embodiment of the present specification, X12 is O.

[0106] According to one embodiment of the present specification, X1 is S.

[0107] According to one embodiment of the present specification, X2 is S.

[0108] According to one embodiment of the present specification, X3 is S.

[0109] According to one embodiment of the present specification, X4 is S.

[0110] According to one embodiment of the present specification, X5 is S.

[0111] According to one embodiment of the present specification, X6 is S.

[0112] According to one embodiment of the present specification, X7 is S.

[0113] According to one embodiment of the present specification, X8 is S.

[0114] According to one embodiment of the present specification, X9 is S.

[0115] According to one embodiment of the present specification, X10 is S.

[0116] According to one embodiment of the present specification, X11 is S.

[0117] According to one embodiment of the present specification, X12 is S.

[0118] According to one embodiment of the present specification, Z1 and Z2 are the same or different and each independently represent a linear or branched alkylene group having 1 to 30 carbon atoms.

[0119] According to one embodiment of the present specification, Z1 and Z2 are the same or different and each independently represent a linear or branched alkylene group having 1 to 20 carbon atoms.

[0120] According to one embodiment of the present specification, Z1 and Z2 are the same or different and each independently represent a linear or branched alkylene group having 1 to 10 carbon atoms.

[0121] According to one embodiment of the present specification, Z1 and Z2 are ethylene groups.

[0122] According to one embodiment of the present specification, Z3 and Z4 are the same or different and each independently represent a linear or branched alkylene group having 1 to 30 carbon atoms.

[0123] According to one embodiment of the present specification, Z3 and Z4 are the same or different and each independently represent a linear or branched alkylene group having 1 to 20 carbon atoms.

[0124] According to one embodiment of the present specification, Z3 and Z4 are the same or different and each independently represent a linear or branched alkylene group having 1 to 10 carbon atoms.

[0125] According to one embodiment of the present specification, Z3 and Z4 are ethylene groups.

[0126] According to one embodiment of the present specification, Z5 and Z6 are the same or different and each independently represent a linear or branched alkylene group having 1 to 30 carbon atoms.

[0127] According to one embodiment of the present specification, Z5 and Z6 are the same or different and each independently represent a linear or branched alkylene group having 1 to 20 carbon atoms.

[0128] According to one embodiment of the present specification, Z5 and Z6 are the same or different and each independently represent a linear or branched alkylene group having 1 to 10 carbon atoms.

[0129] According to one embodiment of the present specification, Z5 and Z6 are ethylene groups.

[0130] According to one embodiment of the present specification, L1 and L2 are the same or different and each independently represent a linear or branched alkyl group having 1 to 30 carbon atoms, or a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms which is substituted or unsubstituted with a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0131] According to one embodiment of the present specification, L1 and L2 are the same or different and each independently represent a linear or branched alkyl group having 1 to 20 carbon atoms, or a monocyclic or polycyclic arylene group having 6 to 20 carbon atoms, substituted or unsubstituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0132] According to one embodiment of the present specification, L1 and L2 are the same or different and each independently represent a phenylene group unsubstituted or substituted with a methyl group, a phenyl group, or a naphthyl group; or a divalent naphthyl group.

[0133] According to one embodiment of the present specification, R1 to R4 are the same or different and each independently represent a hydrogen atom; a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms which is substituted or unsubstituted with a cyano group, a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched alkenyl group having 2 to 30 carbon atoms, or a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms; a fused ring group of a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms and a monocyclic or polycyclic aliphatic hydrocarbon ring having 3 to 30 carbon atoms; or a polycyclic heteroaryl group having 6 to 30 carbon atoms.

[0134] According to one embodiment of the present specification, R1 to R4 are the same or different and each independently represent a hydrogen atom; a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms which is substituted or unsubstituted with a cyano group, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, or a monocyclic or polycyclic heteroaryl group having 2 to 20 carbon atoms; a fused ring group of a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 20 carbon atoms and a monocyclic or polycyclic aliphatic hydrocarbon ring having 3 to 20 carbon atoms; or a polycyclic heteroaryl group having 6 to 20 carbon atoms.

[0135] According to one embodiment of the present specification, R1 to R4 are the same or different and each independently represent a hydrogen atom; a phenyl group unsubstituted or substituted with a cyano group or a methyl group; a naphthyl group unsubstituted or substituted with a cyano group; a dihydroindene group; or a quinoline group.

[0136] According to one embodiment of the present specification, R11 and R12 are the same or different and each independently represent a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 6 to 30 carbon atoms; a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; or a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms, or are bonded to each other to form a monocyclic or polycyclic aliphatic hydrocarbon ring having 6 to 30 carbon atoms and which is substituted or unsubstituted with a linear or branched alkyl group having 1 to 30 carbon atoms.

[0137] According to one embodiment of the present specification, R11 and R12 are the same or different and each independently represent a linear or branched alkyl group having 1 to 20 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 6 to 20 carbon atoms; a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; or a monocyclic or polycyclic heteroaryl group having 2 to 20 carbon atoms, or are bonded to each other to form a monocyclic or polycyclic aliphatic hydrocarbon ring having 6 to 20 carbon atoms and which is substituted or unsubstituted with a linear or branched alkyl group having 1 to 20 carbon atoms.

[0138] According to one embodiment of the present specification, R11 and R12 are the same or different and each independently represent a methyl group or a phenyl group, or are bonded to each other to form a cyclohexane or cyclododecane substituted or unsubstituted with a methyl group.

[0139] According to one embodiment of the present specification, R13 and R14 are the same or different and each independently represent hydrogen or an aryl group having 6 to 30 carbon atoms, or are bonded to adjacent groups to form a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms.

[0140] According to one embodiment of the present specification, R13 and R14 are the same or different and each independently represent hydrogen or an aryl group having 6 to 20 carbon atoms, or are bonded to adjacent groups to form a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 20 carbon atoms.

[0141] According to one embodiment of the present specification, R13 and R14 are the same or different and each independently represent a hydrogen atom; a phenyl group; or a naphthyl group, or are bonded to adjacent groups to form benzene.

[0142] According to one embodiment of the present specification, R15 and R16 are the same or different and each independently represent hydrogen or an aryl group having 6 to 30 carbon atoms.

[0143] According to one embodiment of the present specification, R15 and R16 are the same or different and each independently represent hydrogen or an aryl group having 6 to 20 carbon atoms.

[0144] According to one embodiment of the present specification, R15 and R16 are the same or different and each independently represent a hydrogen atom; a phenyl group; or a naphthyl group.

[0145] According to one embodiment of the present specification, the compound of Formula 1a is any one of the following compounds: [ka] [ka] [ka]

[0146] According to one embodiment of the present specification, the compound of Formula 2a is any one of the following compounds: [ka]

[0147] According to one embodiment of the present specification, the compound of Formula 3a is any one of the following compounds: [ka]

[0148] According to one embodiment of the present specification, the method for producing a polycarbonate resin includes the compound of Chemical Formula 1a, the compound of Chemical Formula 2a, and the compound of Chemical Formula 3a, wherein the compound of Chemical Formula 1a, the compound of Chemical Formula 2a, and the compound of Chemical Formula 3a are contained in an amount of 0.01 mol% to 99.98 mol%: 0.01 mol% to 99.98 mol%: 0.01 mol% to 99.98 mol%, specifically 0.1 mol% to 99.8 mol%: 0.1 mol% to 99.8 mol%: 0.1 mol% to 99.8 mol%, 1 mol% to 98 mol%: 1 mol% to 98 mol%: 1 mol% to 98 mol%, or 5 mol% to 90 mol%: 5 mol% to 90 mol%: 5 mol% to 90 mol%.

[0149] According to one embodiment of the present specification, the method for producing a polycarbonate resin includes the compound of Chemical Formula 1a, two or more compounds of Chemical Formula 2a, and the compound of Chemical Formula 3a, wherein the compound of Chemical Formula 1a, two or more compounds of Chemical Formula 2a, and the compound of Chemical Formula 3a are contained in an amount of 0.01 mol% to 99.98 mol%: 0.01 mol% to 99.98 mol%: 0.01 mol% to 99.98 mol%, specifically 0.1 mol% to 99.8 mol%: 0.1 mol% to 99.8 mol%: 0.1 mol% to 99.8 mol%, 1 mol% to 98 mol%: 1 mol% to 98 mol%: 1 mol% to 98 mol%, or 5 mol% to 90 mol%: 5 mol% to 90 mol%: 5 mol% to 90 mol%.

[0150] When the compounds of Formulae 1a, 2a, and 3a are contained in the above-mentioned amounts, the polycarbonate resin has excellent processability, the glass transition temperature (Tg) and refractive index can be adjusted, and the chain behavior of the polycarbonate resin can be made flexible, which has advantageous technical effects in injection processing of molded products.

[0151] According to one embodiment of the present specification, the polycarbonate precursor is contained in an amount of 50 to 150 parts by mole, preferably 100 parts by mole, relative to a total of 100 parts by mole of the compound of Chemical Formula 1a, the compound of Chemical Formula 2a, and the compound of Chemical Formula 3a in the composition for producing a polycarbonate resin.

[0152] According to one embodiment of the present specification, the polycarbonate precursor is contained in an amount of 50 to 150 parts by mole, preferably 100 parts by mole, relative to a total of 100 parts by mole of the compound of Chemical Formula 1a, two or more compounds of Chemical Formula 2a, and the compound of Chemical Formula 3a in the composition for producing a polycarbonate resin.

[0153] When the polycarbonate precursor is contained in the above molar parts, a polycarbonate resin can be produced that is excellent in transparency, heat resistance, refractive index, birefringence, strength, and processability.

[0154] The composition for producing a polycarbonate resin may further contain a solvent.

[0155] The solvent may be, for example, diphenyl ether, dimethylacetamide, or methanol, but is not limited thereto, and any solvent applicable in the art may be appropriately adopted.

[0156] The solvent may be contained in an amount of 5 to 60 parts by weight relative to 100 parts by weight of the composition for producing a resin.

[0157] The solvent may be contained in an amount of preferably 5 to 50 parts by weight, 7 to 45 parts by weight, or 8 to 40 parts by weight relative to 100 parts by weight of the composition for producing a resin.

[0158] According to one embodiment of the present specification, the polycarbonate precursor is contained in an amount of 50 to 150 parts by weight based on 100 parts by weight of the composition for producing a polycarbonate resin.

[0159] When the polycarbonate precursor is contained in the above-mentioned parts by weight, a polycarbonate resin excellent in transparency, heat resistance, refractive index, birefringence, strength, and processability can be produced.

[0160] In one embodiment of the present specification, the compound of Chemical Formula 1a may be included in an amount of 1 part by weight to 100 parts by weight, or 1 part by weight to 99 parts by weight, based on 100 parts by weight of the composition for producing a polycarbonate resin.

[0161] The compound of Chemical Formula 1a may be included in an amount of preferably 1 to 60 parts by weight, 1 to 50 parts by weight, 1 to 40 parts by weight, 1 to 30 parts by weight, 1 to 20 parts by weight, or 1 to 10 parts by weight, based on 100 parts by weight of the composition for producing a polycarbonate resin.

[0162] In one embodiment of the present specification, the compound of Chemical Formula 2a may be included in an amount of 0 to 99 parts by weight, or 1 to 99 parts by weight, relative to 100 parts by weight of the composition for producing a polycarbonate resin.

[0163] The compound of Chemical Formula 2a may be included in an amount of preferably 1 to 60 parts by weight, 1 to 50 parts by weight, 1 to 40 parts by weight, 1 to 30 parts by weight, 1 to 20 parts by weight, or 1 to 10 parts by weight, based on 100 parts by weight of the composition for producing a polycarbonate resin.

[0164] The two or more compounds of Chemical Formula 2a may be contained in an amount of preferably 1 to 60 parts by weight, 1 to 50 parts by weight, 1 to 40 parts by weight, 1 to 30 parts by weight, 1 to 20 parts by weight, or 1 to 10 parts by weight, based on 100 parts by weight of the composition for producing a polycarbonate resin.

[0165] In one embodiment of the present specification, the compound of Chemical Formula 3a may be included in an amount of 0 to 99 parts by weight, or 1 to 99 parts by weight, relative to 100 parts by weight of the composition for producing a polycarbonate resin.

[0166] The compound of Chemical Formula 3a may be included in an amount of preferably 1 to 60 parts by weight, 1 to 50 parts by weight, 1 to 40 parts by weight, 1 to 30 parts by weight, 1 to 20 parts by weight, or 1 to 10 parts by weight, based on 100 parts by weight of the composition for producing a polycarbonate resin.

[0167] According to one embodiment of the present specification, the polycarbonate precursor is a compound of the following chemical formula A: [Chemical formula A] [ka] In the above chemical formula A, Rb1 and Rb2 are the same or different and each independently represent a halogen group; a hydroxy group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; or a substituted or unsubstituted aryl group; a1 and a2 are each 0 or 1.

[0168] According to one embodiment of the present specification, Rb1 and Rb2 are the same or different and each independently represent a halogen group; a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 6 to 30 carbon atoms; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0169] According to one embodiment of the present specification, Rb1 and Rb2 are the same or different and each independently represent a halogen group; a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 6 to 20 carbon atoms; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0170] According to one embodiment of the present specification, Rb1 and Rb2 are the same or different and each independently represent a halogen group; a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 6 to 30 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0171] According to one embodiment of the present specification, Rb1 and Rb2 are the same or different and each independently represent a halogen group; a linear or branched alkyl group having 1 to 20 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 6 to 20 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0172] According to one embodiment of the present specification, Rb1 and Rb2 are the same or different and each independently represent -Cl; a methyl group; an ethyl group; an n-propyl group; an n-butyl group; an isopropyl group; an isobutyl group; or a phenyl group.

[0173] According to one embodiment of the present specification, the compound represented by formula A is any one selected from the following compounds: [ka]

[0174] The polycarbonate precursor serves to link additional comonomers as needed, and specific examples that can be used in addition to the compound represented by Chemical Formula A include phosgene, triphosgene, diphosgene, bromophosgene, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, and bishaloformates, and any one or a mixture of two or more of these may be used.

[0175] In one embodiment of the present specification, it is more preferred that the polycarbonate resin is polymerized from the compound of Chemical Formula 1a, the compound of Chemical Formula 2a, the compound of Chemical Formula 3a, and the polycarbonate precursor of Chemical Formula A.

[0176] In one embodiment of the present specification, it is more preferred that the polycarbonate resin is polymerized from the compound of Chemical Formula 1a, two or more compounds of Chemical Formula 2a, the compound of Chemical Formula 3a, and the polycarbonate precursor of Chemical Formula A.

[0177] Polymerization of the compound of formula 1a with the polycarbonate precursor of formula A can form the unit of formula 1 described above; polymerization of the compound of formula 2a with the polycarbonate precursor of formula A can form the unit of formula 2 described above; and polymerization of the compound of formula 3a with the polycarbonate precursor of formula A can form the unit of formula 3 described above.

[0178] The compound of Formula 1a and the polycarbonate precursor of Formula A can be polymerized to form the unit of Formula 1 described above.

[0179] The compound of Chemical Formula 1a may be used in an amount of 1 to 100 parts by mole, or 1 to 99 parts by mole, relative to 100 parts by mole of all monomers constituting the polycarbonate resin containing the unit of Chemical Formula 1.

[0180] The polycarbonate precursor of the chemical formula A may be used in an amount of 50 to 150 parts by mole relative to 100 parts by mole of all monomers of the compound of the chemical formula 1a that constitutes the resin.

[0181] The compound of Formula 2a and the polycarbonate precursor of Formula A can be polymerized to form the unit of Formula 2.

[0182] The compound of Chemical Formula 2a may be used in an amount of 1 to 100 parts by mole, or 1 to 99 parts by mole, relative to 100 parts by mole of all monomers constituting the polycarbonate resin containing the unit of Chemical Formula 2.

[0183] The polycarbonate precursor of the chemical formula A may be used in an amount of 50 to 150 parts by mole relative to 100 parts by mole of all monomers of the compound of the chemical formula 2a that constitutes the resin.

[0184] The compound of Formula 3a and the polycarbonate precursor of Formula A can be polymerized to form the unit of Formula 3.

[0185] The compound of Chemical Formula 3a may be used in an amount of 1 to 100 parts by mole, or 1 to 99 parts by mole, relative to 100 parts by mole of all monomers constituting the polycarbonate resin containing the unit of Chemical Formula 3.

[0186] The polycarbonate precursor of the chemical formula A may be used in an amount of 50 to 150 parts by mole relative to 100 parts by mole of all monomers of the compound of the chemical formula 3a that constitutes the resin.

[0187] The polycarbonate precursor of the chemical formula A may be used in an amount of 50 to 150 parts by mole relative to a total of 100 parts by mole of the compound of the chemical formula 1a, the compound of the chemical formula 2a, and the compound of the chemical formula 3a that constitute the resin.

[0188] The polycarbonate precursor of the chemical formula A may be used in an amount of 50 to 150 parts by mole per 100 parts by mole of the total of the compound of the chemical formula 1a, two or more compounds of the chemical formula 2a, and the compound of the chemical formula 3a that constitute the resin.

[0189] Polymerization of the resins herein may be accomplished using methods well known in the art.

[0190] The polymerization is preferably carried out by a melt polycondensation method.

[0191] The melt polycondensation method may use the composition for producing a polycarbonate resin, and may further include a catalyst as needed, and may perform melt polycondensation under heating and further under atmospheric pressure or reduced pressure while removing by-products through a transesterification reaction. The catalyst may be a substance generally used in the art.

[0192] Specifically, the melt polycondensation method is preferably carried out by melting the compound of Chemical Formula 1a, the compound of Chemical Formula 2a, the compound of Chemical Formula 3, and the polycarbonate precursor in a reaction vessel, and then allowing the by-product compounds to remain.

[0193] More specifically, the melt polycondensation method preferably involves melting the compound of Chemical Formula 1a, two or more compounds of Chemical Formula 2a, the compound of Chemical Formula 3, and the polycarbonate precursor in a reaction vessel, and then carrying out the reaction while retaining by-product compounds.

[0194] In order to retain the by-produced compounds, the reaction apparatus may be blocked or the pressure may be controlled by reducing or increasing the pressure.

[0195] The reaction time in this step is from 20 minutes to 600 minutes, preferably from 40 minutes to 450 minutes, and more preferably from 60 minutes to 350 minutes.

[0196] In this case, if the by-product compounds are distilled off immediately after production, the final resin will have a low content of high molecular weight compounds, whereas if the by-product compounds are allowed to remain in the reaction vessel for a certain period of time, the final resin will have a high content of high molecular weight compounds.

[0197] The melt polycondensation method may be carried out continuously or batchwise. The reaction apparatus used for the reaction may be a vertical type equipped with a soken-type impeller, an anchor-type impeller, a Maxblend impeller, a helical ribbon-type impeller, or the like, a horizontal type equipped with a paddle impeller, a lattice impeller, a spectacle impeller, or the like, or an extruder type equipped with a screw. In addition, it is preferable to use a reaction apparatus that is an appropriate combination of these reaction apparatuses, taking into consideration the viscosity of the polymer.

[0198] In the method for producing the polycarbonate resin used in this specification, after the polymerization reaction is completed, the catalyst may be removed or deactivated in order to maintain thermal stability and hydrolytic stability. A method of deactivating the catalyst by adding an acidic substance known in the art is preferably carried out.

[0199] Examples of the acidic substance include esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid; phosphites such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonic acid esters such as diethyl phenylphosphonate; phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids such as boric acid and phenylboric acid; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate; organic halides such as stearic acid chloride, benzoyl chloride, and p-toluenesulfonic acid chloride; alkyl sulfates such as dimethyl sulfate; and organic halides such as benzyl chloride.

[0200] The acidic substance may be used in an amount of 0.1 to 5 parts by mol, preferably 0.1 to 1 part by mol, relative to 100 parts by mol of the catalyst.

[0201] If the amount of the acidic substance is less than 0.1 parts by mole, the deactivation effect will be insufficient, which is not preferred, whereas if the amount is more than 5 parts by mole, the heat resistance of the resin will decrease and the molded product will be prone to coloration, which is not preferred.

[0202] After the catalyst is deactivated, a devolatilization step may be further carried out to remove low-boiling compounds from the resin at a pressure of 0.1 mmHg to 1 mmHg and a temperature of 200° C. to 350° C. For this step, a horizontal apparatus equipped with stirring blades with excellent surface renewal ability, such as paddle blades, lattice blades, or spectacle blades, or a thin-film evaporator is preferably used.

[0203] The resin of the present invention preferably has a minimum content of foreign matter, and filtration of the molten raw material, filtration of the catalyst solution, etc. are preferably carried out.

[0204] The mesh of the filter used for the filtration is preferably 5 μm or less, more preferably 1 μm or less. The produced resin is preferably filtered through a polymer filter. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. The process of collecting resin pellets must be carried out in a low-dust environment, preferably class 6 or less, more preferably class 5 or less.

[0205] Furthermore, examples of methods for molding molded articles containing the polycarbonate resin include, in addition to injection molding, compression molding, casting, roll processing, extrusion molding, and stretching, but are not limited to these.

[0206] Another embodiment herein provides a polycarbonate resin composition comprising a resin according to the above-described embodiment.

[0207] In one embodiment of the present specification, the polycarbonate resin may be contained in an amount of 1 part by weight to 80 parts by weight based on 100 parts by weight of the polycarbonate resin composition.

[0208] In one embodiment of the present specification, the polycarbonate resin composition may further contain a solvent, for example, dimethylacetamide or 1,2-dichlorobenzene.

[0209] The solvent may be included in an amount of 20 to 99 parts by weight based on 100 parts by weight of the polycarbonate resin composition.

[0210] The polycarbonate resin composition may further contain an additional monomer in addition to the compound of Chemical Formula 1a. The additional monomer is not particularly limited, and any monomer generally used in the technical field related to polycarbonates may be appropriately used as long as it does not change the main physical properties of the polycarbonate resin composition. The additional monomer may be used in an amount of 1 to 50 parts by mole per 100 parts by mole of all monomers constituting the resin containing the unit of Chemical Formula 1.

[0211] In addition to the resin containing the unit of Chemical Formula 1, the polycarbonate resin composition may further contain, as necessary, additives such as one or more selected from the group consisting of antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent brighteners, UV absorbers, inorganic additives, pigments, and dyes.

[0212] The additive may be included in an amount of 1 to 99 parts by weight based on 100 parts by weight of the polycarbonate resin composition.

[0213] The types of the antioxidant, plasticizer, antistatic agent, nucleating agent, flame retardant, lubricant, impact modifier, fluorescent brightener, ultraviolet absorber, inorganic additive, pigment, or dye are not particularly limited, and any agent applicable in the relevant technical field may be appropriately adopted.

[0214] Another embodiment of the present specification provides a molded article comprising a resin composition according to the above-described embodiment.

[0215] In one embodiment of the present specification, the molded article may be produced from the polycarbonate resin composition or a cured product thereof.

[0216] An example of a method for manufacturing the molded product may include thoroughly mixing the polycarbonate resin and the additives in a mixer, extruding the mixture in an extruder to prepare pellets, drying the pellets, and then injecting the pellets into an injection molding machine.

[0217] In one embodiment of the present specification, the molded article is an optical lens.

[0218] In one embodiment of the present specification, the optical lens has a thickness of 0.1 μm to 30 mm.

[0219] The optical lens according to an embodiment of the present specification has a high refractive index, and therefore, an optical lens with a small thickness can be realized.

[0220] The optical lens is manufactured using the polycarbonate resin, has a thin thickness, a high refractive index and high transparency, and is preferably applicable to cameras, mobile phones, vehicles, and autonomous driving sensor lenses.

[0221] In one embodiment of the present specification, the molded article is an optical fiber.

[0222] In one embodiment of the present specification, the molded article is an optical film or an optical thin film, which is manufactured using the polycarbonate resin, has a thin thickness, and has excellent light-collecting and light-diffusing effects, and is preferably applicable to backlight modules of liquid crystal displays, flat lenses, metalenses, etc.

[0223] In one embodiment of the present specification, the optical film or optical thin film has a thickness of 0.1 nm to 10 mm.

[0224] In one embodiment of the present specification, the molded article is an optical resin. The optical resin is manufactured using the polycarbonate resin, and has a small thickness, a high refractive index, a low birefringence, and a low optical loss.

[0225] In one embodiment of the present specification, the molded article is an LED encap. [Example]

[0226] The present invention will now be illustrated in more detail by way of examples. [ka]

[0227] Manufacturing Example 1 Monomer 1-1 (3.423 g (0.015 mol)), Monomer 2-1 (14.177 g (0.024 mol)), Monomer 2-2 (8.618 g (0.016 mol)), Monomer 3-1 (16.837 g (0.045 mol)), and 21.422 g (0.100 mol) of diphenylcarbonate were melted and reacted at 250 °C for 5 hours. As the reaction progressed, phenol was generated as a by-product, and the pressure was reduced to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and Resin 1 was obtained as a polymerized molten polymer resin.

[0228] Manufacturing Example 2 Monomer 1-1 (1.072 g (0.0047 mol)), Monomer 2-1 (5.907 g (0.01 mol)), Monomer 2-2 (15.243 g (0.0283 mol)), Monomer 3-1 (21.326 g (0.057 mol)), and 21.422 g (0.100 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a by-product, and the pressure was reduced to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and Resin 2 was obtained as a polymerized molten polymer resin.

[0229] Manufacturing Example 3 Monomer 1-1 (22.829 g (0.100 mol)) and 21.422 g (0.100 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a by-product, and the pressure was reduced to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and Comparative Example Resin 1 was obtained as a polymerized polymer molten resin.

[0230] Manufacturing Example 4 Monomer 3-1 (37.415 g (0.100 mol)) and 21.422 g (0.100 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a by-product, and the pressure was reduced to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and Comparative Example Resin 2 was obtained as a polymerized polymer molten resin.

[0231] Production Example 5 Monomer 2-2 (53.864 g (0.100 mol)) and 21.422 g (0.100 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a by-product, and the pressure was reduced to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and Comparative Example Resin 3 was obtained as a polymerized polymer molten resin.

[0232] Manufacturing Example 6 Monomer 2-1 (59.072 g (0.100 mol)) and 21.422 g (0.100 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a by-product, and the pressure was reduced to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and Comparative Example Resin 4 was obtained as a polymerized polymer molten resin.

[0233] Manufacturing Example 7 Monomer 1-1 (11.41 g (0.05 mol)), Monomer 2-2 (26.931 g (0.05 mol)), and 21.422 g (0.100 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a by-product, and the pressure was reduced to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and Comparative Example Resin 5 was obtained as a polymerized polymer molten resin.

[0234] Manufacturing Example 8 Monomer 1-1 (6.846 g (0.03 mol)), Monomer 2-2 (37.703 g (0.07 mol)), and 21.422 g (0.100 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a by-product, and the pressure was reduced to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and Comparative Example Resin 6 was obtained as a polymerized polymer molten resin.

[0235] Manufacturing Example 9 Monomer 1-1 (11.41 g (0.05 mol)), Monomer 3-1 (18.707 g (0.05 mol)), and 21.422 g (0.100 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a by-product, and the pressure was reduced to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and Comparative Example Resin 7 was obtained as a polymerized polymer molten resin.

[0236] Manufacturing Example 10 Monomer 2-2 (26.931 g (0.05 mol)), Monomer 3-1 (18.707 g (0.05 mol)), and diphenylcarbonate (21.422 g (0.100 mol)) were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a by-product, and the pressure was reduced to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and Comparative Example Resin 8 was obtained as a polymerized polymer molten resin.

[0237] Example The molecular relaxation time, high shear viscosity, residual phenol content, MI (melt index), refractive index, and glass transition temperature of the resin sample polymerized in the above Preparation Example were measured. The molecular relaxation time was measured at 250°C and 0.1 Hz to 100 Hz using a hybrid rheometer (Discovery (HR-2)). A shear force was applied at 250°C until a deformation rate of 30% was reached, and then the force was removed. When the applied shear force reached 1 Pa (= 1 N / m 2 The time it took for the stress to return to 1 Pa was measured, and the viscoelastic behavior of the polymer at high temperatures (250°C) was measured. The shear force was maximized and applied to the extent that the molten polymer moved, at which point the stress reached 100 Pa or more. The stress was then quickly removed and the time it took for the stress to return to 1 Pa was measured, and the results are shown in Table 2 below.

[0238] The high shear viscosity was measured by placing 2 to 5 g of the resin sample in a hybrid rheometer (discovery (HR-2)) at 250° C. and 10 Hz to 63 Hz. The results are shown in Table 2 below.

[0239] The residual phenol content was determined by dissolving 1 g of resin solids in 12 ml of methylene chloride (MC) and 18 ml of methanol (MeOH), filtering through a 0.2 μm pore filter, and then measuring the phenol content by HPLC / UV. The results are shown in Table 2 below (measurement wavelength: 200 μm HPLC, mobile phase A: acetonitrile, mobile phase B: HO, column: Capcellpak C18 (4.6 mm ID × 50 mm, 5 μm), column temperature: 40°C, flow rate: 1 ml / min, injection volume: 5 μl, run time: 10 min).

[0240] The melt index (MI) was measured using a Goettfert Melt Indexer (Mi2.2). A resin sample was dried in an oven at 120°C for more than 5 hours, and the dried sample was placed in the instrument at the measurement temperature (260°C) and melted for 5 minutes. After that, the weight of the sample passing through the nozzle for 5 seconds while applying pressure with a weight of 2.16 kg was measured, and the melt index (MI) was calculated by converting it to g / 10 min, as shown in Table 2 below.

[0241] The glass transition temperature (Tg) of the resin was measured using a differential scanning calorimeter (DSC). 5.5 mg to 8.5 mg of resin sample was heated to 270°C under N2 flow, cooled, and then heated at a heating rate of 10°C / min during the second heating cycle. The glass transition temperature (Tg) was determined from the resulting graph, which is shown in Table 2.

[0242] The refractive index was measured by a prism coupler method at wavelengths of 486 nm, 587 nm, and 656 nm, and the average values ​​are shown in Table 2 below. The refractive indexes measured at each wavelength were all the same.

[0243] Table 1 below shows the molar ratios of the monomers used in the polycarbonate resins used in the examples and comparative examples. [Table 1]

[0244] [Table 2] In Table 2, Tg means glass transition temperature and MI means melt index.

[0245] In Table 2, it can be seen that the resins of Examples 1 and 2 of the polycarbonate resin according to one embodiment of the present specification contain the first unit, the second unit, and the third unit, and the relaxation time of the polycarbonate resin is 1 to 15 seconds or 2 to 15 seconds at 250°C, and the residual phenol content is less than 3000 ppm. Specifically, the resins of Examples 1 and 2 have a relaxation time of 3.39 to 14.2 seconds at 250°C and a residual phenol content of 470 to 720 ppm.

[0246] In contrast, the polycarbonate resins of Comparative Examples 1 to 4, which are resins containing the first unit, the second unit, or the third unit, respectively, and the polycarbonate resins of Comparative Examples 5 to 8, which contain only two of the first unit, the second unit, or the third unit, have a relaxation time of less than 1 second or more than 15 seconds at 250°C and / or a residual phenol content of more than 3000 ppm. When the relaxation time is less than 1 second, the viscosity is low, and the low viscosity and short relaxation time of the resin make processing very difficult. When the relaxation time is more than 15 seconds, the viscosity is high, and the high viscosity and long relaxation time of the resin increase the processing load and cause phenomena such as weld lines, cracks, warpage, birefringence, and unmolded parts during injection molding.

[0247] Furthermore, if the residual phenol content exceeds 3000 ppm, the molecular weight of the polycarbonate resin will decrease, resulting in a decrease in strength and physical properties, which can cause many problems, such as cracking of the injected product during processing.

[0248] Although Comparative Examples 2, 3, 6, and 8 have higher refractive indices than Examples 1 and 2, their relaxation times at 250°C are less than 1 second or more than 15 seconds, making them difficult to process and commercialize.

[0249] In addition, Comparative Examples 3 and 8 have higher refractive indices than Examples 1 and 2, but the residual phenol content exceeds 3000 ppm, which reduces the molecular weight of the polycarbonate resin, resulting in reduced strength and physical properties, causing many problems such as cracking of the injected product during processing, and reducing processing stability.

[0250] Therefore, the polycarbonate resin according to one embodiment of the present specification has a relaxation time of 1 to 15 seconds or 2 to 15 seconds at 250°C and a residual phenol content of less than 3000 ppm, resulting in a relatively short molecular relaxation time. This allows for fast cooling in the mold during injection molding, reduces processing load, shortens the time between filling cycles, and reduces relaxation time. Furthermore, because the residual phenol content is 3000 ppm or less, there is little molecular weight loss during processing. Therefore, phenomena such as weld lines, cracks, warpage, birefringence, and undermolding during injection molding are reduced, resulting in excellent processing stability.

Claims

1. The relaxation time is 1 to 15 seconds at 250°C, and the residual phenol content is 3000 ppm or less. It comprises a first unit of the following chemical formula 1: a second unit of the following chemical formula 2: and a third unit of the following chemical formula 3: A polycarbonate resin comprising a first unit of the following Chemical Formula 1, a second unit of the following Chemical Formula 2, and a third unit of the following Chemical Formula 3 in a ratio of 0.01 mol % to 99.98 mol %: 0.01 mol % to 99.98 mol %: 0.01 mol % to 99.98 mol %, respectively: [Chemical formula 1] 【Chemistry 1】 In the above Chemical Formula 1, X1 to X4 are the same or different and each independently represents O or S; R1 to R4 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted heteroaryl group; Z1 and Z2 are the same or different and each independently represent a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; R and R are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or are bonded to each other to form a substituted or unsubstituted hydrocarbon ring; R101 and R102 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; r101 is 1 or 2, and when r101 is 2, the two R101 are the same or different from each other; r102 is 1 or 2, and when r102 is 2, the two R102 are the same or different from each other; m and n are each an integer from 0 to 6, p is an integer from 1 to 6; When m, n, and p are each 2 or more, the structures in the two or more brackets may be the same or different, * indicates a site connected to the main chain of the resin. [Chemical formula 2] 【Chemistry 2】 In the above Chemical Formula 2, X5 to X8 are the same or different and each independently represents O or S; L1 and L2 are the same or different and each independently represent a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group; R and R are the same or different and each independently represent a hydrogen atom; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or are bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; Z and Z are the same or different and each independently represent a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; m' and n' are each an integer from 0 to 6, p' is an integer from 1 to 6, r13 and r14 each represent an integer of 1 to 4, When r13, r14, m', n', and p' are each 2 or more, the structures in the two or more brackets are the same or different from each other, * indicates a site connected to the main chain of the resin. [Chemical formula 3] 【Transformation 3】 In the above Chemical Formula 3, X9 to X12 are the same or different and each independently represents O or S; Z5 and Z6 are the same or different and each independently represent a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; R15 and R16 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or are bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; m″ and n″ are each an integer from 0 to 6; p″ is an integer from 1 to 6; r15 and r16 each represent an integer of 1 to 6; When r15, r16, m'', n'', and p'' are each 2 or more, the structures in the two or more brackets are the same or different from each other, * indicates the site connected to the main chain of the resin.

2. 2. The polycarbonate resin according to claim 1, wherein the high shear viscosity of the polycarbonate resin is 10 Pa·s to 200 Pa·s at one or more of 250°C, 10 Hz and 250°C, 63 Hz.

3. 2. The polycarbonate resin according to claim 1, wherein the relaxation time of the polycarbonate resin is 2 to 15 seconds.

4. 2. The polycarbonate resin according to claim 1, having an MI (melt index) of 5 to 150.

5. 2. The polycarbonate resin of claim 1, comprising two or more second units of Formula 2.

6. A compound of formula 1a: A compound of formula 2a: A compound of formula 3a:

10. A method for producing the polycarbonate resin of claim 1, comprising polymerizing a composition for producing a polycarbonate resin comprising a polycarbonate precursor: [Chemical formula 1a] 【Chemistry 4】 In the above formula 1a, X1 to X4 are the same or different and each independently represents O or S; R1 to R4 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted heteroaryl group; Z1 and Z2 are the same or different and each independently represent a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; R and R are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or are bonded to each other to form a substituted or unsubstituted hydrocarbon ring; R101 and R102 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; r101 is 1 or 2, and when r101 is 2, the two R101 are the same or different from each other; r102 is 1 or 2, and when r102 is 2, the two R102 are the same or different from each other; m and n are each an integer from 0 to 6, When m and n are each 2 or more, the structures in the two or more parentheses may be the same or different, [Chemical formula 2a] 【Transformation 5】 [Chemical formula 3a] 【Transformation 6】 In the above formulas 2a and 3a, X5 to X12 are the same or different and each independently represents O or S; L1 and L2 are the same or different and each independently represent a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group; Z3 to Z6 are the same or different and each independently represent a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; R13 to R16 are the same or different and each independently represent hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or are bonded to adjacent groups to form a substituted or unsubstituted hydrocarbon ring; r13 and r14 each represent an integer of 1 to 4, r15 and r16 each represent an integer of 1 to 6; m', m'', n', and n'' are each an integer from 0 to 6; When each of r13 to r16, m', m'', n', and n'' is 2 or more, the structures in the two or more brackets may be the same or different.

7. 7. The method for producing a polycarbonate resin according to claim 6, wherein the polycarbonate precursor is a compound represented by the following chemical formula A: [Chemical formula A] 【Transformation 7】 In the above chemical formula A, Rb1 and Rb2 are the same or different and each independently represent a halogen group; a hydroxy group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; or a substituted or unsubstituted aryl group; a1 and a2 are each 0 or 1.

8. A polycarbonate resin composition comprising the polycarbonate resin according to claim 1.

9. A molded article comprising the polycarbonate resin composition according to claim 8.

10. The molded article according to claim 9, which is an optical lens.

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