Polycarbonate copolymer, its production method, and composition containing same

Abstract

The polycarbonate copolymer of the present invention is a polycarbonate copolymer containing units derived from at least one or more primary dihydroxyl compounds and units derived from at least two or more secondary dihydroxyl compounds, and the polycarbonate copolymer has a pencil hardness of H or more as measured by a pencil hardness test (ISO 15184) and a glass transition temperature (Tg) of about 90° C. to about 160° C. as measured by ISO 11357. The polycarbonate copolymer is excellent in heat resistance, scratch resistance, moldability, light resistance, weather resistance, transparency, mechanical strength, etc.

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate copolymer, a method for producing the same, and a composition containing the same. More specifically, the present invention relates to a polycarbonate copolymer excellent in heat resistance, scratch resistance, moldability, light resistance, weather resistance, transparency, mechanical strength, etc., a method for producing the same, and a composition containing the same. [Background technology]

[0002] Polycarbonate is a thermoplastic polymer that contains carbonate ester (-COO-) as a repeating unit in the main chain. Existing polycarbonates are mainly produced through the reaction of bisphenol-A (BPA) and phosgene (COCl2). While this polycarbonate exhibits excellent heat resistance, impact resistance, and flame retardancy, it is relatively poor in light resistance, transparency, and scratch resistance.

[0003] Furthermore, existing polycarbonates have a repeating aromatic ring structure, which causes yellowing when exposed to sunlight, including ultraviolet rays, resulting in reduced transmittance for light in certain wavelength ranges and breakage of the polymer chains, making them difficult to apply to fields requiring weather resistance.

[0004] On the other hand, it is known that if the monomer BPA remains in polycarbonate, it acts as an endocrine disruptor in the body. Therefore, various regulations are being tightened when using existing polycarbonate in products that come into contact with the human body, such as baby products, and medical products.

[0005] Furthermore, phosgene gas is a highly toxic substance subject to environmental regulations, and requires a separate cooling device for storage, making it difficult to store and manage.

[0006] Therefore, there is a demand for polycarbonates that overcome the above-mentioned shortcomings of existing polycarbonates and that are excellent in heat resistance, scratch resistance, moldability, light resistance, weather resistance, transparency, mechanical strength, etc. Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a polycarbonate copolymer excellent in heat resistance, scratch resistance, moldability, light resistance, weather resistance, transparency, mechanical strength, etc.

[0008] Another object of the present invention is to provide a method for producing said polycarbonate copolymer.

[0009] It is still another object of the present invention to provide a composition comprising said polycarbonate copolymer.

[0010] The above and other objects of the present invention can all be achieved by the present invention described below. [Means for solving the problem]

[0011] 1. One aspect of the present invention relates to a polycarbonate copolymer, which contains units derived from at least one primary dihydroxyl compound and units derived from at least two secondary dihydroxyl compounds, and which has a pencil hardness of H or higher as measured by a pencil hardness test (ISO 15184) and a glass transition temperature (Tg) of about 90°C to about 160°C as measured by ISO 11357.

[0012] 2. In the specific example of 1 above, the polycarbonate copolymer may contain about 1 mol % to about 30 mol % of units derived from a secondary dihydroxyl compound represented by the following chemical formula 4b among all units derived from dihydroxyls:

[0013] [Formula 4b] [ka]

[0014] In the above chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.

[0015] 3. In the specific example of 1 or 2 above, the polycarbonate copolymer may contain, among all units derived from dihydroxyls, about 5 mol % to about 45 mol % of units derived from primary dihydroxyl compounds, about 45 mol % to about 85 mol % of units derived from secondary dihydroxyl compounds represented by the following chemical formula 4a, and about 1 mol % to about 30 mol % of units derived from secondary dihydroxyl compounds represented by the following chemical formula 4b:

[0016] [Chemical formula 4a] [ka]

[0017] In the above chemical formula 4a, R7 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

[0018] [Formula 4b] [ka]

[0019] In the above chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.

[0020] 4. One aspect of the present invention relates to a polycarbonate copolymer, which contains about 5 mol % to about 95 mol % of at least one first repeating unit represented by the following chemical formula 1, and about 5 mol % to about 95 mol % of at least two second repeating units represented by the following chemical formula 2:

[0021] [Chemical formula 1] [ka]

[0022] In Chemical Formula 1, R1 is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxylene group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

[0023] [Chemical formula 2] [ka]

[0024] In the above Chemical Formula 2, R2 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

[0025] 5. In the specific example of 4 above, the polycarbonate copolymer may contain about 5 mol % to about 45 mol % of the first repeating unit, about 45 mol % to about 85 mol % of the second repeating unit represented by the following chemical formula 2a, and about 1 mol % to about 30 mol % of the second repeating unit represented by the following chemical formula 2b:

[0026] [Chemical formula 2a] [ka]

[0027] In the above chemical formula 2a, R7 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

[0028] [Chemical formula 2b] [ka]

[0029] In the above chemical formula 2b, R4 and R6 are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.

[0030] 6. In the specific example of 4 or 5, the first repeating unit is selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, and at least one or more primary dihydroxyl compounds including one or more of ethylene glycol, undecaethylene glycol, dodecaethylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecanedimethanol, decalindimethanol, tricyclotetradecane dimethanol, norbornane dimethanol, adamantane dimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, and bicyclo[2.2.2]octane-2,3-dimethanol, and at least one or more carbonic acid diester compounds.

[0031] 7. In the specific examples of 4 to 6 above, the second repeating unit may be derived from a secondary dihydroxyl compound including two or more of 1,4:3,6-dianhydrohexitol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, tricyclodecanediol, pentacyclopentadecanediol, decalindiol, tricyclotetradecanediol, norbornanediol, adamantanediol, 2,2-bis(4-hydroxycyclohexyl)propane, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and at least one or more carbonate diester compounds.

[0032] 8. In any of the specific examples 4 to 7 above, the polycarbonate copolymer may further include a third repeating unit derived from at least one tertiary dihydroxyl compound and at least one or more carbonate diester compounds.

[0033] 9. In any of the specific examples 4 to 8 above, the polycarbonate copolymer may have a pencil hardness of H or higher when measured by a pencil hardness test (ISO 15184), and may have a glass transition temperature (Tg) of about 90°C to about 160°C, as determined by ISO 11357, by heating a 10 mg sample at 220°C for 1 minute at a heating rate of 10°C per minute, cooling at a rate of 10°C per minute, and then heating the sample to 220°C at the same heating rate.

[0034] 10. In any of the specific examples 4 to 9, the polycarbonate copolymer may have a dynamic viscosity of about 8.5 cps to about 16 cps, as measured at 25°C using a Brookfield dynamic viscometer, of a solution prepared by dissolving 0.5 g of a sample in 14.5 g of a mixed solvent of hexafluoroisopropanol and dichloromethane.

[0035] 11. Another aspect of the present invention relates to a method for producing a polycarbonate copolymer, which comprises melting a dihydroxyl compound containing about 5 mol % to about 95 mol % of at least one primary dihydroxyl compound represented by the following chemical formula 3 and about 5 mol % to about 95 mol % of at least two or more secondary dihydroxyl compounds represented by the following chemical formula 4, together with at least one carbonate diester compound to obtain a melt, and then polycondensing the melt in the presence of a catalyst.

[0036] [Chemical formula 3] [ka]

[0037] In Chemical Formula 3, R1 is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxylene group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

[0038] [Chemical formula 4] [ka]

[0039] In the above Chemical Formula 4, R2 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

[0040] 12. In the specific example 11, the dihydroxyl compound may contain about 5 mol % to about 45 mol % of the primary dihydroxyl compound, about 45 mol % to about 85 mol % of a secondary dihydroxyl compound represented by the following chemical formula 4a, and about 1 mol % to about 30 mol % of a secondary dihydroxyl compound represented by the following chemical formula 4b:

[0041] [Chemical formula 4a] [ka]

[0042] In the above chemical formula 4a, R7 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

[0043] [Formula 4b] [ka]

[0044] In the above chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.

[0045] 13. In the specific example of 11 or 12, the dihydroxyl compound can further include at least one tertiary dihydroxyl compound, and the tertiary dihydroxyl compound can include one or more of 1,1'-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)cyclohexane, and bis(4-hydroxyphenyl)cyclopentane.

[0046] 14. In the specific examples 11 to 13, the carbonic acid diester compound can include one or more of diphenyl carbonate, ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate.

[0047] 15. Yet another aspect of the present invention relates to a composition containing a polycarbonate copolymer, the composition containing the polycarbonate copolymer according to any one of 1 to 10 above. [Effects of the Invention]

[0048] The present invention provides a polycarbonate copolymer excellent in heat resistance, scratch resistance, moldability, light resistance, weather resistance, transparency, mechanical strength, etc., a method for producing the same, and a composition containing the same. DETAILED DESCRIPTION OF THE INVENTION

[0049] The present invention will be described in detail below.

[0050] In this specification, the term "a to b" representing a numerical range is defined as "a or more and b or less."

[0051] (Polycarbonate copolymer) A polycarbonate copolymer according to one embodiment of the present invention is produced from three or more dihydroxyl compound monomers, which have an aromatic ring structure, few double bonds, and few triple bonds, and preferably no double bonds, excluding bisphenol-A, which inhibits eco-friendliness.

[0052] A polycarbonate copolymer according to one embodiment of the present invention comprises units derived from at least one primary dihydroxyl compound and units derived from at least two secondary dihydroxyl compounds, and may have a pencil hardness of H or greater as measured by the pencil hardness test (ISO 15184) and a glass transition temperature (Tg) of about 90°C to about 160°C as measured by ISO 11357.

[0053] In a specific example, the polycarbonate copolymer may contain about 1 mol % to about 30 mol % of units derived from a secondary dihydroxyl compound represented by the following chemical formula 4b, based on all units derived from dihydroxyls:

[0054] [Formula 4b] [ka]

[0055] In the chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.

[0056] In a specific example, the polycarbonate copolymer may contain, among all units derived from dihydroxyls, about 5 mol % to about 45 mol % of units derived from primary dihydroxyl compounds, about 45 mol % to about 85 mol % of units derived from secondary dihydroxyl compounds represented by the following chemical formula 4a, and about 1 mol % to about 30 mol % of units derived from secondary dihydroxyl compounds represented by the following chemical formula 4b:

[0057] [Chemical formula 4a] [ka]

[0058] In the above formula 4a, R7 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

[0059] [Formula 4b] [ka]

[0060] In the above formula 4b, R4 and R6 are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.

[0061] In a specific example, the molar ratio of the secondary dihydroxyl compound represented by Formula 4a to the secondary dihydroxyl compound represented by Formula 4b can be about 2:1 to about 8.5:1, for example, about 5:1 to about 8.2:1, specifically about 6:1 to about 8:1.

[0062] In a specific example, the primary dihydroxyl compound may be contained in an amount of about 5 mol % to about 45 mol %, for example, about 8 mol % to about 40 mol %, specifically about 10 mol % to about 35 mol %, based on 100 mol % of all dihydroxyl compounds.

[0063] In a specific example, the molar ratio of the primary dihydroxyl compound (the primary dihydroxyl compound represented by the following Chemical Formula 3) to the secondary dihydroxyl compound represented by the Chemical Formula 4a may be about 1:1.2 to about 1:8.

[0064] In a specific example, the contents of the primary dihydroxyl compound (the primary dihydroxyl compound represented by the following Chemical Formula 3) and the secondary dihydroxyl compound represented by the Chemical Formula 4b may satisfy the following Equation 1:

[0065] [Number 1] Content of primary dihydroxyl compounds >= Content of secondary dihydroxyl compounds represented by formula 4b

[0066] Furthermore, a polycarbonate copolymer according to one embodiment of the present invention can contain at least one first repeating unit represented by the following chemical formula 1 and at least two second repeating units represented by the following chemical formula 2:

[0067] [Chemical formula 1] [ka]

[0068] In Chemical Formula 1, R1 is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxylene group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

[0069] [Chemical formula 2] [ka]

[0070] In the above Chemical Formula 2, R2 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

[0071] Here, the term "substituted" means that a hydrogen atom is substituted with an alkyl group having 1 to 10 carbon atoms, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a cycloalkyl group having 3 to 10 carbon atoms, a heterocycloalkyl group having 3 to 10 carbon atoms, or a combination thereof.

[0072] Furthermore, the "alkyl", "alkoxy" and other substituents containing an "alkyl" moiety include both straight-chain and branched-chain forms, and the "cycloalkyl" includes both polycyclic ring structures such as saturated monocyclic and saturated bicyclic rings having 4 to 20 carbon atoms.

[0073] In a specific example, the polycarbonate copolymer may have a content of the first repeating unit of about 5 mol % to about 95 mol % and a content of the second repeating unit of about 5 mol % to about 95 mol % out of 100 mol % of all repeating units. Within these ranges, the polycarbonate copolymer may have excellent heat resistance, scratch resistance, moldability, light resistance, weather resistance, transparency, mechanical strength, etc.

[0074] In a specific example, the polycarbonate copolymer may contain about 5 mol % to about 45 mol % of the first repeating unit, about 45 mol % to about 85 mol % of the second repeating unit represented by the following chemical formula 2a, and about 1 mol % to about 30 mol % of the second repeating unit represented by the following chemical formula 2b:

[0075] [Chemical formula 2a] [ka]

[0076] In the above formula 2a, R7 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

[0077] [Chemical formula 2b] [ka]

[0078] In the above formula 2b, R4 and R6 are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.

[0079] In specific examples, the first repeating unit is ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, ), 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, triethylene glycol glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, undecaethylene glycol, dodecaethylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol;CHDM), tricyclodecanedimethanol, pentacyclopentadecanedimethanol, decalindimethanol, tricyclotetradecanedimethanol, norbornanedimethanol, adamantanedimethanol, 3,9-bis(1,1-dimethyl-2-methylpropional), The dihydroxyl group may be derived from, but is not limited to, primary dihydroxyl compounds, including one or more of 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, and bicyclo[2.2.2]octane-2,3-dimethanol, and at least one carbonate diester compound;

[0080] In specific examples, the second repeating unit is 1,4:3,6-dianhydrohexitol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, tricyclodecanediol, pentacyclopentadecanediol, decalindiol, or the like. The dihydroxyl group may be derived from, but is not limited to, secondary dihydroxyl compounds including two or more of 2,2-bis(4-hydroxycyclohexyl)propane, 2,2-bis(4-hydroxycyclohexyl)propane, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and at least one or more carbonic acid diester compounds.

[0081] In a specific example, the secondary dihydroxyl compound can include 1,4:3,6-dianhydrohexitol and 2,2-bis(4-hydroxycyclohexyl)propane, and / or 2,2,4,4-tetramethyl-1,3-cyclobutanediol, etc. Here, the 1,4:3,6-dianhydrohexitol can be isomannide, isosorbide, and / or isoidide, preferably isosorbide.

[0082] In a specific example, the second repeating unit may include a repeating unit represented by Chemical Formula 2a and a repeating unit represented by Chemical Formula 2b, and the molar ratio of the repeating unit represented by Chemical Formula 2a to the repeating unit represented by Chemical Formula 2b may be about 2:1 to about 8.5:1, for example, about 5:1 to about 8.2:1, specifically about 6:1 to about 8:1, but is not limited thereto.

[0083] In an embodiment, the polycarbonate copolymer can further include a third repeat unit derived from at least one tertiary dihydroxyl compound and at least one or more carbonic acid diester compounds.

[0084] In specific examples, the tertiary dihydroxyl compound can include 1,1'-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)cyclopentane, and combinations thereof.

[0085] In a specific example, the content of the third repeating unit may be 0 mol % to about 20 mol % based on a total of 100 mol % of the first repeating unit, the second repeating unit, and the third repeating unit. When the third repeating unit is included, the polycarbonate copolymer may have better heat resistance.

[0086] In a specific example, the polycarbonate copolymer may have a pencil hardness of H or more as measured by a pencil hardness test (ISO 15184).

[0087] In a specific example, the polycarbonate copolymer may have a glass transition temperature (Tg) of about 90°C to about 160°C, for example, about 100°C to about 155°C, at the transition point obtained when a 10 mg sample is heated at a rate of 10°C per minute, held at 220°C for 1 minute, cooled at a rate of 10°C per minute, and then heated to 220°C at the same heating rate according to ISO 11357.

[0088] In a specific example, the polycarbonate copolymer may have a dynamic viscosity of about 8.5 cps to about 16 cps, for example, about 9 cps to about 12 cps, as measured at 25°C using a Brookfield dynamic viscometer, where 0.5 g of the sample is dissolved in 14.5 g of a mixed solvent of hexafluoroisopropanol and dichloromethane.

[0089] As described above, the polycarbonate copolymer is a multi-component copolymer obtained by mixing (copolymerizing) the primary dihydroxyl compound and the secondary dihydroxyl compound as the dihydroxyl compound, which solves the brittleness problem that occurs when only the secondary dihydroxyl compound is used, and can simultaneously improve heat resistance and scratch resistance.

[0090] (Method for producing polycarbonate copolymer) A polycarbonate according to one embodiment of the present invention can be produced by a production method including: (1) melting a dihydroxyl compound containing about 5 mol % to about 95 mol % of at least one primary dihydroxyl compound represented by the following chemical formula 3 and about 5 mol % to about 95 mol % of at least two or more secondary dihydroxyl compounds represented by the following chemical formula 4, together with at least one carbonate diester compound to obtain a melt; and (2) condensation polymerizing the melt in the presence of a catalyst.

[0091] [Chemical formula 3] [ka]

[0092] In Chemical Formula 3, R1 is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxylene group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

[0093] [Chemical formula 4] [ka]

[0094] In the above Chemical Formula 4, R2 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

[0095] Step (1) In step (1), dihydroxyl compounds, including at least one of the primary dihydroxyl compounds and at least two of the secondary dihydroxyl compounds, and at least one carbonic acid diester compound are melted.

[0096] In a specific example, the dihydroxyl compound may contain about 5 mol % to about 45 mol % of the primary dihydroxyl compound, about 45 mol % to about 85 mol % of a secondary dihydroxyl compound represented by the following chemical formula 4a, and about 1 mol % to about 30 mol % of a secondary dihydroxyl compound represented by the following chemical formula 4b:

[0097] [Chemical formula 4a] [ka]

[0098] In the above chemical formula 4a, R7 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

[0099] [Formula 4b] [ka]

[0100] In the above formula 4b, R4 and R6 are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.

[0101] In a specific example, the dihydroxyl compound may further include the tertiary dihydroxyl compound in addition to the primary dihydroxyl compound and the secondary dihydroxyl compound.

[0102] In a specific example, the carbonic acid diester compound may be a compound represented by the following chemical formula 5:

[0103] [Chemical formula 5] AO-CO-O-A'

[0104] In the above Chemical Formula 5, A and A' are each independently a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 1 to 18 carbon atoms.

[0105] In a specific example, the carbonic acid diester compound may include, but is not limited to, one or more of diphenyl carbonate, ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Preferably, the carbonic acid diester compound may be diphenyl carbonate.

[0106] In a specific example, the content of the carbonate diester compound may be about 0.9 mol to about 1.1 mol per about 1 mol of the dihydroxyl compound, and within this range, the polycarbonate copolymer may have excellent heat resistance, scratch resistance, moldability, light resistance, weather resistance, transparency, mechanical strength, etc.

[0107] In a specific example, the above compounds can be melted at about 150° C. to about 250° C., but there is no particular limitation to this temperature range as long as these compounds are sufficiently melted.

[0108] Step (2) In step (2), the melt obtained in step (1) is subjected to polycondensation in the presence of a catalyst.

[0109] In an embodiment, the catalyst may comprise an alkali metal catalyst, an alkaline earth metal catalyst, or a mixture thereof.

[0110] In a specific example, the alkali metal catalyst may include one or more of lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), cesium hydroxide (CsOH), lithium carbonate (Li2CO3), sodium carbonate (Na2CO3), potassium carbonate (K2CO3), cesium carbonate (Cs2CO3), lithium acetate (LiOAc), sodium acetate (NaOAc), potassium acetate (KOAc), and cesium acetate (CsOAc), but is not particularly limited thereto.

[0111] In specific examples, the alkaline earth metal catalyst may include one or more of calcium hydroxide (Ca(OH)), barium hydroxide (Ba(OH)), magnesium hydroxide (Mg(OH)), strontium hydroxide (Sr(OH)), calcium carbonate (CaCO), barium carbonate (BaCO), magnesium carbonate (MgCO), strontium carbonate (SrCO), calcium acetate (Ca(OAc)), barium acetate (Ba(OAc)), magnesium acetate (Mg(OAc)), and strontium acetate (Sr(OAc)).

[0112] In a specific example, the catalyst content may be about 50 ppm to about 2,000 ppm relative to about 1 mole of the total dihydroxyl compounds, and within this range, the polycarbonate copolymer may have excellent heat resistance, scratch resistance, moldability, light resistance, weather resistance, transparency, mechanical strength, etc.

[0113] Meanwhile, the alkali metal and / or alkaline earth metal catalyst may be used together with a base catalyst such as an ammonium base or an amine, a phosphorus base, or a boron base compound, and the base catalyst may be used alone or in combination, and the amount used is not particularly limited.

[0114] Furthermore, during the melt polycondensation, additives such as an antioxidant and a heat stabilizer may be added as needed.

[0115] In specific examples, the antioxidants and heat stabilizers may include, for example, hindered phenols, hydroquinones, phosphites, and substituted compounds thereof.

[0116] In a specific example, the polycondensation may include (2-1) a primary reaction at a pressure of about 0.5 bar to about 5.0 bar and a temperature of about 150°C to about 250°C for about 0.5 to about 5.0 hours, and (2-2) a secondary reaction at a pressure of about 0.001 bar to about 0.5 bar and a temperature of about 190°C to about 250°C for about 0.5 to about 5.0 hours. By carrying out the reaction in step 2-2 after the dihydroxyl compound and the carbonate diester compound are fully reacted in the reaction in step 2-1, the monomer conversion rate can be increased, resulting in the synthesis of a copolymer with a higher molecular weight. In particular, a two-stage reaction is preferred because a high initial reaction temperature can accelerate the thermal decomposition of the monomer and polymer.

[0117] (composition) A composition according to an embodiment of the present invention contains the polycarbonate copolymer. For example, the composition can be produced as a composition further containing additional resin components and additives in addition to the polycarbonate copolymer.

[0118] In specific examples, the additives may include, but are not limited to, antioxidants, heat stabilizers, light absorbers, color formers, lubricants, colorants, conductive agents, nucleation agents, flame retardants, plasticizers, antistatic agents, combinations thereof, and the like.

[0119] In particular embodiments, the antioxidant and heat stabilizer may be the same as or different from those described in the method for making the polycarbonate copolymer.

[0120] In specific examples, the light absorber may be resorcinol, salicylate, or the like.

[0121] In specific examples, phosphites, hydrophosphites, and the like can be used as color formers.

[0122] In a specific example, the lubricant may be montanic acid, stearyl alcohol, or the like.

[0123] In a specific example, dyes, pigments, and the like can be used as colorants.

[0124] In a specific example, carbon black or the like can be used as the conductive agent or nucleating agent.

[0125] The type and amount of the additives are not particularly limited as long as they do not impair the physical properties, particularly the transparency, of the produced polycarbonate copolymer.

[0126] In a specific example, there is no particular limitation on the method for producing the polycarbonate copolymer composition, and a method for producing a polycarbonate composition known in the technical field to which the present invention pertains can be used as is or with appropriate modifications, and the resin components and additives described above can be mixed in any order without any particular order restrictions. For example, the required amounts of the resins and additives can be melted and extruded at a temperature of about 160°C to about 270°C using a single-screw and / or twin-screw extruder to produce a polycarbonate copolymer composition in pellet form.

[0127] (molded product) A molded article according to one embodiment of the present invention may be formed from the polycarbonate copolymer or a composition containing the polycarbonate copolymer. The method for producing the molded article is not particularly limited, and any method known in the art to which the present invention pertains may be used. For example, the molded article may be produced by molding the polycarbonate copolymer or a composition containing the polycarbonate copolymer using a conventional method such as injection molding, extrusion molding, casting molding, blow molding, rotational molding, or film molding.

[0128] In a specific example, the molded article is formed from the polycarbonate copolymer or a composition containing the same and may have excellent heat resistance, scratch resistance, moldability, light resistance, weather resistance, transparency, mechanical strength, etc. As a result, the molded article can be used for medical supplies, daily necessities, food containers, baby products, automobile interior and exterior materials, electronic product exterior materials, optical materials, glass substitute materials, solar energy materials, mobile phone materials, smart watch materials, safety products, industrial materials, 3D printing materials, building materials, cosmetic containers, etc.

[0129] The present invention will be described in more detail below with reference to examples. However, these examples are merely for illustrative purposes and should not be construed as limiting the present invention.

[0130] (Example) Example 1 A reactor equipped with a stirrer was charged with dihydroxyl compounds containing 10 mol% 1,4-butanediol as the primary dihydroxyl compound, 80 mol% isosorbide and 10 mol% 2,2-bis(4-hydroxycyclohexyl)propane as the secondary dihydroxyl compounds, and 1 mol of diphenyl carbonate per mol of the dihydroxyl compounds as the carbonate diester compound. 500 ppm (per mol of the total dihydroxyl compounds) of NaCO3 as a catalyst and 0.1 wt% triphenyl phosphite as a thermal stabilizer were added, and the temperature was raised to 180°C to melt the mixture and stirred for 1 hour. The temperature was then raised to 200°C and primary polymerization was carried out under a reduced pressure of 0.1 bar. The temperature was then gradually raised to 250°C and the pressure further reduced to 0.0013 bar to carry out the secondary polymerization reaction, producing a polycarbonate copolymer. The physical properties of the prepared polycarbonate copolymer specimens were evaluated by the following methods, and the results are shown in Table 1 below.

[0131] Example 2 A polycarbonate copolymer was prepared in the same manner as in Example 1, except that 20 mol % of 1,4-butanediol was used as the primary dihydroxyl compound, and 70 mol % of isosorbide and 10 mol % of 2,2-bis(4-hydroxycyclohexyl)propane were used as the secondary dihydroxyl compounds. The physical properties of the prepared polycarbonate copolymer specimens were evaluated using the following methods, and the results are shown in Table 1 below.

[0132] Example 3 A polycarbonate copolymer was prepared in the same manner as in Example 1, except that 35 mol% of 1,4-butanediol was used as the primary dihydroxyl compound, and 50 mol% of isosorbide and 15 mol% of 2,2-bis(4-hydroxycyclohexyl)propane were used as the secondary dihydroxyl compounds. The physical properties of the prepared polycarbonate copolymer specimens were evaluated using the following methods, and the results are shown in Table 1 below.

[0133] (Comparative Example 1) A polycarbonate copolymer was prepared in the same manner as in Example 1, except that 20 mol% of 1,4-butanediol was used as the primary dihydroxyl compound and 80 mol% of isosorbide was used as the secondary dihydroxyl compound. The physical properties of the prepared polycarbonate copolymer specimens were evaluated by the following methods, and the results are shown in Table 1 below.

[0134] (Comparative Example 2) A polycarbonate copolymer was prepared in the same manner as in Example 1, except that no primary dihydroxyl compound was used, and 80 mol % of isosorbide and 20 mol % of 2,2-bis(4-hydroxycyclohexyl)propane were used as secondary dihydroxyl compounds. The physical properties of the prepared polycarbonate copolymer specimens were evaluated by the following methods, and the results are shown in Table 1 below.

[0135] (Comparative Example 3) A polycarbonate copolymer was prepared in the same manner as in Example 1, except that no primary dihydroxyl compound was used and 100 mol% of isosorbide was used as the secondary dihydroxyl compound. The physical properties of the prepared polycarbonate copolymer specimens were evaluated by the following methods, and the results are shown in Table 1 below.

[0136] (Method of measuring physical properties) (1) Evaluation of scratch resistance: The pencil hardness of the specimens was evaluated by a pencil hardness test (ISO 15184).

[0137] (2) Glass transition temperature (Tg, unit: °C): In accordance with ISO 11357, a 10 mg sample was measured using a differential scanning calorimeter (DSC) by heating the sample at a rate of 10°C per minute, maintaining the temperature at 220°C for 1 minute, then cooling the sample at a rate of 10°C per minute, and then heating the sample to 220°C at the same heating rate. The glass transition temperature (Tg) was measured at the transition point.

[0138] (3) Dynamic viscosity (unit: cps): 0.5 g of the polycarbonate copolymer sample was dissolved in 14.5 g of a mixed solvent of hexafluoroisopropanol and dichloromethane, and the dynamic viscosity of the solution was measured at 25°C using a Brookfield dynamic viscometer (DV-II+Pro viscometer).

[0139] [Table 1]

[0140] From the above results, it can be seen that the polycarbonate copolymers of the present invention (Examples 1 to 3) are multicomponent copolymers obtained by mixing (copolymerizing) two or more primary and secondary dihydroxyl compounds as the dihydroxyl compounds, and can solve the problems of reduced scratch resistance, etc., that occur when only one secondary dihydroxyl compound is used, as in Comparative Example 1, and the problems of brittleness (pencil hardness measurement impossible, reduced scratch resistance) that occur when only a secondary dihydroxyl compound is used, as in Comparative Examples 2 and 3, and can simultaneously improve heat resistance (glass transition temperature) and scratch resistance. Furthermore, it was confirmed that the polycarbonate copolymers of the present invention have excellent moldability (dynamic viscosity), light resistance, weather resistance, transparency, mechanical strength, etc.

[0141] The present invention has been described above with reference to the preferred embodiments. Those skilled in the art will recognize that the present invention can be embodied in various modified forms without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative rather than a restrictive perspective. The scope of the present invention is defined by the claims, not the foregoing description, and all variations within the scope of the claims are intended to be embraced by the present invention.

[0142] (Addendum) (Appendix 1) units derived from at least one primary dihydroxyl compound, and units derived from at least two or more secondary dihydroxyl compounds, The polycarbonate copolymer has a pencil hardness of H or more when measured by a pencil hardness test (ISO 15184), A polycarbonate copolymer having a glass transition temperature (Tg) of about 90°C to about 160°C as measured by ISO 11357.

[0143] (Appendix 2) The polycarbonate copolymer according to Appendix 1, wherein the polycarbonate copolymer contains about 1 mol % to about 30 mol % of units derived from a secondary dihydroxyl compound represented by the following chemical formula 4b among all units derived from dihydroxyls: [Formula 4b] [ka] (In the above chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.)

[0144] (Appendix 3) The polycarbonate copolymer contains, in all dihydroxyl-derived units, about 5 mol % to about 45 mol % of units derived from primary dihydroxyl compounds; about 45 mol % to about 85 mol % of units derived from a secondary dihydroxyl compound represented by the following chemical formula 4a: Attachment 1: A polycarbonate copolymer according to Appendix 1, comprising about 1 mol % to about 30 mol % of units derived from a secondary dihydroxyl compound represented by the following chemical formula 4b: [Chemical formula 4a] [ka] (In the above chemical formula 4a, R7 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.) [Formula 4b] [ka] (In the above chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.)

[0145] (Appendix 4) About 5 mol % to about 95 mol % of at least one first repeating unit represented by the following chemical formula 1, and A polycarbonate copolymer containing about 5 mol % to about 95 mol % of at least two or more types of second repeating units represented by the following chemical formula 2: [Chemical formula 1] [ka] (In the above Chemical Formula 1, R1 is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxylene group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.) [Chemical formula 2] [ka] (In the above chemical formula 2, R2 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.)

[0146] (Appendix 5) The polycarbonate copolymer is about 5 mol % to about 45 mol % of the first repeating unit, about 45 mol % to about 85 mol % of a second repeating unit represented by the following chemical formula 2a, and 5. The polycarbonate copolymer according to claim 4, which contains about 1 mol % to about 30 mol % of the second repeating unit represented by the following chemical formula 2b: [Chemical formula 2a] [ka] (In the above chemical formula 2a, R7 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.) [Chemical formula 2b] [ka] (In the above chemical formula 2b, R4 and R6 are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.)

[0147] (Appendix 6) The first repeating unit is selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, and undecanediol. 5. The polycarbonate copolymer of claim 4, wherein the polycarbonate copolymer is derived from primary dihydroxyl compounds comprising one or more of the following: ethylene glycol, dodecaethylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecanedimethanol, decalin dimethanol, tricyclotetradecane dimethanol, norbornane dimethanol, adamantane dimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, and bicyclo[2.2.2]octane-2,3-dimethanol; and at least one or more carbonic acid diester compounds.

[0148] (Appendix 7) 5. The polycarbonate copolymer of claim 4, wherein the second repeat unit is derived from a secondary dihydroxyl compound including two or more of 1,4:3,6-dianhydrohexitol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, tricyclodecanediol, pentacyclopentadecanediol, decalindiol, tricyclotetradecanediol, norbornanediol, adamantanediol, 2,2-bis(4-hydroxycyclohexyl)propane, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and at least one carbonate diester compound.

[0149] (Appendix 8) 5. The polycarbonate copolymer of claim 4, further comprising a third repeat unit derived from at least one tertiary dihydroxyl compound and at least one or more carbonic acid diester compounds.

[0150] (Appendix 9) The polycarbonate copolymer is The pencil hardness of the specimen measured by the pencil hardness test (ISO 15184) is H or more, and A polycarbonate copolymer according to Appendix 4, having a glass transition temperature (Tg) of about 90°C to about 160°C at the transition point obtained when a 10 mg sample is heated in accordance with ISO 11357 at a heating rate of 10°C per minute, held at 220°C for 1 minute, cooled at a cooling rate of 10°C per minute, and then heated to 220°C at the same heating rate.

[0151] (Appendix 10) The polycarbonate copolymer according to Appendix 4, wherein the dynamic viscosity of a solution obtained by dissolving 0.5 g of a sample in 14.5 g of a mixed solvent of hexafluoroisopropanol and dichloromethane is about 8.5 cps to about 16 cps, as measured at 25°C using a Brookfield dynamic viscometer.

[0152] (Appendix 11) A dihydroxyl compound containing about 5 mol % to about 95 mol % of at least one primary dihydroxyl compound represented by the following chemical formula 3 and about 5 mol % to about 95 mol % of at least two secondary dihydroxyl compounds represented by the following chemical formula 4, and at least one carbonate diester compound are melted to obtain a melt; and polycondensing the melt in the presence of a catalyst. [Chemical formula 3] [ka] (In the above Chemical Formula 3, R1 is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxylene group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.) [Chemical formula 4] [ka] (In the above chemical formula 4, R2 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.)

[0153] (Appendix 12) The dihydroxyl compound is about 5 mol % to about 45 mol % of the primary dihydroxyl compound; about 45 mol % to about 85 mol % of a secondary dihydroxyl compound represented by the following chemical formula 4a: 12. A method for producing a polycarbonate copolymer according to claim 11, which contains about 1 mol % to about 30 mol % of a secondary dihydroxyl compound represented by the following chemical formula 4b: [Chemical formula 4a] [ka] (In the above chemical formula 4a, R7 is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.) [Formula 4b] [ka] (In the above chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.)

[0154] (Appendix 13) 12. The method for producing a polycarbonate copolymer according to claim 11, wherein the dihydroxyl compound further comprises at least one tertiary dihydroxyl compound, and the tertiary dihydroxyl compound comprises one or more of 1,1'-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)cyclohexane, and bis(4-hydroxyphenyl)cyclopentane.

[0155] (Appendix 14) 12. The method for producing a polycarbonate copolymer according to claim 11, wherein the carbonate diester compound includes at least one of diphenyl carbonate, ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate.

[0156] (Appendix 15) A composition comprising the polycarbonate copolymer according to any one of claims 1 to 10.

Claims

1. units derived from at least one primary dihydroxyl compound; and units derived from at least two or more secondary dihydroxyl compounds, The polycarbonate copolymer has a pencil hardness of H or more as measured by a pencil hardness test (ISO 15184), A polycarbonate copolymer having a glass transition temperature (Tg) of about 90°C to about 160°C as measured by ISO 11357.

2. The polycarbonate copolymer according to claim 1, wherein the polycarbonate copolymer contains from about 1 mol % to about 30 mol % of units derived from a secondary dihydroxyl compound represented by the following chemical formula 4b among all units derived from dihydroxyls. [Chemical formula 4b] 【Chemistry 1】 (In the above Chemical Formula 4b, R ４ and R ６ are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms; R ５ is a linear or branched alkylene group having 1 to 10 carbon atoms.

3. The polycarbonate copolymer contains, in all dihydroxyl-derived units, from about 5 mol % to about 45 mol % of units derived from primary dihydroxyl compounds; From about 45 mol % to about 85 mol % of units derived from a secondary dihydroxyl compound represented by formula 4a:

2. The polycarbonate copolymer of claim 1, comprising from about 1 mol % to about 30 mol % of units derived from a secondary dihydroxyl compound represented by formula 4b: [Chemical formula 4a] 【Chemistry 2】 (In the above Chemical Formula 4a, R ７ is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms. [Chemical formula 4b] 【Chemistry 3】 (In the above Chemical Formula 4b, R ４ and R ６ are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms; R ５ is a linear or branched alkylene group having 1 to 10 carbon atoms.

4. About 5 mol % to about 95 mol % of at least one first repeat unit represented by the following Chemical Formula 1, and A polycarbonate copolymer comprising about 5 mol % to about 95 mol % of at least two or more second repeating units represented by the following chemical formula 2: [Chemical formula 1] 【Chemistry 4】 (In the above Chemical Formula 1, R １ is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxylene group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms. [Chemical formula 2] 【Chemistry 5】 (In the above Chemical Formula 2, R ２ is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

5. The polycarbonate copolymer is about 5 mol % to about 45 mol % of the first repeat unit; About 45 mol % to about 85 mol % of a second repeat unit represented by the following chemical formula 2a, and The polycarbonate copolymer according to claim 4, comprising about 1 mol % to about 30 mol % of the second repeat unit represented by the following chemical formula 2b: [Chemical formula 2a] 【Chemistry 6】 (In the above formula 2a, R ７ is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms. [Chemical formula 2b] 【Chemistry 7】 (In the above formula 2b, R ４ and R ６ are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms; R ５ is a linear or branched alkylene group having 1 to 10 carbon atoms.

6. The first repeating unit is selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, undecaethylene glycol, 5. The polycarbonate copolymer of claim 4, which is derived from primary dihydroxyl compounds comprising one or more of ethylene glycol, dodecaethylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, decalin dimethanol, tricyclotetradecane dimethanol, norbornane dimethanol, adamantane dimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, and bicyclo[2.2.2]octane-2,3-dimethanol, and at least one or more carbonate diester compounds.

7. 5. The polycarbonate copolymer of claim 4, wherein the second repeat unit is derived from a secondary dihydroxyl compound comprising two or more of 1,4:3,6-dianhydrohexitol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, tricyclodecanediol, pentacyclopentadecanediol, decalindiol, tricyclotetradecanediol, norbornanediol, adamantanediol, 2,2-bis(4-hydroxycyclohexyl)propane, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and at least one carbonate diester compound.

8. 5. The polycarbonate copolymer of claim 4, wherein said polycarbonate copolymer further comprises a third repeat unit derived from at least one tertiary dihydroxyl compound and at least one or more carbonic acid diester compounds.

9. The polycarbonate copolymer is The pencil hardness of the specimen measured by the pencil hardness test (ISO 15184) is H or more, and The polycarbonate copolymer according to claim 4, which has a glass transition temperature (Tg) of about 90°C to about 160°C at the transition point obtained when a 10 mg sample is heated at a heating rate of 10°C per minute, held at 220°C for 1 minute, cooled at a cooling rate of 10°C per minute, and then heated to 220°C at the same heating rate according to ISO 11357.

10. The polycarbonate copolymer according to claim 4, wherein the polycarbonate copolymer has a dynamic viscosity of about 8.5 cps to about 16 cps as measured at 25° C. using a Brookfield dynamic viscometer in a solution of 0.5 g of a sample dissolved in 14.5 g of a mixed solvent of hexafluoroisopropanol and dichloromethane.

11. Melting a dihydroxyl compound containing about 5 mol % to about 95 mol % of at least one primary dihydroxyl compound represented by the following chemical formula 3 and about 5 mol % to about 95 mol % of at least two secondary dihydroxyl compounds represented by the following chemical formula 4, and at least one carbonate diester compound to obtain a melt; and polycondensing the melt in the presence of a catalyst. [Chemical formula 3] 【Chemistry 8】 (In the above Chemical Formula 3, R １ is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxylene group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms. [Chemical formula 4] 【Chemistry 9】 (In the above Chemical Formula 4, R ２ is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms.

12. The dihydroxyl compound is from about 5 mol % to about 45 mol % of said primary dihydroxyl compound; about 45 mol % to about 85 mol % of a secondary dihydroxyl compound represented by formula 4a:

12. The method of claim 11, further comprising about 1 mol % to about 30 mol % of a secondary dihydroxyl compound represented by the following formula 4b: [Chemical formula 4a] 【Chemistry 10】 (In the above Chemical Formula 4a, R ７ is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms, or a substituted or unsubstituted cycloalkoxylene group having 4 to 20 carbon atoms. [Chemical formula 4b] 【Chemistry 11】 (In the above Chemical Formula 4b, R ４ and R ６ are each independently a cycloalkylene group or a cycloalkoxylene group having 4 to 10 carbon atoms; R ５ is a linear or branched alkylene group having 1 to 10 carbon atoms.

13. The method for producing a polycarbonate copolymer according to claim 11, wherein the dihydroxyl compound further comprises at least one tertiary dihydroxyl compound, the tertiary dihydroxyl compound comprising one or more of 1,1'-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)cyclohexane, and bis(4-hydroxyphenyl)cyclopentane.

14. The method for producing a polycarbonate copolymer according to claim 11, wherein the carbonate diester compound includes at least one of diphenyl carbonate, ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate.

15. A composition comprising the polycarbonate copolymer of any one of claims 1 to 10.

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