Polycarbonate copolymer, method for producing the same, and composition containing the 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 having excellent 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 Art

[0002] Polycarbonate refers to a thermoplastic polymer containing 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). Such polycarbonates exhibit excellent heat resistance, impact resistance, and flame retardancy, but their light resistance, transmittance, scratch resistance, etc. are relatively poor.

[0003] In addition, since existing polycarbonates have an aromatic ring as a repeating structure, yellowing occurs due to sunlight containing ultraviolet rays, resulting in a lower transmittance for light in some wavelength regions and breakage of the polymer chains, making it difficult to apply them to fields requiring weather resistance.

[0004] On the other hand, it is known that when the monomer BPA remains in the polycarbonate, it acts as an endocrine disruptor in the living body. Therefore, existing polycarbonates are subject to strengthened regulations when used in products that come into contact with the human body, such as baby products, and various medical supplies.

[0005] In addition, phosgene gas is a substance subject to environmental regulations due to its high toxicity, and there is a problem that it is difficult to store and manage because a separate cooling device is required for its storage.

[0006] Therefore, there is a need for a polycarbonate that overcomes the shortcomings of existing polycarbonates and possesses superior heat resistance, scratch resistance, moldability, light resistance, weather resistance, transparency, and mechanical strength. [Overview of the project] [Problems that the invention aims to solve]

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

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

[0009] Another object of the present invention is to provide a composition comprising the polycarbonate copolymer.

[0010] All of the above and other objectives of the present invention can be achieved by the present invention as described below. [Means for solving the problem]

[0011] 1. One aspect of the present invention relates to a polycarbonate copolymer. The polycarbonate copolymer comprises units derived from at least one primary dihydroxyl compound and units derived from at least two secondary dihydroxyl compounds, wherein the polycarbonate copolymer has a pencil hardness of H or higher 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.

[0012] 2. In the specific example of paragraph 1 above, the polycarbonate copolymer may contain approximately 1 mol% to approximately 30 mol% of units derived from a secondary dihydroxyl compound represented by the following chemical formula 4b within the total dihydroxyl units.

[0013] [Formula 4b] [ka]

[0014] In the above chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or 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 examples of 1 or 2 above, the polycarbonate copolymer may contain, among the total units derived from dihydroxyl, approximately 5 mol% to approximately 45 mol% of units derived from a primary dihydroxyl compound, approximately 45 mol% to approximately 85 mol% of units derived from a secondary dihydroxyl compound represented by the following chemical formula 4a, and approximately 1 mol% to approximately 30 mol% of units derived from a secondary dihydroxyl compound 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 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. The polycarbonate copolymer contains about 5 mol% to about 95 mol% of at least one or more first repeating units represented by the following Chemical Formula 1, and about 5 mol% to about 95 mol% of at least two or more second repeating units represented by the following Chemical Formula 2.

[0021] [Chemical Formula 1] [Chemical Structure] [[ID=ll]]

[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][[ID=lg]] [Chemical Structure]

[0024] In 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 can contain 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 about 1 mol% to about 30 mol% of a second repeating unit represented by the following Chemical Formula 2b.

[0026] [Chemical Formula 2a] [Chemical Structure]

[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 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 examples of 4 or 5 above, 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, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decate These may be derived from primary dihydroxyl compounds comprising one or more of the following: ethylene glycol, undecaethylene glycol, dodecaethylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, decalindimethanol, tricyclotetradecanedimethanol, norbornanedimethanol, adamantanedimethanol, 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, as well as from at least one diester carbonate compound.

[0031] 7. In the specific examples of 4 to 6 above, the second repeating unit may be derived from a secondary dihydroxyl compound containing two or more of the following: 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, as well as from at least one diester carbonate compound.

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

[0033] 9. In any of the specific examples in 4 to 8 above, the polycarbonate copolymer has a pencil hardness of H or higher when measured by a pencil hardness test (ISO 15184), and according to ISO 11357, when 10 mg of the sample is heated at a rate of 10°C per minute and held at 220°C for 1 minute, then cooled at a rate of 10°C per minute, and then heated to 220°C at the same rate, the glass transition temperature (Tg) at the transition point obtained may be approximately 90°C to approximately 160°C.

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

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

[0036] [Chemical formula 3] [ka]

[0037] 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.

[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 of 11 above, 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 the secondary dihydroxyl compound represented by the following chemical formula 4a, and about 1 mol% to about 30 mol% of the 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 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 examples of 11 or 12 above, the dihydroxyl compound may further include at least one tertiary dihydroxyl compound, the tertiary dihydroxyl compound may 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 described in 11 to 13 above, the diester carbonate compound may include one or more of diphenyl carbonate, dityl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate.

[0047] 15. Yet another aspect of the present invention relates to compositions comprising a polycarbonate copolymer. The composition comprises a polycarbonate copolymer according to any of the above 1 to 10. [Effects of the Invention]

[0048] The present invention provides a polycarbonate copolymer with excellent 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. [Modes for carrying out the invention]

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

[0050] In this specification, the numerical range "a~b" is defined as "greater than or equal to a and less than or equal to b".

[0051] (Polycarbonate copolymer) A polycarbonate copolymer according to one specific example of the present invention is produced from three or more dihydroxyl compound monomers that have an aromatic ring structure, fewer double bonds and triple bonds, and preferably none of these, excluding bisphenol-A which inhibits eco-friendliness, etc.

[0052] A polycarbonate copolymer according to one specific example 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 can have a pencil hardness of H or higher when 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.

[0053] In a specific example, the polycarbonate copolymer may contain approximately 1 mol% to approximately 30 mol% of units derived from a secondary dihydroxyl compound represented by the following chemical formula 4b, within the total units derived from dihydroxyl.

[0054] [Formula 4b] [ka]

[0055] In chemical formula 4b, R4 and R6 are independently cycloalkylene or cycloalkoxylene groups 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 the total units derived from dihydroxyl, approximately 5 mol% to approximately 45 mol% of units derived from a primary dihydroxyl compound, approximately 45 mol% to approximately 85 mol% of units derived from a secondary dihydroxyl compound represented by the following chemical formula 4a, and approximately 1 mol% to approximately 30 mol% of units derived from a secondary dihydroxyl compound represented by the following chemical formula 4b.

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

[0058] 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.

[0059] [Formula 4b] [ka]

[0060] In the aforementioned chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or 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 chemical formula 4a to the secondary dihydroxyl compound represented by chemical formula 4b can be approximately 2:1 to approximately 8.5:1, for example, approximately 5:1 to approximately 8.2:1, and specifically approximately 6:1 to approximately 8:1.

[0062] In a specific example, the primary dihydroxyl compound may be present 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%, of 100 mol% of the total dihydroxyl compound.

[0063] In a specific example, the molar ratio of the primary dihydroxyl compound (represented by chemical formula 3 below) to the secondary dihydroxyl compound represented by chemical formula 4a can be approximately 1:1.2 to approximately 1:8.

[0064] In a specific example, the content of the primary dihydroxyl compound (the primary dihydroxyl compound represented by chemical formula 3 below) and the secondary dihydroxyl compound represented by chemical formula 4b may satisfy the following formula 1.

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

[0066] Furthermore, a polycarbonate copolymer according to one specific example of the present invention may include 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 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.

[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, "substitution" means that the hydrogen atom is substituted with an alkyl group having 1 to 10 carbon atoms, a halogen atom, a nitro group, a cyano group, a hydroxyl 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 substituted compounds containing the "alkyl," "alkoxy," and other "alkyl" portions include both linear and branched chain forms, and the "cycloalkyl" includes both saturated monocyclic and saturated bicyclic polycyclic structures with 4 to 20 carbon atoms.

[0073] In a specific example, the polycarbonate copolymer may have a content of approximately 5 mol% to approximately 95 mol% of the first repeating units and a content of approximately 5 mol% to approximately 95 mol% of the total repeating units. Within this range, the polycarbonate copolymer may exhibit excellent heat resistance, scratch resistance, moldability, light resistance, weather resistance, transparency, mechanical strength, and the like.

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

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

[0076] 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.

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

[0078] In the above chemical formula 2b, R4 and R6 are each independently a cycloalkylene group or 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, and 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, norbornanediethanol, adamantanediethanol, 3,9-bis(1,1-di The primary dihydroxyl compound may be derived from, but is not limited to, one or more primary dihydroxyl compounds containing methyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane and bicycle[2.2.2]octane-2,3-dimethanol, as well as from at least one or more diester carbonate compounds.

[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 Secondary dihydroxyl compounds comprising two or more of the following: calindiol, tricyclotetradecanediol, norbornanediol, adamantanediol, 2,2-bis(4-hydroxycyclohexyl)propane, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, as well as compounds derived from at least one diester carbonate compound, may be, but are not limited to, those derived from these.

[0081] In specific examples, the secondary dihydroxyl compound may 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, 1,4:3,6-dianhydrohexitol may be an isomannide, isosorbide, and / or isoidide, and is preferably isosorbide.

[0082] In a specific example, the second repeating unit may include the repeating unit represented by chemical formula 2a and the 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 approximately 2:1 to approximately 8.5:1, for example approximately 5:1 to approximately 8.2:1, specifically approximately 6:1 to approximately 8:1, but is not limited thereto.

[0083] In a specific example, the polycarbonate copolymer may further comprise a third repeating unit derived from at least one tertiary dihydroxyl compound and at least one or more diester carbonate compounds.

[0084] In specific examples, the tertiary dihydroxyl compound may 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 can be 0 mol% to about 20 mol% of the total 100 mol% of the first, second, and third repeating units. When the third repeating unit is included, the polycarbonate copolymer may exhibit superior heat resistance.

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

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

[0088] In a specific example, the polycarbonate copolymer can have a dynamic viscosity of approximately 8.5 cps to approximately 16 cps, for example, approximately 9 cps to approximately 12 cps, when a solution prepared by dissolving 0.5 g of the sample in a mixed solvent of hexafluoroisopropanol and dichloromethane is measured at 25°C using a Brookfield dynamic viscometer.

[0089] Thus, the polycarbonate copolymer is a multi-component copolymer obtained by always mixing (copolymerizing) the primary dihydroxyl compound and the secondary dihydroxyl compound as the dihydroxyl compound, thereby solving the brittleness problem that occurs when only the secondary dihydroxyl compound is applied, and simultaneously improving heat resistance and scratch resistance.

[0090] (Method for producing polycarbonate copolymer) A specific example of the present invention can be produced by a production method comprising: (1) melting a dihydroxyl compound containing at least one primary dihydroxyl compound represented by the following chemical formula 3 in an amount of about 5 mol% to about 95 mol%, and at least two secondary dihydroxyl compounds represented by the following chemical formula 4 in an amount of about 5 mol% to about 95 mol%, and at least one diester carbonate compound to obtain a molten product; and (2) condensing the molten product in the presence of a catalyst.

[0091] [Chemical formula 3] [ka]

[0092] 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.

[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), a dihydroxyl compound comprising at least one primary dihydroxyl compound and at least two secondary dihydroxyl compounds, and at least one diester carbonate compound are melted.

[0096] In a specific example, the dihydroxyl compound may contain approximately 5 mol% to approximately 45 mol% of the primary dihydroxyl compound, approximately 45 mol% to approximately 85 mol% of the secondary dihydroxyl compound represented by the following chemical formula 4a, and approximately 1 mol% to approximately 30 mol% of the 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 aforementioned chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or 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 specific examples, diester carbonate compounds can be compounds 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 specific examples, the diester carbonate 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 diester carbonate compound may be diphenyl carbonate.

[0106] In a specific example, the content of the diester carbonate compound can be approximately 0.9 moles to approximately 1.1 moles per approximately 1 mole of the dihydroxyl compound. Within this range, the polycarbonate copolymer can exhibit excellent heat resistance, scratch resistance, moldability, light resistance, weather resistance, transparency, mechanical strength, and the like.

[0107] In specific examples, the above compounds can be melted at approximately 150°C to 250°C, but the temperature range is not particularly limited as long as these compounds are sufficiently melted.

[0108] Step (2) In step (2), the molten material obtained in step (1) is subjected to condensation polymerization in the presence of a catalyst.

[0109] In specific examples, the catalyst may include an alkali metal catalyst, an alkaline earth metal catalyst, or a mixture thereof.

[0110] In specific examples, the alkali metal catalyst may include, but is not particularly limited to, one or more of the following: 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).

[0111] In specific examples, the alkaline earth metal catalyst may include, but is not particularly limited to, one or more of the following: calcium hydroxide (Ca(OH)2), barium hydroxide (Ba(OH)2), magnesium hydroxide (Mg(OH)2), strontium hydroxide (Sr(OH)2), calcium carbonate (CaCO3), barium carbonate (BaCO3), magnesium carbonate (MgCO3), strontium carbonate (SrCO3), calcium acetate (Ca(OAc)2), barium acetate (Ba(OAc)2), magnesium acetate (Mg(OAc)2), and strontium acetate (Sr(OAc)2).

[0112] In specific examples, the content of the catalyst can range from approximately 50 ppm to approximately 2,000 ppm per approximately 1 mole of the total dihydroxyl compound. Within this range, the polycarbonate copolymer can exhibit excellent heat resistance, scratch resistance, moldability, light resistance, weather resistance, transparency, mechanical strength, and the like.

[0113] On the other hand, the alkali metal and / or alkaline earth metal catalyst can be used together with a base catalyst such as an ammonium or amine base, a phosphorus base, or a boron base compound, and the base catalyst can be used alone or in combination, with no particular limit on the amount used.

[0114] Furthermore, during melt condensation polymerization, additives such as antioxidants and heat stabilizers may be added as needed.

[0115] In specific examples, examples of the antioxidant and heat stabilizer include hindered phenol, hydroquinone, phosphite, and compounds substituted therewith.

[0116] In specific examples, the condensation polymerization 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 hours 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 hours to about 5.0 hours. By thoroughly reacting the dihydroxyl compound and the diester carbonate compound through the reaction in step 2-1, and then carrying out the reaction in step 2-2, the monomer conversion rate can be increased, and copolymers with even higher molecular weights can be synthesized. In particular, if the initial reaction temperature is high, the thermal decomposition of the monomer and polymer may be accelerated, so it is preferable to carry out the reaction in two steps.

[0117] (composition) One specific example of the present invention is a composition comprising the polycarbonate copolymer. For example, the composition may be manufactured further comprising additional resin components or additives in addition to the polycarbonate copolymer.

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

[0119] In specific examples, the antioxidant and heat stabilizer may be the same as those described in the method for producing the polycarbonate copolymer, or they may be different.

[0120] In specific examples, resorcinol, salicylate, and the like can be used as light absorbers.

[0121] In specific examples, phosphates, hydrophosphite, and the like can be used as colorants.

[0122] In specific examples, montanic acid, stearyl alcohol, and the like can be used as lubricants.

[0123] In specific examples, dyes and pigments can be used as colorants.

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

[0125] Here, the type and amount of the additive are not particularly limited, as long as they do not impair the physical properties of the manufactured polycarbonate copolymer, especially its transparency.

[0126] In specific examples, there are no special restrictions on the method for producing the polycarbonate copolymer composition. Methods for producing polycarbonate compositions known in the art to which the present invention belongs can be used as is or with appropriate modifications. The resin components and additives described above can be freely selected and mixed in any order without any special order restrictions. For example, the required amount of each of the above resins and additives can be melted and extruded using a single-screw and / or twin-screw extruder at a temperature of about 160°C to about 270°C to produce a polycarbonate copolymer composition in pellet form.

[0127] (molded product) A molded article according to one embodiment of the present invention can be formed from the polycarbonate copolymer or a composition containing the polycarbonate copolymer. There are no special restrictions on the method of producing the molded article, and methods known in the art to which the present invention belongs can be used. For example, the polycarbonate copolymer or a composition containing the polycarbonate copolymer can be molded by conventional methods such as injection molding, extrusion molding, casting molding, blow molding, rotational molding, and film molding to produce a molded article.

[0128] In specific examples, the molded article may be 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 in medical supplies, household goods, food containers, infant products, interior and exterior materials for automobiles, exterior materials for electronic products, optical materials, glass substitute materials, solar energy materials, mobile phone materials, smartwatch materials, safety products, industrial materials, 3D printing materials, building materials, cosmetic containers, etc.

[0129] The present invention will be described more specifically below with reference to examples, but such examples are for illustrative purposes only and should not be construed as limiting the present invention.

[0130] (Examples) (Example 1) In a reactor equipped with a stirrer, a dihydroxyl compound containing 10 mol% of 1,4-butanediol as the primary dihydroxyl compound, 80 mol% of isosorbide and 10 mol% of 2,2-bis(4-hydroxycyclohexyl)propane as the secondary dihydroxyl compound, and 1 mole of diphenyl carbonate per mole of the total dihydroxyl compound were packed. Na2CO3 500 ppm (per mole of total dihydroxyl compound) was added as a catalyst, and 0.1 wt% of triphenyl phosphite was added as a heat stabilizer. The temperature was then raised to 180°C to melt the mixture, and it was stirred for 1 hour. Subsequently, the temperature was raised to 200°C, and primary polymerization was carried out under reduced pressure of 0.1 bar. The temperature was then gradually raised to 250°C, and the pressure was further reduced to 0.0013 bar to carry out the secondary reaction polymerization and produce a polycarbonate copolymer. The physical properties of the manufactured polycarbonate copolymer specimens were evaluated using the following method, and the results are shown in Table 1 below.

[0131] (Example 2) Polycarbonate copolymers were 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 method described below, and the results are shown in Table 1 below.

[0132] (Example 3) Polycarbonate copolymers were 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 method described below, and the results are shown in Table 1 below.

[0133] (Comparative Example 1) Polycarbonate copolymers were 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 using the method described below, and the results are shown in Table 1 below.

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

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

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

[0137] (2) Glass transition temperature (Tg, unit: °C): According to ISO 11357, 10 mg of the sample was heated at a rate of 10 °C per minute using a differential scanning calorimeter (DSC), held at 220 °C for 1 minute, then cooled at a rate of 10 °C per minute, and the glass transition temperature (Tg) was measured at the transition point obtained when the sample was heated to 220 °C at the same heating rate.

[0138] (3) Dynamic viscosity (unit: cps): The dynamic viscosity of a solution prepared by dissolving 0.5 g of the polycarbonate copolymer sample in a mixed solvent of 14.5 g of hexafluoroisopropanol and dichloromethane 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 1-3) are multi-component copolymers obtained by always mixing and applying (copolymerizing) the primary dihydroxyl compound and two or more secondary dihydroxyl compounds as the dihydroxyl compound. This solves the problem of reduced scratch resistance when using one type of secondary dihydroxyl compound, as in Comparative Example 1, and the problem of brittleness (inability to measure pencil hardness, reduced scratch resistance) when using only secondary dihydroxyl compounds, as in Comparative Examples 2 and 3, and simultaneously improves 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, primarily focusing on its embodiments. Those with ordinary skill in the art to which the present invention pertains will understand that the present invention can be embodied in modified forms that do not deviate from its essential characteristics. Therefore, the disclosed embodiments should be considered illustrative, not restrictive. The scope of the present invention is defined in the claims, not in the foregoing description, and all differences within an equivalent scope are to be interpreted as being included within the scope of the present invention.

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

[0143] (Note 2) The polycarbonate copolymer described in Appendix 1 contains, in which units derived from a secondary dihydroxyl compound represented by the following chemical formula 4b are present in an amount of approximately 1 mol% to approximately 30 mol% of the total dihydroxyl units. [Formula 4b] [ka] (In the above chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.)

[0144] (Note 3) The aforementioned polycarbonate copolymer contains units derived from all dihydroxyls, Units derived from primary dihydroxyl compounds are present in approximately 5 mol% to 45 mol%. Approximately 45 mol% to approximately 85 mol% of units derived from the secondary dihydroxyl compound represented by the following chemical formula 4a, and A polycarbonate copolymer as described in Appendix 1, containing approximately 1 mol% to approximately 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 cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.)

[0145] (Note 4) At least one type of first repeating unit represented by the following chemical formula 1 is present in an amount of approximately 5 mol% to approximately 95 mol%, and A polycarbonate copolymer containing at least two types of second repeating units represented by the following chemical formula 2 in an amount of approximately 5 mol% to approximately 95 mol%. [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] (Note 5) The aforementioned polycarbonate copolymer is The first repeating unit is made up of approximately 5 mol% to approximately 45 mol%, The second repeating unit represented by the chemical formula 2a below is present in an amount of approximately 45 mol% to approximately 85 mol%, and, A polycarbonate copolymer as described in Appendix 4, containing approximately 1 mol% to approximately 30 mol% of the second repeating unit represented by the chemical formula 2b below. [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 cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.)

[0147] (Note 6) 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, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, undecanediol A polycarbonate copolymer according to Appendix 4, derived from a primary dihydroxyl compound comprising one or more of the following: ethylene glycol, dodecaethylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, decalindimethanol, tricyclotetradecanedimethanol, norbornanedimethanol, adamantanedimethanol, 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 diester carbonate compounds.

[0148] (Note 7) The polycarbonate copolymer described in Appendix 4, wherein the second repeating unit is derived from a secondary dihydroxyl compound comprising two or more of the following: 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, as well as at least one diester carbonate compound.

[0149] (Note 8) The polycarbonate copolymer according to Appendix 4, further comprising a third repeating unit derived from at least one tertiary dihydroxyl compound and at least one or more diester carbonate compounds.

[0150] (Note 9) The aforementioned polycarbonate copolymer is The pencil hardness of the test specimen measured by the pencil hardness test (ISO 15184) is H or higher, and, A polycarbonate copolymer as described in Appendix 4, wherein, according to ISO 11357, 10 mg of the sample is heated at a rate of 10°C per minute, maintained at 220°C for 1 minute, then cooled at a rate of 10°C per minute, and the temperature is raised to 220°C at the same heating rate, resulting in a glass transition temperature (Tg) of approximately 90°C to approximately 160°C at the transition point obtained.

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

[0152] (Note 11) A dihydroxyl compound containing at least one primary dihydroxyl compound represented by the following chemical formula 3 in an amount of approximately 5 mol% to approximately 95 mol%, and at least two secondary dihydroxyl compounds represented by the following chemical formula 4 in an amount of approximately 5 mol% to approximately 95 mol%, is melted with at least one diester carbonate compound to obtain a melt, and A method for producing a polycarbonate copolymer, comprising condensing the molten material 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] (Note 12) The aforementioned dihydroxyl compound The aforementioned primary dihydroxyl compound is contained in an amount of approximately 5 mol% to approximately 45 mol%, Approximately 45 mol% to approximately 85 mol% of the secondary dihydroxyl compound represented by the following chemical formula 4a, and A method for producing a polycarbonate copolymer as described in Appendix 11, comprising approximately 1 mol% to approximately 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 cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.)

[0154] (Note 13) The method for producing a polycarbonate copolymer according to Appendix 11, wherein the dihydroxyl compound may further comprise 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.

[0155] (Note 14) The method for producing a polycarbonate copolymer as described in Appendix 11, wherein the carbonic acid diester compound comprises one or more of diphenyl carbonate, ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate.

[0156] (Note 15) A composition comprising a polycarbonate copolymer as described in any one of the appendices 1 to 10.

Claims

1. Among the units derived from total dihydroxyl, Units derived from primary dihydroxyl compounds are used in amounts of 5 mol% to 45 mol%, A unit derived from the secondary dihydroxyl compound represented by the following chemical formula 4a is used in an amount of 45 mol% to 85 mol%, and This is a polycarbonate copolymer containing 1 mol% to 30 mol% of units derived from a secondary dihydroxyl compound represented by the following chemical formula 4b. [Chemical formula 4a] 【Chemistry 1】 (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.) [Chemical formula 4b] 【Chemistry 2】 (In the above chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.) The aforementioned polycarbonate copolymer has a pencil hardness of H or higher when measured by a pencil hardness test (ISO 15184). A polycarbonate copolymer having a glass transition temperature (Tg) of 90°C to 160°C as measured by ISO 11357.

2. At least one of the following chemical formulas 1 is present in a quantity of 5 mol% to 45 mol%, and The second repeating unit represented by the chemical formula 2a below is present in an amount of 45 mol% to 85 mol%, and A polycarbonate copolymer containing 1 mol% to 30 mol% of the second repeating unit represented by the following chemical formula 2b. [Chemical formula 1] 【Transformation 3】 (In the above chemical formula 1, R １ This includes single bonds, substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms, substituted or unsubstituted alkoxylene groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkylene groups having 4 to 20 carbon atoms, or substituted or unsubstituted cycloalkoxylene groups having 4 to 20 carbon atoms. [Chemical formula 2a] 【Chemistry 4】 (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] 【Transformation 5】 (In the above chemical formula 2b, R4 and R6 are each independently a cycloalkylene group or cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.)

3. 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, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, undecaethylene A polycarbonate copolymer according to claim 2, derived from a primary dihydroxyl compound comprising one or more of the following: lenglycol, dodecaethylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, decalindimethanol, tricyclotetradecanedimethanol, norbornanedimethanol, adamantanedimethanol, 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 diester carbonate compounds.

4. The polycarbonate copolymer according to claim 2, wherein the second repeating unit is derived from a secondary dihydroxyl compound comprising two or more of the following: 1,4:3,6-dianehydrohexitol, 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, as well as at least one diester carbonate compound.

5. The polycarbonate copolymer according to claim 2, further comprising a third repeating unit derived from at least one tertiary dihydroxyl compound and at least one or more diester carbonate compounds.

6. The aforementioned polycarbonate copolymer is The pencil hardness of the test specimen measured by the pencil hardness test (ISO 15184) is H or higher, and, The polycarbonate copolymer according to claim 2, wherein, according to ISO 11357, 10 mg of the sample is heated at a rate of 10°C per minute and maintained at 220°C for 1 minute, then cooled at a rate of 10°C per minute, and when heated to 220°C at the same rate, the glass transition temperature (Tg) at the transition point obtained is 90°C to 160°C.

7. The polycarbonate copolymer according to claim 2, wherein the dynamic viscosity of the solution obtained by dissolving 0.5 g of the sample in a mixed solvent of hexafluoroisopropanol and dichloromethane is measured at 25°C using a Brookfield dynamic viscometer is 8.5 cps to 16 cps.

8. A dihydroxyl compound containing 5 mol% to 45 mol% of at least one primary dihydroxyl compound represented by the following chemical formula 3, 45 mol% to 85 mol% of a secondary dihydroxyl compound represented by the following chemical formula 4a, and 1 mol% to 30 mol% of a secondary dihydroxyl compound represented by the following chemical formula 4b, and at least one diester carbonate compound, is melted to obtain a molten product, and A method for producing a polycarbonate copolymer, comprising condensing the molten material in the presence of a catalyst. [Chemical formula 3] 【Transformation 6】 (In the above chemical formula 3, R １ This includes single bonds, substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms, substituted or unsubstituted alkoxylene groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkylene groups having 4 to 20 carbon atoms, or substituted or unsubstituted cycloalkoxylene groups having 4 to 20 carbon atoms. [Chemical formula 4a] 【Transformation 7】 (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.) [Chemical formula 4b] 【Transformation 8】 (In the above chemical formula 4b, R4 and R6 are each independently a cycloalkylene group or cycloalkoxylene group having 4 to 10 carbon atoms, and R5 is a linear or branched alkylene group having 1 to 10 carbon atoms.)

9. The method for producing a polycarbonate copolymer according to claim 8, wherein the dihydroxyl compound may further comprise 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.

10. The method for producing a polycarbonate copolymer according to claim 8, wherein the carbonic acid diester compound comprises one or more of diphenyl carbonate, ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate.

11. A composition comprising the polycarbonate copolymer according to any one of claims 1 to 7.

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