Polycarbonate resin and its manufacturing method

Abstract

The present application relates to a polycarbonate resin containing a unit of Chemical Formula 1; and a unit of Chemical Formula 2, a method for producing the same, a polycarbonate resin composition containing the same, and a molded article containing the polycarbonate resin composition.

Description

[Technical field]

[0001] This application claims the benefit of the filing date of Korean Patent Application No. 10-2022-0035981, filed with the Korean Intellectual Property Office on March 23, 2022, the entire contents of which are incorporated herein by reference.

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

[0003] The higher the refractive index of an optical material, the thinner the optical lens needed to achieve the same level of correction, which allows for thinner and lighter lenses to be manufactured, thus enabling the miniaturization of various devices in which the lenses are used.

[0004] Generally, when the refractive index of an optical material increases, there is a problem that the Abbe's number decreases, and a certain level of transparency is required for use as an optical material. Summary of the Invention [Problem to be solved by the invention]

[0005] One embodiment of the present specification provides a polycarbonate resin having a novel structure and a method for producing the same.

[0006] Another embodiment of the present specification provides a polycarbonate resin composition containing a polycarbonate resin having a novel structure and a molded article produced from the polycarbonate resin composition. [Means for solving the problem]

[0007] One embodiment of the present specification provides a polycarbonate resin comprising a unit of the following Chemical Formula 1 and a unit of the following Chemical Formula 2: [ka] In the above Chemical Formulas 1 and 2, Ar1 and Ar2 are the same or different and each independently represent a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; R1 is hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; R2 and R3 are different from each other and each independently represent hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted silyl group; an aryl group substituted or unsubstituted with deuterium, a halogen group, a hydroxy group, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryloxy group, an arylthio group, an alkylthio group, an aryl group, or a heteroaryl group; or a substituted or unsubstituted heteroaryl group; r1 is 1 or 2, and when said r1 is 2, said two R1 are the same or different from each other; r2 and r3 each represent an integer of 1 to 4, and when r2 is 2 or more, the two or more R2s are the same or different from each other, and when r3 is 2 or more, the two or more R3s are the same or different from each other, L1 and L2 are the same or different and each independently represents a substituted or unsubstituted arylene group; X1 to X8 are the same or different and each independently represents O; or S; Z1 to Z4 are the same or different and each independently represents a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; a, b, c, and d are the same or different and each independently represents an integer of 1 to 10. When a, b, c, and d are each 2 or more, the structures in the parentheses are the same or different. * indicates the site connected to the main chain of the resin.

[0008] One embodiment of the present specification provides a method for producing a polycarbonate resin, comprising the step of polymerizing a composition for producing a polycarbonate resin, the composition comprising: a compound represented by the following formula 1a; a compound represented by the following formula 2a; and a polycarbonate precursor. [ka] In the above formulas 1a and 2a, Ar1 and Ar2 are the same or different and each independently represent a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; R1 is hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; R2 and R3 are different from each other and each independently represent hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted silyl group; an aryl group substituted or unsubstituted with deuterium, a halogen group, a hydroxy group, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryloxy group, an arylthio group, an alkylthio group, an aryl group, or a heteroaryl group; or a substituted or unsubstituted heteroaryl group; r1 is 1 or 2, and when said r1 is 2, said two R1 are the same or different from each other; r2 and r3 each represent an integer of 1 to 4, and when r2 is 2 or more, the two or more R2s are the same or different from each other, and when r3 is 2 or more, the two or more R3s are the same or different from each other, L1 and L2 are the same or different and each independently represents a substituted or unsubstituted arylene group; X1 to X8 are the same or different and each independently represents O; or S; Z1 to Z4 are the same or different and each independently represents a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; a, b, c, and d are the same or different and each independently represents an integer of 1 to 10, and when a, b, c, and d are each 2 or more, the structures in the parentheses are the same or different.

[0009] Another embodiment of the present disclosure provides a polycarbonate resin composition comprising a polycarbonate resin according to the above-described embodiment.

[0010] Another embodiment of the present invention provides a molded article comprising the polycarbonate resin composition according to the above-described embodiment. Effect of the Invention

[0011] The polycarbonate resin according to one embodiment of the present specification has a high refractive index and high transparency.

[0012] By using the polycarbonate resin according to one embodiment of the present specification, it is possible to obtain an excellent optical lens, optical film, optical thin film, or optical resin having a small thickness. [Brief description of the drawings]

[0013] [Figure 1] FIG. 13 is a graph showing the lens thickness reduction rate depending on the refractive index difference. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] This specification will be explained in more detail below. The relationship between molecular structure and refractive index, known as the Lorentz-Lorenz formula, shows that the refractive index of a substance made of molecules increases by increasing the electron density of the molecule and decreasing the molecular volume.

[0015] The resin containing the unit of Chemical Formula 1 has a small molecular volume and excellent packing ability due to the core structure of Chemical Formula 1 being a phenylene group, and can improve the refractive index of the resin. In addition, when Ar1 and Ar2 are electron-rich substituents such as substituted or unsubstituted aryl groups or substituted or unsubstituted heteroaryl groups, the electron density of the structure represented by Chemical Formula 1 can be increased, thereby further improving the refractive index of the resin.

[0016] The substituents of the benzene rings on both sides of the fluorene structure of Chemical Formula 2 form an asymmetric structure and include R2 and R3 as substituents, thereby increasing the electron density and improving the refractive index of a molded article containing the polycarbonate resin.

[0017] That is, the resin according to the present specification contains the unit of Chemical Formula 1 and the unit of Chemical Formula 2, so that the reactivity is improved and the resin can be easily produced, and the refractive index of the resin can be improved by increasing the electron density of each core structure. Therefore, the polycarbonate resin according to one embodiment of the present specification has a high refractive index and high transparency, and an optical lens, optical film, or optical resin using the same can be thin and exhibit excellent optical properties.

[0018] Throughout this specification, the term "combinations thereof" contained in a Markush form phrase means a mixture or combination of one or more selected from the group of elements set forth in the Markush form phrase, and is meant to include one or more selected from the group of elements.

[0019] In this specification, examples of the substituents are described below, but are not limited to these.

[0020] In this specification, [ka] means the site to be linked.

[0021] In this specification, the term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position of the substitution is not limited as long as it is a position at which a hydrogen atom is substituted, i.e., a position at which a substituent can be substituted, and when two or more substituents are substituted, the two or more substituents may be the same or different from each other.

[0022] As used herein, the term "substituted or unsubstituted" means substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a hydroxy group; a cyano group; an alkyl group; a cycloalkyl group; an alkoxy group; an alkenyl group; an aryloxy group; an arylthio group; an alkylthio group; a silyl group; an aryl group; a fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; and a heteroaryl group, or substituted with a substituent in which two or more of the substituents exemplified above are linked, or having no substituents at all.

[0023] In the present specification, the term "two or more substituents are linked" refers to the fact that a hydrogen atom of any one of the substituents is linked to another substituent. For example, the term "two substituents are linked" refers to the fact that a phenyl group and a naphthyl group are linked to each other. [ka] In addition, the linking of three substituents includes not only the linking of (substituent 1)-(substituent 2)-(substituent 3) successively, but also the linking of (substituent 1) to (substituent 2) and (substituent 3). For example, a phenyl group, a naphthyl group, and an isopropyl group are linked to form [ka] The above definitions also apply to the case where four or more substituents are connected.

[0024] In this specification, examples of the halogen group include fluorine, chlorine, bromine, and iodine.

[0025] In this specification, the alkyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a 1-methylbutyl group, a 1-ethylbutyl group, a pentyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 4-methyl-2-pentyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 4-methyl-2-pentyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a hexyl group, a 2-ethylbutyl group, a hexyl group, a 2-methylpent ... Examples of alkyl groups include, but are not limited to, butyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl groups.

[0026] In this specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 3-methylcyclopentyl group, a 2,3-dimethylcyclopentyl group, a cyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 2,3-dimethylcyclohexyl group, a 3,4,5-trimethylcyclohexyl group, a 4-tert-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group, but are not limited to these.

[0027] In this specification, the alkoxy group may be a straight chain, a branched chain, or a cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, but it is preferable that the number of carbon atoms is 1 to 30. Specific examples of the alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a sec-butoxy group, an n-pentyloxy group, a neopentyloxy group, an isopentyloxy group, an n-hexyloxy group, a 3,3-dimethylbutyloxy group, a 2-ethylbutyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, a benzyloxy group, and a p-methylbenzyloxy group.

[0028] In this specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 3-methyl-1-butenyl group, a 1,3-butadienyl group, an allyl group, a 1-phenylvinyl-1-yl group, a 2-phenylvinyl-1-yl group, a 2,2-diphenylvinyl-1-yl group, a 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl group, a 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, a stilbenyl group, and a styrenyl group, but are not limited thereto.

[0029] In this specification, the aryl group is not particularly limited, but preferably has 6 to 50 carbon atoms, and the aryl group may be monocyclic or polycyclic.

[0030] When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably is 6 to 30. Specific examples of the monocyclic aryl group include, but are not limited to, a phenyl group, a biphenyl group, and a terphenyl group.

[0031] When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 10 to 50. Specific examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a phenalene group, a perylene group, a chrysene group, and a fluorene group.

[0032] As used herein, the fluorene groups may be substituted and adjacent groups may be linked together to form a ring.

[0033] When the fluorene group is substituted, [ka] These include, but are not limited to:

[0034] In this specification, the term "adjacent" may refer to a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent sterically closest to the substituent, or another substituent substituted on the atom on which the substituent is substituted. For example, two substituents substituted at the ortho positions on a benzene ring and two substituents substituted on the same carbon atom on an aliphatic ring can be interpreted as "adjacent" groups to each other.

[0035] In this specification, the heteroaryl group includes one or more non-carbon atoms, i.e., heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, S, etc. The number of carbon atoms is not particularly limited, but is preferably 2 to 30, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a pyridine group, a bipyridine group, a pyrimidine group, a triazine group, a triazole group, an acridine group, a pyridazine group, a pyrazine group, a quinoline group, a quinazoline group, a quinoxaline group, a phthalazine group, a pyridopyrimidine group, a pyridopyrazine group, a pyrazinopyrazine group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuran group, and a phenanthridine group. Examples of such an alkyl group include, but are not limited to, phenanthridine, phenanthroline, isoxazole, thiadiazole, dibenzofuran, dibenzosilole, phenoxathiine, phenoxazine, phenothiazine, dihydroindenocarbazole, spirofluorenexanthene, spirofluorenethioxanthene, tetrahydronaphthothiophene, tetrahydronaphthofuran, tetrahydrobenzothiophene, and tetrahydrobenzofuran.

[0036] In this specification, the silyl group may be an alkylsilyl group, an arylsilyl group, an alkylarylsilyl group, a heteroarylsilyl group, etc. The alkyl group in the alkylsilyl group may be the above-mentioned exemplified alkyl group, the aryl group in the arylsilyl group may be the above-mentioned exemplified aryl group, the alkyl group and the aryl group in the alkylarylsilyl group may be the above-mentioned exemplified alkyl group, and the heteroaryl group in the heteroarylsilyl group may be the above-mentioned exemplified heterocyclic group.

[0037] In this specification, the hydrocarbon ring group may be an aromatic hydrocarbon ring group, an aliphatic hydrocarbon ring group, or a condensed ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring, and may be selected from the above-mentioned exemplified cycloalkyl group, aryl group, and combinations thereof. Examples of the hydrocarbon ring group include, but are not limited to, a phenyl group, a cyclohexyl group, an adamantyl group, a bicyclo[2.2.1]heptyl group, a bicyclo[2.2.1]octyl group, a tetrahydronaphthalene group, a tetrahydroanthracene group, a 1,2,3,4-tetrahydro-1,4-methanonaphthalene group, a 1,2,3,4-tetrahydro-1,4-ethanonaphthalene group, a spirocyclopentanefluorene group, a spiroadamantanefluorene group, and a spirocyclohexanefluorene group.

[0038] In this specification, the aryloxy group may be represented by -ORo, and the above description of the aryl group applies to Ro.

[0039] In this specification, the arylthio group may be represented by -SRs1, and the above description of the aryl group applies to Rs1.

[0040] In this specification, the alkylthio group may be represented by -SRs2, and the above description of the alkyl group applies to Rs2.

[0041] In this specification, the alkylene group refers to an alkyl group having two bonding positions, i.e., a divalent group. The above description of the alkyl group may be applied to these groups, except that they are both divalent groups.

[0042] In the present specification, a cycloalkylene group refers to a cycloalkyl group having two bonding positions, i.e., a divalent group. The above description of the cycloalkyl group may be applied to these groups, except that they are both divalent groups.

[0043] In this specification, a divalent fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring means a fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring having two bonding positions, i.e., a divalent group. The above description of the fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring may be applied to these groups, except that they are each divalent groups.

[0044] In the present specification, an arylene group refers to an aryl group having two bonding positions, i.e., a divalent group. The above description of the aryl group may be applied to these groups, except that they are both divalent groups.

[0045] According to one embodiment of the present specification, the polycarbonate resin further includes a unit of the following chemical formula 3: [ka] In the above Chemical Formula 3, L11 is a substituted or unsubstituted alkylene group; a substituted or unsubstituted cycloalkylene group; a substituted or unsubstituted divalent fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted arylene group; l11 is an integer of 1 to 5, and when l11 is 2 or more, the two or more L11 are the same or different from each other, X11 to X14 are the same or different and each independently represents O; or S; Z11 and Z12 are the same or different and each independently represents a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; a' and b' are the same or different and each independently represents an integer of 0 to 10. When a' and b' are each 2 or more, the structures in the parentheses are the same or different. * indicates the site connected to the main chain of the resin.

[0046] The polycarbonate resin further contains the unit represented by Chemical Formula 3, which can complement the glass transition temperature (Tg) of the resin containing the units represented by Chemical Formula 1 and Chemical Formula 2, or can make the chain behavior of the polycarbonate resin flexible, resulting in a technical effect advantageous to the injection processing of molded articles.

[0047] One embodiment of the present specification provides a polycarbonate resin comprising: units of Chemical Formula 1; units of Chemical Formula 2; and units of Chemical Formula 3.

[0048] According to one embodiment of the present specification, r2 is 1.

[0049] According to one embodiment of the present specification, the chemical formula 2 is any one of the following chemical formulas 2-1 to 2-4. [ka] In the above Chemical Formulas 2-1 to 2-4, The definitions of Z3, Z4, X5 to X8, c, d, L1, L2, and R2 are the same as those in Chemical Formula 2 above.

[0050] According to one embodiment of the present specification, the Ar1 and Ar2 are the same or different and each independently represent a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms substituted or unsubstituted with a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms; or a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms substituted or unsubstituted with a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, the R1 is hydrogen, the X1 to X4 are O, and the Z1 and Z2 are the same or different and each independently represent a linear or branched alkylene group having 1 to 30 carbon atoms.

[0051] According to one embodiment of the present specification, the R2 and R3 are different from each other and each independently represent hydrogen; or an unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; the L1 and L2 are the same or different from each other and each independently represent a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms; the X4 to X8 are O; and the Z3 and Z4 are the same or different from each other and each independently represent a linear or branched alkylene group having 1 to 30 carbon atoms.

[0052] According to one embodiment of the present specification, Ar1 and Ar2 are the same or different and each independently represents a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0053] According to one embodiment of the present specification, Ar1 and Ar2 are the same or different and each independently represents a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0054] According to one embodiment of the present specification, Ar1 and Ar2 are the same or different and each independently represents a polycyclic aryl group having 10 to 30 carbon atoms.

[0055] According to one embodiment of the present specification, Ar1 and Ar2 are the same or different and each independently represents a polycyclic aryl group having 10 to 20 carbon atoms.

[0056] According to one embodiment of the present specification, Ar1 and Ar2 are naphthyl groups.

[0057] According to one embodiment of the present specification, R1 is hydrogen.

[0058] According to one embodiment of the present specification, X1 is O.

[0059] According to one embodiment of the present specification, X2 is O.

[0060] According to one embodiment of the present specification, X3 is O.

[0061] According to one embodiment of the present specification, X4 is O.

[0062] According to one embodiment of the present specification, Z1 and Z2 are the same or different and each independently represents a linear or branched alkylene group having 1 to 30 carbon atoms.

[0063] According to one embodiment of the present specification, Z1 and Z2 are the same or different and each independently represents a linear or branched alkylene group having 1 to 20 carbon atoms.

[0064] According to one embodiment of the present specification, Z1 and Z2 are the same or different and each independently represents an ethylene group or an isopropylene group.

[0065] According to one embodiment of the present specification, R2 and R3 are different from each other and each independently represent a hydrogen atom or an unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0066] According to one embodiment of the present specification, R2 and R3 are different from each other and each independently represents a hydrogen atom or an unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0067] According to one embodiment of the present specification, R2 and R3 are different from each other and each independently represents a hydrogen atom or an unsubstituted polycyclic aryl group having 10 to 30 carbon atoms.

[0068] According to one embodiment of the present specification, R2 and R3 are different from each other and each independently represent a hydrogen atom or an unsubstituted polycyclic aryl group having 10 to 20 carbon atoms.

[0069] According to one embodiment of the present specification, R2 and R3 are different from each other and each independently represent a hydrogen atom or a naphthyl group.

[0070] According to one embodiment of the present specification, R2 is a naphthyl group.

[0071] According to one embodiment of the present specification, R3 is hydrogen.

[0072] According to one embodiment of the present specification, L1 and L2 are the same or different and each independently represents a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms.

[0073] According to one embodiment of the present specification, L1 and L2 are the same or different and each independently represents a monocyclic or polycyclic arylene group having 6 to 20 carbon atoms.

[0074] According to one embodiment of the present specification, L1 and L2 are the same or different and each independently represents a polycyclic arylene group having 10 to 30 carbon atoms.

[0075] According to one embodiment of the present specification, L1 and L2 are the same or different and each independently represents a polycyclic arylene group having 10 to 20 carbon atoms.

[0076] According to one embodiment of the present specification, L1 and L2 are divalent naphthalene groups.

[0077] According to one embodiment of the present specification, X5 is O.

[0078] According to one embodiment of the present specification, X6 is O.

[0079] According to one embodiment of the present specification, X7 is O.

[0080] According to one embodiment of the present specification, X8 is O.

[0081] According to one embodiment of the present specification, Z3 and Z4 are the same or different and each independently represents a linear or branched alkylene group having 1 to 30 carbon atoms.

[0082] According to one embodiment of the present specification, Z3 and Z4 are the same or different and each independently represents a linear or branched alkylene group having 1 to 20 carbon atoms.

[0083] According to one embodiment of the present specification, Z3 and Z4 are ethylene groups.

[0084] According to one embodiment of the present specification, a is 1.

[0085] According to one embodiment of the present specification, b is 1.

[0086] According to one embodiment of the present specification, c is 1.

[0087] According to one embodiment of the present specification, d is 1.

[0088] According to one embodiment of the present specification, a is 0.

[0089] According to one embodiment of the present specification, b is 0.

[0090] According to one embodiment of the present specification, c is 0.

[0091] According to one embodiment of the present specification, d is 0.

[0092] According to one embodiment of the present specification, L11 is a monocyclic or polycyclic alkylene group having 1 to 30 carbon atoms; a divalent fused ring group of a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aliphatic hydrocarbon ring having 3 to 30 carbon atoms; or a monocyclic or polycyclic arylene group having 6 to 50 carbon atoms which is substituted or unsubstituted with a linear or branched alkyl group having 1 to 30 carbon atoms, or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0093] According to one embodiment of the present specification, L11 is a monocyclic or polycyclic alkylene group having 1 to 20 carbon atoms; a divalent fused ring group of a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 20 carbon atoms and an aliphatic hydrocarbon ring having 3 to 20 carbon atoms; or a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms substituted or unsubstituted with a linear or branched alkyl group having 1 to 20 carbon atoms, or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0094] According to one embodiment of the present specification, L11 is a methylene group substituted or unsubstituted with a methyl group; an isopropylene group; a phenylene group substituted or unsubstituted with a methyl group or a phenyl group; a divalent naphthalene group; or a divalent fluorene group.

[0095] According to one embodiment of the present specification, the l11 is 1.

[0096] According to one embodiment of the present specification, the l11 is 2, and the two L11 are the same or different from each other.

[0097] According to one embodiment of the present specification, the l11 is 3, and the three L11 are the same or different from each other.

[0098] According to one embodiment of the present specification, X11 is O.

[0099] According to one embodiment of the present specification, X12 is O.

[0100] According to one embodiment of the present specification, X13 is O.

[0101] According to one embodiment of the present specification, X14 is O.

[0102] According to one embodiment of the present specification, Z11 and Z12 are the same or different and each independently represents a linear or branched alkylene group having 1 to 30 carbon atoms.

[0103] According to one embodiment of the present specification, Z11 and Z12 are the same or different and each independently represents a linear or branched alkylene group having 1 to 20 carbon atoms.

[0104] According to one embodiment of the present specification, Z11 and Z12 are ethylene groups.

[0105] According to one embodiment of the present specification, a′ is 1.

[0106] According to one embodiment of the present specification, b' is 1.

[0107] According to one embodiment of the present specification, a' is 0.

[0108] According to one embodiment of the present specification, b' is 0.

[0109] According to one embodiment of the present specification, the polycarbonate resin may have -OH; -SH; -CO2CH3; -Cl; or -OC6H5 as a terminal group.

[0110] In one embodiment of the present specification, the weight average molecular weight of the polycarbonate resin is 5,000 g / mol to 500,000 g / mol, preferably 7,000 g / mol to 400,000 g / mol, 8,000 g / mol to 300,000 g / mol, or 9,000 g / mol to 200,000 g / mol, more preferably 10,000 g / mol to 100,000 g / mol, 10,000 g / mol to 80,000 g / mol, 15,000 g / mol to 70,000 g / mol, or 18,000 g / mol to 65,000 g / mol.

[0111] In one embodiment of the present invention, the number average molecular weight of the polycarbonate resin is 2,000 g / mol to 250,000 g / mol, 3,000 g / mol to 200,000 g / mol, 4,000 g / mol to 180,000 g / mol, or 5,000 g / mol to 150,000 g / mol, preferably 8,000 g / mol to 100,000 g / mol.

[0112] When the polycarbonate resin satisfies the above-mentioned ranges of weight average molecular weight and number average molecular weight, the polycarbonate resin can have optimal fluidity and processability.

[0113] The weight average molecular weight and number average molecular weight of the polycarbonate resin are weight average molecular weights calculated in terms of polystyrene.

[0114] In this specification, the weight average molecular weight and number average molecular weight of polycarbonate resin and oligomers used in its production can be measured by gel permeation chromatography (GPC) using polystyrene standard (PS standard) using Agilent 1200 series. Specifically, it can be measured using Agilent 1200 series equipment using Polymer Laboratories PLgel MIX-B 300 mm long column, at a measurement temperature of 40 ° C, a solvent used is tetrahydrofuran (THF), and a flow rate of 1 mL / min. Samples of polycarbonate resin or oligomer are each prepared to a concentration of 10 mg / 10 mL, and then supplied in an amount of 10 μL, and the weight average molecular weight (Mw) value is derived using a calibration curve formed using polystyrene standard. In this case, nine types of polystyrene standards with molecular weights (g / mol) of 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000 are used.

[0115] In one embodiment of the present specification, the glass transition temperature (Tg) of the polycarbonate resin may be 80° C. to 200° C., or 85° C. to 190° C., preferably 100° C. to 180° C., 120° C. to 170° C., or 130° C. to 160° C., specifically 85.0° C. to 168.0° C.

[0116] When the polycarbonate resin satisfies the above glass transition temperature range, it has excellent heat resistance and injectability, and when it is mixed with a resin having a glass transition temperature different from the above range to produce a polycarbonate resin composition, the glass transition temperature can be easily adjusted, and the physical properties targeted in the present specification can be satisfied.

[0117] The glass transition temperature (Tg) can be measured using a differential scanning calorimeter (DSC). Specifically, the glass transition temperature can be measured from a graph obtained by heating 5.5 mg to 8.5 mg of the polycarbonate resin sample to 270° C. in a nitrogen atmosphere, cooling the sample, and then heating the sample at a heating rate of 10° C. / min during the second heating and scanning the sample.

[0118] In one embodiment of the present specification, the polycarbonate resin has a refractive index of 1.50 to 1.75 measured at a wavelength of 587 nm. The refractive index is preferably 1.65 to 1.712, and may be specifically 1.607 to 1.709. When the resin satisfies the refractive index range, it is possible to manufacture a thin and lightweight optical lens when the resin is applied to a molded product such as an optical lens.

[0119] In one embodiment of the present specification, the Abbe number of the resin measured and calculated at wavelengths of 486, 587, and 656 nm may be 5 to 45. It may be preferably 10 to 25, and more preferably 14 to 20. Specifically, it may be 14.0 to 26.5.

[0120] When the resin satisfies the Abbe number range, there is an effect that dispersion is small and clarity is high when the resin is applied to a molded product such as an optical lens. Specifically, the Abbe number is the refractive index (n D , n F , n C ) and the Abbe number can be calculated using the following formula: Abbe number = (n D -1) / (n F -n C )

[0121] The refractive index and Abbe number may be measured from a film prepared by spin-coating a solution prepared by dissolving the resin in a solvent on a silicon wafer, and the coated film may be measured at 20° C. using an ellipsometer to obtain a result value according to the wavelength of light. The coating by spin-coating may be performed at a rotation speed of 150 rpm to 300 rpm, and the thickness of the coated film may be 5 μm to 20 μm. The silicon wafer is not particularly limited, and may be appropriately adopted as long as it can measure the refractive index and Abbe number of the resin composition according to the present specification. The solvent may be dimethylacetamide or 1,2-dichlorobenzene, and the solution may be prepared by dissolving the resin sample at 10 wt % based on the total weight of the solution.

[0122] One embodiment of the present specification provides a method for producing a polycarbonate resin, comprising the step of polymerizing a composition for producing a polycarbonate resin, the composition comprising: a compound represented by the following formula 1a; a compound represented by the following formula 2a; and a polycarbonate precursor. [ka] In the above formulas 1a and 2a, Ar1 and Ar2 are the same or different and each independently represent a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; R1 is hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; R2 and R3 are different from each other and each independently represent hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted silyl group; an aryl group substituted or unsubstituted with deuterium, a halogen group, a hydroxy group, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryloxy group, an arylthio group, an alkylthio group, an aryl group, or a heteroaryl group; or a substituted or unsubstituted heteroaryl group; r1 is 1 or 2, and when said r1 is 2, said two R1 are the same or different from each other; r2 and r3 each represent an integer of 1 to 4, and when r2 is 2 or more, the two or more R2s are the same or different from each other, and when r3 is 2 or more, the two or more R3s are the same or different from each other, L1 and L2 are the same or different and each independently represents a substituted or unsubstituted arylene group; X1 to X8 are the same or different and each independently represents O; or S; Z1 to Z4 are the same or different and each independently represents a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; a, b, c, and d are the same or different and each independently represents an integer of 1 to 10, and when a, b, c, and d are each 2 or more, the structures in the parentheses are the same or different.

[0123] According to one embodiment of the present specification, the method for producing a polycarbonate resin further includes a compound of the following chemical formula 3a, and the compound of the chemical formula 1a, the compound of the chemical formula 2a, and the compound of the chemical formula 3a are included in an amount of 0.01 mol% to 99.99 mol%: 0.01 mol% to 99.99 mol%: 0 mol% to 99.98 mol%, specifically, 0.1 mol% to 99.9 mol%: 0.1 mol% to 99.9 mol%: 0 mol% to 99.8 mol%, more specifically, 1 mol% to 99 mol%: 1 mol% to 99 mol%: 0 mol% to 98 mol%, 5 mol% to 95 mol%: 95 mol% to 5 mol%: 0 mol% to 90 mol%, or 10 mol% to 90 mol%: 90 mol% to 10 mol%: 0 mol% to 80 mol%. [ka] In the above Chemical Formula 3a, L11 is a substituted or unsubstituted alkylene group; a substituted or unsubstituted cycloalkylene group; a substituted or unsubstituted divalent fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted arylene group; l11 is an integer of 1 to 5, and when l11 is 2 or more, the two or more L11 are the same or different from each other, X11 to X14 are the same or different and each independently represents O; or S; Z11 and Z12 are the same or different and each independently represents a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; a' and b' are the same or different and each independently represents an integer of 0 to 10, and when a' and b' are each 2 or greater, the structures in the respective parentheses are the same or different.

[0124] One embodiment of the present specification provides a method for producing the polycarbonate resin, comprising polymerizing a composition for producing a polycarbonate resin, the composition including the compound of the formula 1a, the compound of the formula 2a, and a polycarbonate precursor. The compound of the formula 1a and the compound of the formula 2a are contained in an amount of 0.01 mol% to 99.99 mol%: 99.99 mol% to 0.01 mol%. Specifically, the compound is contained in an amount of 0.1 mol% to 99.9 mol%: 99.9 mol% to 0.1 mol%, 1 mol% to 99 mol%: 99 mol% to 1 mol%, 5 mol% to 95 mol%: 95 mol% to 5 mol%, or 10 mol% to 90 mol%: 90 mol% to 10 mol%.

[0125] When the compounds of Formulae 1a and 2a are contained in the above amounts, the polymerizable composition is easy to polymerize, has a refractive index in a wide range or a high refractive index depending on the substituents, and has a wide range of glass transition temperatures.

[0126] One embodiment of the present specification provides a method for producing the polycarbonate resin, comprising the step of polymerizing a composition for producing a polycarbonate resin, the composition comprising: the compound of formula 1a; the compound of formula 2a; the compound of formula 3a; and a polycarbonate precursor. The compound of Chemical Formula 1a, the compound of Chemical Formula 2a, and the compound of Chemical Formula 3a are contained in an amount of 0.01 mol% to 99.99 mol%: 0.01 mol% to 99.99 mol%: 0 mol% to 99.98 mol%, specifically, 0.1 mol% to 99.9 mol%: 0.1 mol% to 99.9 mol%: 0 mol% to 99.8 mol%, more specifically, 1 mol% to 99 mol%: 1 mol% to 99 mol%: 0 mol% to 98 mol%, 5 mol% to 95 mol%: 95 mol% to 5 mol%: 0 mol% to 90 mol%, or 10 mol% to 90 mol%: 90 mol% to 10 mol%: 0 mol% to 80 mol%.

[0127] When the compounds of the formulae 1a, 2a, and 3a are contained in the above amounts, the glass transition temperature (Tg) and refractive index can be adjusted, and the chain behavior of the polycarbonate resin can be made flexible, which has advantageous technical effects on the injection processing of molded articles.

[0128] The composition for producing a polycarbonate resin may further contain a solvent.

[0129] The solvent may be, for example, diphenyl ether, dimethylacetamide, or methanol, but is not limited thereto, and any solvent applicable in the art may be appropriately adopted.

[0130] The solvent may be contained in an amount of 5 parts by weight to 60 parts by weight based on 100 parts by weight of the composition for producing a resin.

[0131] The solvent may be preferably contained in an amount of 5 parts by weight to 50 parts by weight, 7 parts by weight to 45 parts by weight, or 8 parts by weight to 40 parts by weight with respect to 100 parts by weight of the composition for producing a resin.

[0132] According to one embodiment of the present specification, the compound may include two or more of the formula 1a, wherein the two or more formulae 1a are the same or different from each other.

[0133] In one embodiment of the present invention, the compound of formula 1a may be any one selected from the following compounds, but is not limited thereto: [ka]

[0134] In one embodiment of the present invention, the compound of Formula 2a may be, but is not limited to, the following compound: [ka]

[0135] In one embodiment of the present invention, the compound of formula 3a may be, but is not limited to, the following compounds: [ka]

[0136] In one embodiment of the present specification, the compound of Chemical Formula 1a may be included in an amount of 1 part by weight to 99 parts by weight based on 100 parts by weight of the composition for producing a polycarbonate resin.

[0137] The compound of the chemical formula 1a may be included in an amount of preferably 1 to 60 parts by weight, 1 to 50 parts by weight, 1 to 40 parts by weight, 1 to 30 parts by weight, 1 to 20 parts by weight, or 1 to 10 parts by weight, based on 100 parts by weight of the composition for producing a polycarbonate resin.

[0138] In one embodiment of the present specification, the compound of Chemical Formula 2a may be included in an amount of 1 part by weight to 99 parts by weight based on 100 parts by weight of the composition for producing a polycarbonate resin.

[0139] The compound of Chemical Formula 2a may be included in an amount of preferably 1 to 60 parts by weight, 1 to 50 parts by weight, 1 to 40 parts by weight, 1 to 30 parts by weight, 1 to 20 parts by weight, or 1 to 10 parts by weight, based on 100 parts by weight of the composition for producing a polycarbonate resin.

[0140] In one embodiment of the present specification, the polycarbonate precursor may be contained in an amount of 1 part by weight to 60 parts by weight based on 100 parts by weight of the composition for producing a polycarbonate resin.

[0141] The polycarbonate precursor may be contained in an amount of preferably 1 to 60 parts by weight, 1 to 55 parts by weight, 1 to 50 parts by weight, 1 to 45 parts by weight, or 1 to 40 parts by weight, relative to 100 parts by weight of the composition for producing a polycarbonate resin.

[0142] In one embodiment of the present specification, the compound of Chemical Formula 3a may be included in an amount of 0 to 98 parts by weight based on 100 parts by weight of the composition for producing a polycarbonate resin.

[0143] The compound of the chemical formula 3a may be included in an amount of preferably 0 to 60 parts by weight, 1 to 50 parts by weight, 0 to 40 parts by weight, 0 to 30 parts by weight, 0 to 20 parts by weight, or 0 to 10 parts by weight, based on 100 parts by weight of the composition for producing a polycarbonate resin.

[0144] According to one embodiment of the present specification, the polycarbonate precursor is represented by the following chemical formula A: [ka] In the above chemical formula A, Rb1 and Rb2 are the same or different and each independently represents a halogen group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group; a1 and a2 are each 0 or 1.

[0145] According to one embodiment of the present specification, Rb1 and Rb2 are the same or different and each independently represent a halogen group; a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0146] According to one embodiment of the present specification, Rb1 and Rb2 are the same or different and each independently represent a halogen group; a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0147] According to one embodiment of the present specification, Rb1 and Rb2 are the same or different and each independently represent a halogen group; a linear or branched alkyl group having 1 to 30 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0148] According to one embodiment of the present specification, Rb1 and Rb2 are the same or different and each independently represent a halogen group; a linear or branched alkyl group having 1 to 20 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0149] According to one embodiment of the present specification, Rb1 and Rb2 are the same or different and each independently represents -Cl; a methyl group; an ethyl group; an n-propyl group; an isopropyl group; an n-butyl group; or a phenyl group.

[0150] According to one embodiment of the present specification, the chemical formula A is any one selected from the following compounds: [ka]

[0151] In the case of polyester resin, the precursor [ka] The molecular weight of the precursor of polycarbonate resin is [ka] Since the refractive index is higher than that of the polycarbonate resin, the specific gravity of the resin is high. The precursor has a low concentration of diol monomer, which realizes high refractive index, so the refractive index of the polycarbonate resin is relatively higher than that of polyester resin. In addition, polyester resin has a disadvantage that the yellow index is generally high due to the long conjugated bond due to the structural characteristics of polyester resin compared to polycarbonate resin, and intramolecular hydrogen bond.

[0152] The polycarbonate precursor serves to link additional comonomers as necessary, and specific examples applicable to the compound represented by formula A include phosgene, triphosgene, diphosgene, bromophosgene, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, and bishaloformates, and any one or a mixture of two or more of these may be used.

[0153] In one embodiment of the present specification, the polycarbonate resin is preferably polymerized from the compound of formula 1a; the compound of formula 2a; and the polycarbonate precursor of formula A.

[0154] The compound of Formula 1a and the polycarbonate precursor of Formula A can be polymerized to form the unit of Formula 1.

[0155] The compound of the chemical formula 1a may be used in an amount of 1 to 99 parts by mole based on 100 parts by mole of all monomers constituting the polycarbonate resin containing the unit of the chemical formula 1.

[0156] The polycarbonate polyester precursor of the chemical formula A may be used in an amount of 1 to 150 parts by mol, or 50 to 150 parts by mol, per 100 parts by mol of the total monomers of the compound of the chemical formula 1a constituting the resin.

[0157] The compound of Formula 2a and the polycarbonate precursor of Formula A can be polymerized to form the unit of Formula 2.

[0158] The compound of the chemical formula 2a may be used in an amount of 1 to 99 parts by mole based on 100 parts by mole of all monomers constituting the polycarbonate resin containing the unit of the chemical formula 2.

[0159] The polycarbonate polyester precursor of the chemical formula A may be used in an amount of 1 to 150 parts by mol, or 50 to 150 parts by mol, per 100 parts by mol of the total monomers of the compound of the chemical formula 2a constituting the resin.

[0160] In one embodiment of the present specification, the polycarbonate resin may further include a unit of the above formula 3.

[0161] The compound of Formula 3a and the polycarbonate precursor of Formula A can be polymerized to form the unit of Formula 3.

[0162] The compound of the chemical formula 3a may be used in an amount of 0 to 98 parts by mole based on 100 parts by mole of all monomers constituting the polycarbonate resin containing the unit of the chemical formula 3.

[0163] The polycarbonate polyester precursor of the chemical formula A may be used in an amount of 1 to 150 parts by mol, or 50 to 150 parts by mol, per 100 parts by mol of the total monomers of the compound of the chemical formula 3a constituting the resin.

[0164] Polymerization of the resins according to the present invention may employ methods well known in the art.

[0165] The polymerization is preferably carried out by a melt polycondensation method.

[0166] The melt polycondensation method may use the composition for producing a polycarbonate resin, and may further include a catalyst as necessary, and may perform melt polycondensation under heating and further under normal or reduced pressure while removing by-products by ester exchange reaction. As the catalyst, a substance generally applied in the technical field may be adopted.

[0167] Specifically, the melt polycondensation method is preferably carried out by melting the compound of formula 1a, the compound of formula 2a, and the polycarbonate precursor in a reaction vessel, and then carrying out the reaction while retaining by-product compounds. The preparation method may further include the compound of formula 3a.

[0168] In order to retain the by-produced compound, the reaction apparatus may be blocked or the pressure may be controlled by reducing or increasing the pressure.

[0169] The reaction time for this step is from 20 minutes to 600 minutes, preferably from 40 minutes to 450 minutes, and more preferably from 60 minutes to 300 minutes.

[0170] In this case, if the by-product compounds are distilled off immediately after production, the final resin will have a low content of polymers, whereas if the by-product compounds are allowed to remain in the reaction vessel for a certain period of time, the final resin will have a high content of polymers.

[0171] The melt polycondensation method may be carried out in a continuous manner or in a batch manner. The reaction apparatus used in the reaction may be a vertical type equipped with an anchor-type impeller, a Max Blend impeller, a helical ribbon-type impeller, or the like, a horizontal type equipped with a paddle impeller, a lattice impeller, a spectacle impeller, or the like, or an extruder type equipped with a screw. In addition, taking into consideration the viscosity of the polymer, it is preferable to use a reaction apparatus that is an appropriate combination of these reaction apparatuses.

[0172] In the method for producing the polycarbonate resin used in this specification, the catalyst may be removed or deactivated after the polymerization reaction is completed in order to maintain thermal stability and hydrolytic stability. A method for deactivating the catalyst by adding an acidic substance known in the art can be preferably carried out.

[0173] Examples of the acidic substance include esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid; phosphites such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite; and the like. Preferred examples of the organic halides that are used include phosphate esters such as monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphonic acid, and the like; phosphonic acid esters such as diethyl phenylphosphonate; phosphines such as triphenylphosphine, bis(diphenylphosphino)ethane, and the like; boric acid, phenylboric acid, and the like; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate, and the like; organic halides such as stearic acid chloride, benzoyl chloride, and p-toluenesulfonic acid chloride, and the like; alkyl sulfates such as dimethyl sulfate, and the like; and organic halides such as benzyl chloride, and the like.

[0174] The acidic substance may be used in an amount of 0.1 to 5 parts by mol, preferably 0.1 to 1 part by mol, based on 100 parts by mol of the catalyst.

[0175] If the amount of the acidic substance is less than 0.1 parts by mole, the deactivation effect will be insufficient, which is undesirable, whereas if the amount is more than 5 parts by mole, the heat resistance of the resin will decrease and the molded product will tend to be discolored, which is undesirable.

[0176] After the catalyst is deactivated, a volatilization step may be further carried out to remove low boiling point compounds in the resin at a pressure of 0.1 mmHg to 1 mmHg and a temperature of 200° C. to 350° C. For this step, a horizontal device equipped with stirring blades with excellent surface renewal ability, such as paddle blades, lattice blades, and spectacle blades, or a thin film evaporator is preferably used.

[0177] The resin of the present invention preferably has a minimum content of foreign matter, and filtration of the molten raw material, filtration of the catalyst solution, etc. are preferably carried out.

[0178] The mesh of the filter used for the filtration is preferably 5 μm or less, more preferably 1 μm or less. The generated resin is preferably filtered through a polymer filter. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. The process of collecting the resin pellets must be in a low dust environment, preferably class 6 or less, more preferably class 5 or less.

[0179] In addition, examples of methods for molding molded articles containing the polycarbonate resin include, in addition to injection molding, compression molding, casting, roll processing, extrusion molding, and stretching, but are not limited to these.

[0180] Another embodiment herein provides a polycarbonate resin composition comprising a resin according to the above-described embodiment.

[0181] In one embodiment of the present specification, the polycarbonate resin may be included in an amount of 1 part by weight to 80 parts by weight based on 100 parts by weight of the polycarbonate resin composition.

[0182] In one embodiment of the present specification, the polycarbonate resin composition may further include a solvent. The solvent may be, for example, dimethylacetamide or 1,2-dichlorobenzene.

[0183] The solvent may be included in an amount of 20 parts by weight to 99 parts by weight based on 100 parts by weight of the polycarbonate resin composition.

[0184] The polycarbonate resin composition may further include an additional monomer in addition to the compound of formula 1a and the compound of formula 2a. The additional monomer is not particularly limited, and a monomer generally applied in the technical field related to polycarbonate may be appropriately adopted within a range that does not change the main physical properties of the polycarbonate resin composition. The additional monomer may be used in an amount of 1 to 50 parts by mole relative to 100 parts by mole of the total monomers constituting the resin containing the unit of formula 1.

[0185] In addition to the resin containing the unit of Chemical Formula 1 and the unit of Chemical Formula 2, the polycarbonate resin composition may further contain, as necessary, additives such as one or more selected from the group consisting of antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent brighteners, ultraviolet absorbers, pigments, and dyes.

[0186] The additive may be included in an amount of 1 part by weight to 99 parts by weight based on 100 parts by weight of the polycarbonate resin composition.

[0187] The types of the antioxidant, plasticizer, antistatic agent, nucleating agent, flame retardant, lubricant, impact modifier, fluorescent brightener, ultraviolet absorber, pigment, or dye are not particularly limited, and any agent applicable in the relevant technical field may be appropriately adopted.

[0188] Another embodiment of the present invention provides a molded article comprising the polycarbonate resin composition according to the above-described embodiment.

[0189] In one embodiment of the present specification, the molded article may be produced from the polycarbonate resin composition or a cured product thereof.

[0190] An example of a method for producing the molded product may include a step of thoroughly mixing the resin containing the unit of Chemical Formula 1 and the additive in a mixer, extruding the mixture in an extruder to prepare pellets, drying the pellets, and then injecting the pellets in an injection molding machine.

[0191] In one embodiment of the present specification, the molded article is an optical lens.

[0192] In one embodiment of the present specification, the optical lens has a thickness of 0.1 μm to 30 mm.

[0193] The optical lens has different focal positions where light is focused in a lens of the same thickness depending on the difference in refractive index. This is shown in FIG. 1. This is because the refractive index is increased to change the focal positions between the camera lens and the image sensor, and between the eyeglass lens and the human pupil, and to focus at the same position, thereby making the lens or film thinner. The optical lens according to one embodiment of the present specification has a high refractive index, making it possible to realize an optical lens with a thin thickness.

[0194] The optical lens is manufactured using the polycarbonate resin, has a small thickness, a high refractive index and high transparency, and is preferably applicable to cameras.

[0195] In one embodiment of the present specification, the molded product is an optical film or an optical thin film. The optical film or the optical thin film is manufactured using the polycarbonate resin, has a small thickness, and has excellent light collecting and diffusing effects, and can be preferably applied to a backlight module of a liquid crystal display, a flat lens, a metalens, etc.

[0196] In one embodiment of the present specification, the optical film or optical thin film has a thickness of 0.1 nm to 10 mm.

[0197] In one embodiment of the present specification, the molded article is an optical resin. The optical resin is manufactured using the polycarbonate resin, has a small thickness, a high refractive index, a low birefringence, and a low optical loss.

[0198] The optical resin according to an embodiment of the present specification has a high refractive index and a low birefringence, and has low optical loss. The optical resin according to an embodiment of the present specification has a glass transition temperature of 80°C to 200°C, which is very high or not low in heat resistance compared to conventional general optical materials, and is therefore easy to process and exhibits excellent heat resistance. If the glass transition temperature exceeds 200°C, the melt flow index increases, making processing difficult, and if the glass transition temperature is less than 80°C, the poor heat resistance results in a decrease in weather resistance due to the external environment. For this reason, there are few optical resins according to an embodiment of the present specification that have suitable thermal properties and realize a high refractive index. EXAMPLES

[0199] The present invention will now be illustrated in more detail by way of examples.

[0200] Production Example 1. Production of Resin 1 Monomer 1-1 (31.537g (0.070mol)), Monomer 2-1 (14.358g (0.030mol)), and diphenylcarbonate (21.422g (0.100mol)) were melted and reacted at 250℃ for 5 hours. As the reaction proceeded, phenol was generated as a by-product, and the pressure reduction was adjusted to a maximum of 1Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create a normal pressure atmosphere, and Resin 1 was obtained as a polymerized polymer molten resin. [ka]

[0201] Production Examples 2 to 16. Production of Resins 2 to 16 Resins 2 to 16 were obtained in the same manner as in Production Example 1, except that the monomers in Table 1 below were used in the following parts by weight instead of Monomers 1-1 and 2-1 in Production Example 1. [ka]

[0202] [Table 1]

[0203] Experimental Example The molecular weight and molecular weight distribution of the polymerized resin samples were confirmed by gel permeation chromatography (GPC), and a thermogram was obtained using a differential scanning calorimeter (DSC) to investigate the thermal properties. To measure the refractive index and Abbe number, an ellipsometer was used after film formation to obtain the results according to the wavelength of light.

[0204] The molecular weight by gel permeation chromatography (GPC) was measured by dissolving the resin sample in tetrahydrofuran (THF stabilized with BHT (butylhydroxytoluene)) as a solvent at a concentration of 1.0 mg / 1 ml, filtering the solution through a syringe filter, injecting it, and measuring the results at 40°C, which are shown in Table 2 below. A Waters RI detector was used, and two Agilent PLgel MIXED-B columns were used.

[0205] The glass transition temperature (Tg) of the resin was measured using a differential scanning calorimeter (DSC). 5.5 mg to 8.5 mg of a resin sample was heated to 270°C under N2 flow, cooled, and then heated at a heating rate of 10°C / min during the second heating, and the glass transition temperature (Tg) was obtained from the graph obtained, which is shown in Table 2 below.

[0206] To measure the refractive index and Abbe number of the resin, the polymerized resin powder sample was dissolved in dimethylacetamide solvent at 10% by weight based on the total weight of the polymer solution to prepare a polymer solution, which was then spin-coated onto a silicon wafer at a rotation speed of 220 rpm to form a film with a thickness of 20 μm. An ellipsometer was then used at 20° C. to obtain the results according to the wavelength of light, which are listed in Table 2 below. Specifically, the refractive index was measured at a wavelength of 589 nm, and the Abbe number was measured at the refractive index (n D , n F , n C ) were measured, and the Abbe number was calculated using the following formula: Abbe number = (n D -1) / (n F -n C )

[0207] [Table 2]

[0208] In Table 2, Mn is the number average molecular weight, Mw is the weight average molecular weight, PDI is the polydispersity index, RI is the refractive index, Tg is the glass transition temperature, and the refractive index is a value measured at a wavelength of 587 nm.

[0209] According to Table 2, the resin according to the embodiment of the present invention includes a unit of Chemical Formula 1 and a unit of Chemical Formula 2. In particular, since the core structure of Chemical Formula 1 is a phenylene group, it has been confirmed that the molecular volume is small and the packing ability is excellent, thereby improving the refractive index of the resin.

[0210] In addition, since Ar1 and Ar2 have electron-rich substituents, the electron density is high, and since the benzene ring of the fluorene core structure of Chemical Formula 2 is substituted with the electron-rich R2 substituent, the electron density of the fluorene core structure is high, and therefore the refractive index of the polycarbonate resin containing it is improved.

[0211] In addition, by further including the unit of Chemical Formula 3 in addition to the unit of Chemical Formula 1 and the unit of Chemical Formula 2, the glass transition temperature (Tg) and refractive index can be adjusted and the chain behavior of the polycarbonate resin can be made flexible, which has advantageous technical effects in injection processing of molded products.

Claims

1. A polycarbonate resin comprising a unit of the following chemical formula 1 and a unit of the following chemical formula 2: [Formula 1] In the above Chemical Formulas 1 and 2, Ar1 and Ar2 are the same or different and each independently represent a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; R1 is hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; R2 and R3 are different from each other and each independently represents hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted silyl group; an aryl group substituted or unsubstituted with deuterium, a halogen group, a hydroxy group, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryloxy group, an arylthio group, an alkylthio group, an aryl group, or a heteroaryl group; or a substituted or unsubstituted heteroaryl group; r1 is 2, and the two R1 are the same or different; r2 and r3 are 4, the four R2 are the same or different from each other, and the four R3 are the same or different from each other; L1 and L2 are the same or different and each independently represents a substituted or unsubstituted arylene group; X1 to X8 are the same or different and each independently represents O; or S; Z1 to Z4 are the same or different and each independently represents a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; a, b, c, and d are the same or different and each independently represents an integer from 1 to 10. When a, b, c, and d are each 2 or more, the structures in the parentheses are the same or different. * indicates the site connected to the main chain of the resin.

2. The polycarbonate resin of claim 1 further comprises a unit of the following formula 3: [Case 2] In the above Chemical Formula 3, L11 is a substituted or unsubstituted alkylene group; a substituted or unsubstituted cycloalkylene group; a substituted or unsubstituted divalent fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted arylene group; l11 is an integer of 1 to 5, and when l11 is 2 or more, the two or more L11 are the same or different from each other, X11 to X14 are the same or different and each independently represents O; or S; Z11 and Z12 are the same or different, and each independently represents a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; a' and b' are the same or different and each independently represents an integer of 0 to 10. When a' and b' are each 2 or more, the structures in the parentheses are the same or different. * indicates the site connected to the main chain of the resin.

3. Ar1 and Ar2 are the same or different, and each independently represents a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms which is substituted or unsubstituted with a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms; or a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms which is substituted or unsubstituted with a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, R1 is hydrogen; X1 to X4 are O, 2. The polycarbonate resin according to claim 1, wherein Z1 and Z2 are the same or different and each independently represents a linear or branched alkylene group having 1 to 30 carbon atoms.

4. R2 and R3 are different from each other and each independently represent a hydrogen atom or an unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; L1 and L2 are the same or different and each independently represents a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms, X5 to X8 are O; 2. The polycarbonate resin according to claim 1, wherein Z3 and Z4 are the same or different and each independently represents a linear or branched alkylene group having 1 to 30 carbon atoms.

5. The polycarbonate resin of claim 1, having a weight average molecular weight (Mw) of 5,000 g / mol to 500,000 g / mol.

6. 2. The polycarbonate resin according to claim 1, which has a refractive index of 1.50 to 1.75 measured at a wavelength of 587 nm.

7. The polycarbonate resin according to claim 1, having a glass transition temperature (Tg) of 80°C to 200°C.

8. 2. The polycarbonate resin according to claim 1, having an Abbe number of 5 to 45 measured at wavelengths of 486, 587, and 656 nm.

9. A compound of formula 1a: A compound of formula 2a: A method for producing the polycarbonate resin according to any one of claims 1 to 8, comprising a step of polymerizing a composition for producing a polycarbonate resin comprising a polycarbonate precursor: [C3] In the above formulas 1a and 2a, Ar1 and Ar2 are the same or different and each independently represent a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; R1 is hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; R2 and R3 are different from each other and each independently represents hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted silyl group; an aryl group substituted or unsubstituted with deuterium, a halogen group, a hydroxy group, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryloxy group, an arylthio group, an alkylthio group, an aryl group, or a heteroaryl group; or a substituted or unsubstituted heteroaryl group; r1 is 2, and the two R1 are the same or different; r2 and r3 are 4, the four R2 are the same or different from each other, and the four R3 are the same or different from each other; L1 and L2 are the same or different and each independently represents a substituted or unsubstituted arylene group; X1 to X8 are the same or different and each independently represents O; or S; Z1 to Z4 are the same or different and each independently represents a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; a, b, c, and d are the same or different and each independently represents an integer of 1 to 10, and when a and b are each 2 or more, the structures in the parentheses are the same or different.

10. The method for producing a polycarbonate resin according to claim 9, further comprising a compound represented by the following formula 3a, wherein the compound represented by the formula 1a, the compound represented by the formula 2a, and the compound represented by the formula 3a are contained in an amount of 0.01 mol% to 99.99 mol%: 0.01 mol% to 99.99 mol%: 0 mol% to 99.98 mol%: [C4] In the above Chemical Formula 3a, L11 is a substituted or unsubstituted alkylene group; a substituted or unsubstituted cycloalkylene group; a substituted or unsubstituted divalent fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted arylene group; l11 is an integer of 1 to 5, and when l11 is 2 or more, the two or more L11 are the same or different from each other, X11 to X14 are the same or different and each independently represents O; or S; Z11 and Z12 are the same or different, and each independently represents a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group; a' and b' are the same or different and each independently represents an integer of 0 to 10, and when a' and b' are each 2 or more, the structures in the respective parentheses are the same or different.

11. The method for producing a polycarbonate resin according to claim 9, wherein the polycarbonate precursor is represented by the following chemical formula A: [C5] In the above chemical formula A, Rb1 and Rb2 are the same or different and each independently represents a halogen group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group; a1 and a2 each is 0 or 1.

12. A polycarbonate resin composition comprising the polycarbonate resin according to any one of claims 1 to 8.

13. A molded article comprising the polycarbonate resin composition according to claim 12.

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