Polycarbonate resin and method for manufacturing the same

Abstract

The present application relates to a polycarbonate resin containing a unit of Chemical Formula 1, 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 as of the filing date of Korean Patent Application No. 10-2022-0082384, filed with the Korean Intellectual Property Office on 5 July 2022, and all its contents are incorporated herein by reference.

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

[0003] When the refractive index of an optical material is high, the thickness of the optical lens required to achieve the same level of correction becomes thinner. As a result, the higher the refractive index of the optical material, the thinner and lighter the lens can be manufactured, enabling miniaturization of various devices that use lenses.

[0004] Generally, when the refractive index of an optical material increases, the Abbe's number decreases, and a certain level of transparency is required for use as an optical material. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] One embodiment of this specification aims to provide a polycarbonate resin with a novel structure and a method for producing the same.

[0006] Another embodiment of this specification aims to provide a polycarbonate resin composition comprising a polycarbonate resin of a novel structure and a molded article manufactured from the polycarbonate resin composition. [Means for solving the problem]

[0007] One embodiment of this specification provides a polycarbonate resin comprising the unit of the following chemical formula 1. [ka] In the aforementioned chemical formula 1, X1-X4 are either identical or different from each other, and each is independently either O or S. R1 and R3 are identical or different from each other and are independently a cyano group or a phenyl group substituted with a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group having 10 or more carbon atoms; a fused ring group of a substituted or unsubstituted aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted heteroaryl group. R2 and R4 are either identical or different from each other, and independently of each other, are: hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; a fused ring group of a substituted or unsubstituted aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted heteroaryl group. R5 and R6 are either identical or different from each other, and independently of each other, are substituted or unsubstituted alkylene groups; or substituted or unsubstituted cycloalkylene groups. R11 and R12 are either identical or different from each other, and independently of each other are a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or bonded to each other to form a substituted or unsubstituted aromatic hydrocarbon ring group. R101 and R102 are either identical or different from each other, and independently of each other are hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group. r101 is 1 or 2, and if r101 is 2, the two R101s are either the same or different from each other. r102 is 1 or 2, and if r102 is 2, the two R102s are either the same or different from each other. m and n are integers from 0 to 6, p is an integer from 1 to 6. If m, n, and p are each 2 or greater, the structures within each set of parentheses are either identical or different from one another. * means a site linked to the main chain of the resin.

[0008] One embodiment of the present specification provides a method for producing the polycarbonate resin, which includes polymerizing a composition for producing a polycarbonate resin containing a compound of the following Chemical Formula 1a and a polycarbonate precursor.

Chemical formula

[0009] One embodiment of the present specification provides a polycarbonate resin composition containing the polycarbonate resin according to the above-described embodiment.

[0010] One embodiment of the present specification provides a molded article containing the polycarbonate resin composition according to the above-described embodiment.

Advantages 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, excellent optical lenses, optical films, optical thin films, optical resins, optical fibers, or LED encaps can be obtained with a thin thickness.

Modes for Carrying Out the Invention

[0013] Hereinafter, the present specification will be described in more detail.

[0014] According to one embodiment of the present specification, the polycarbonate resin containing the unit of Chemical Formula 1 increases the electron density of the molecule and reduces the volume of the molecule from the relational expression between the molecular structure and the refractive index known by Lorentz-Lorenz's formula, and it can be seen that the refractive index of the substance composed of the molecules increases. Further, since the core structure of Chemical Formula 1 is a derivative of BPA (bisphenol A), the volume of the molecule is small, it has excellent ability to be packed, and the refractive index of the resin can be improved.

[0015] Also, since R1 to R4 are electron-rich substituents, the electron density of the structure of Chemical Formula 1 can be increased, and the refractive index of the resin can be further improved. Therefore, the polycarbonate resin according to one embodiment of the present specification has a high refractive index and high transparency, and an optical lens, an optical film, or an optical resin using the same can be thin in thickness and exhibit excellent optical properties.

[0016] In addition, since it can further contain any one or more units of Chemical Formulas 2-1 to 2-3, it can complement the glass transition temperature (Tg) of the unit of Chemical Formula 1 or make the chain behavior of the unit of Chemical Formula 1 flexible, and has a technical effect advantageous for injection molding of molded products.

[0017] Throughout the present specification, the term "these combinations" included in the Markush-form expression means one or more mixtures or combinations selected from the group consisting of the components described in the Markush-form expression, and means including one or more selected from the group consisting of the components.

[0018] In the present specification, examples of substituents are described below, but are not limited thereto.

[0019] In the present specification,

Chemical Formula

[0020] In this specification, the term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced by another substituent, and the position of substitution is not limited to any position where a hydrogen atom can be substituted, i.e., any position where a substituent can be substituted, and if two or more substituents are substituted, the two or more substituents may be the same or different from one another.

[0021] In this specification, the term "substituted or unsubstituted" means substituted with one or more substituents selected from the group consisting of deuterium; halogen groups; hydroxyl groups; cyano groups; alkyl groups; cycloalkyl groups; alkoxy groups; alkenyl groups; aryloxy groups; arylthio groups; alkylthio groups; silyl groups; aryl groups; fused ring groups of aromatic hydrocarbon rings and aliphatic hydrocarbon rings; and heterocyclic groups; substituted with substituents in which two or more of the above-described substituents are linked; or having no substituents at all.

[0022] In this specification, the linking of two or more substituents means that a hydrogen atom of any one substituent is linked to another substituent. For example, the linking of two substituents means that a phenyl group and a naphthyl group are linked, [ka] It can be a substituent. Furthermore, the linking of three substituents includes not only the sequential linking of (substituent 1)-(substituent 2)-(substituent 3), but also the linking of (substituent 2) and (substituent 3) to (substituent 1). For example, a phenyl group, a naphthyl group, and an isopropyl group can be linked. [ka] It can be a substituent. The definition described above also applies to the linking of four or more substituents.

[0023] Examples of halogen groups used herein include fluorine, chlorine, bromine, or iodine.

[0024] In this specification, alkyl groups may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, and hexyl group. Examples of but are limited to butyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group, isohexyl group, 2-methylpentyl group, 4-methylhexyl group, and 5-methylhexyl group.

[0025] In this specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms. Specifically, examples include, but are not limited to, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, and adamantyl group.

[0026] In this specification, the alkoxy group may be linear, branched, or cyclic. The number of carbon atoms in the alkoxy group is not particularly limited, but it is preferably 1 to 30. Specifically, examples include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, and p-methylbenzyloxy.

[0027] 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, but are not limited to, vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1-butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl group, stilbenyl group, and styrenyl group.

[0028] In this specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

[0029] When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but it is preferably between 6 and 50 carbon atoms. Specifically, examples of monocyclic aryl groups include, but are not limited to, phenyl groups, biphenyl groups, and terphenyl groups.

[0030] When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited, but it is preferably 10 to 50 carbon atoms. Specifically, examples of polycyclic aryl groups include, but are not limited to, naphthyl, anthracene, phenanthrene, triphenylene, pyrene, phenalene, perylene, chrysene, and fluorene groups.

[0031] In this specification, the fluorene group may be substituted, or adjacent groups may bond to each other to form a ring.

[0032] Examples of the aforementioned fluorene group include: [ka] These are some examples, but they are not limited to these.

[0033] In this specification, “adjacent” groups may mean a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent that is stereostructically 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 position in a benzene ring, and two substituents substituted on the same carbon in an aliphatic ring, can be interpreted as “adjacent” groups.

[0034] In this specification, a heteroaryl group comprises one or more non-carbon atoms and heteroatoms. Specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but is preferably 2 to 30, and the heteroaryl group may be monocyclic or polycyclic. Examples of heteroaryl groups include thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, pyridine, bipyridine, pyrimidine, triazine, triazole, acridine, pyridazine, pyrazine, quinoline, quinazoline, quinoxaline, phthalazine, pyridopyrimidine, pyridopyrazine, pyrazinopyrazine, isoquinoline, indole, carbazole, benzoxazole, benzimidazole, benzothiazole, benzocarbazole, benzothiophene, dibenzothiophene, benzofuran, and phenanthridine groups. Examples include, but are not limited to, phenanthridine, phenanthroline, isoxazole, thiadiazole, dibenzofuran, dibenzosilol, phenoxathiine, phenoxazine, phenothiazine, dihydroindenocarbazole, spirofluorenexanthene, spirofluorenthoxanthene, tetrahydronaphthothiophene, tetrahydronaphthofuran, tetrahydrobenzothiophene, and tetrahydrobenzofuran.

[0035] In this specification, the silyl group may be an alkylsilyl group, an arylsilyl group, an alkylarylsilyl group, a heteroarylsilyl group, and the like. The alkyl group in the alkylsilyl group may be one of the examples of alkyl groups described above, the aryl group in the arylsilyl group may be one of the examples of aryl groups described above, the alkyl group and aryl group in the alkylarylsilyl group may be one of the examples of alkyl group and aryl group described above, and the heteroaryl group in the heteroarylsilyl group may be one of the examples of heteroaryl group described above.

[0036] In this specification, the hydrocarbon ring group may be an aromatic hydrocarbon ring group, an aliphatic hydrocarbon ring group, or a fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring, and may be selected from the examples of cycloalkyl groups, aryl groups, 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.

[0037] In this specification, a heterocyclic group comprises one or more non-carbon atoms and heteroatoms, and specifically, the heteroatoms may comprise one or more atoms selected from the group consisting of O, N, Se, and S. The heterocyclic group may be monocyclic or polycyclic, and may be an aromatic heterocyclic group; an aliphatic heterocyclic group; a fused ring group of an aromatic heterocyclic and an aliphatic heterocyclic; a fused ring group of an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and an aromatic heterocyclic; or a fused ring group of an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and an aliphatic heterocyclic. The aromatic heterocyclic group may be selected from the examples of heteroaryl groups.

[0038] In this specification, an aliphatic heterocyclic group means an aliphatic ring group containing one or more heteroatoms. An aliphatic heterocyclic group includes all aliphatic ring groups with single bonds, aliphatic ring groups containing multiple bonds, or aliphatic ring groups in which rings containing single and multiple bonds are fused. Examples of aliphatic heterocyclic groups include, but are not limited to, epoxy groups, oxirane groups, tetrahydrofuran groups, 1,4-dioxane groups, pyrrolidine groups, piperidine groups, morpholine groups, oxepan groups, azocane groups, thiocane groups, tetrahydronaphthothiophene groups, tetrahydronaphthofuran groups, tetrahydrobenzothiophene groups, and tetrahydrobenzofuran groups.

[0039] In this specification, the aryloxy group may also be represented as -ORo, where Ro is as described above for aryl groups.

[0040] In this specification, the arylthio group may also be represented by -SRs1, where the Rs1 is as described above for aryl groups.

[0041] In this specification, the alkylthio group may also be represented by -SRs2, where the Rs2 is as described above for alkyl groups.

[0042] In this specification, an alkylene group means a group with two bonding positions on an alkyl group, i.e., a divalent group. The above-mentioned description of alkyl groups may apply, except that each of these is a divalent group.

[0043] In this specification, a cycloalkylene group means a group with two bonding positions on a cycloalkyl group, i.e., a divalent group. The above-mentioned description of cycloalkyl groups may apply, except that each of these is a divalent group.

[0044] In this specification, a fused ring group of a divalent aromatic hydrocarbon ring and an aliphatic hydrocarbon ring means a group in which there are two bonding positions on the fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring, i.e., a divalent group. The above description of a fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring may apply, except that these are each divalent groups.

[0045] In this specification, an arylene group means a group with two bonding positions to an aryl group, i.e., a divalent group. The description of the aryl group described above may apply, except that these are each divalent groups.

[0046] In this specification, hydrogen refers to hydrogen, deuterium, or tritium.

[0047] In one embodiment of this specification, the portion of chemical formula 1 in which a substituent is not indicated may mean that hydrogen, deuterium, or tritium is substituted.

[0048] Preferred embodiments of the present invention will be described in detail below. However, embodiments of the present invention may be modified into various forms, and the scope of the present invention is not limited to the embodiments described later.

[0049] According to one embodiment of this specification, the unit of chemical formula 1 may be present in the polycarbonate resin in one or more units, and if it is present in two or more units, each unit may be the same or different from one another.

[0050] According to one embodiment of this specification, the polycarbonate resin further comprises one or more units from the following chemical formulas 2-1 to 2-3. [ka] In the above chemical formulas 2-1 to 2-3, L'11 and L''11 are identical or different from each other, and independently of each other, are a substituted or unsubstituted alkylene group; a substituted or unsubstituted cycloalkylene group; or a substituted or unsubstituted arylene group. X11-X14 are either identical or different from each other, and each is independently O; or S. Z11 and Z12 are identical or different from each other, and independently of each other, are substituted or unsubstituted alkylene groups; or substituted or unsubstituted cycloalkylene groups. a' and b' are either identical or different, and are independently integers between 0 and 10. If a' and b' are each 2 or greater, then the structures within each set of parentheses are either identical or different. * indicates a part that is connected to the main chain of the resin.

[0051] According to one embodiment of this specification, R101 is hydrogen. According to one embodiment of this specification, R102 is hydrogen.

[0052] According to one embodiment of this specification, the chemical formula 1 is the following chemical formula 1-1. [ka] In the above chemical formula 1-1, The definitions of *, m, n, p, R1-R6, R11, R12, and X1-X4 are the same as those in Chemical Formula 1 above.

[0053] According to one embodiment of this specification, X1 to X4 are identical or different from each other, and each is independently O or S. R1 and R3 are identical or different from each other and are independently a phenyl group substituted with a cyano group or a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic aryl group having 10 to 30 carbon atoms substituted or unsubstituted with a cyano group, a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched alkenyl group having 2 to 30 carbon atoms, or a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms; a fused ring group of a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms and a monocyclic or polycyclic aliphatic hydrocarbon ring having 3 to 30 carbon atoms; or a polycyclic heteroaryl group having 6 to 30 carbon atoms. R2 and R4 are either identical or different from each other, and are independently of each other: hydrogen; a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 6 to 30 carbon atoms; a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms substituted or unsubstituted with a cyano group, a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched alkenyl group having 2 to 30 carbon atoms, or a monocyclic or polycyclic heterocyclic heterocyclic group having 2 to 30 carbon atoms; a fused ring group of a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms and a monocyclic or polycyclic aliphatic hydrocarbon ring having 3 to 30 carbon atoms; or a polycyclic heteroaryl group having 6 to 30 carbon atoms. R5 and R6 are either identical or different from each other, and are independently a linear or branched alkylene group having 2 to 30 carbon atoms; or a monocyclic or polycyclic cycloalkylene group having 6 to 30 carbon atoms. R11 and R12 are either identical or different from each other, and independently consist of a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 6 to 30 carbon atoms; a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; or a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms, or are bonded to each other to form a polycyclic aromatic hydrocarbon ring having 10 to 30 carbon atoms.

[0054] According to one embodiment of this specification, R1 to R4 are identical or different from each other and each independently has one of the following structures. [ka]

[0055] In the above structure, Y1 and Y2 are independently either O or S. Any one of G1 to G8 is a site that bonds to chemical formula 1, and the remaining G1 to G8 that do not bond to chemical formula 1 are either identical or different to each other, and each is independently a hydrogen atom; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted hydrocarbon ring group; or a substituted or unsubstituted heterocyclic group. Any one of G9 to G16 is a site that bonds to chemical formula 1, and the remaining G9 to G16 that do not bond to chemical formula 1 are either identical or different to each other, and each is independently a hydrogen atom; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted hydrocarbon ring group; or a substituted or unsubstituted heterocyclic group. Any one of G17 to G26 is a site that bonds to chemical formula 1, and the remaining G17 to G26 that do not bond to chemical formula 1 are either identical or different to each other, and each is independently a hydrogen atom; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted hydrocarbon ring group; or a substituted or unsubstituted heterocyclic group. Any one of G27 to G38 is a site that bonds to chemical formula 1, and the remaining G27 to G38 that do not bond to chemical formula 1 are either identical or different from each other, and each is independently a hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted hydrocarbon ring group; or a substituted or unsubstituted heterocyclic group. Any one of G39 to G46 is a site that bonds to chemical formula 1, and the remaining G39 to G46 that do not bond to chemical formula 1 are either identical or different to each other and are independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted hydrocarbon ring group; or a substituted or unsubstituted heterocyclic group. Any one of G47 to G52 is a site that bonds to chemical formula 1, and the remaining G47 to G52 that do not bond to chemical formula 1 are either identical or different from each other, and each is independently a hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted hydrocarbon ring group; or a substituted or unsubstituted heterocyclic group. Any one of G53 to G59 is a site that bonds to chemical formula 1, and the remaining G53 to G59 that do not bond to chemical formula 1 are either identical or different to each other, and each is independently a hydrogen atom; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted hydrocarbon ring group; or a substituted or unsubstituted heterocyclic group. Any one of G60 to G67 is a site that bonds to chemical formula 1, and the remaining G60 to G67 that do not bond to chemical formula 1 are either identical or different from each other, and each is independently a hydrogen atom; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted hydrocarbon ring group; or a substituted or unsubstituted heterocyclic group. Any one of G68 to G76 is a site that bonds to chemical formula 1, and the remaining G68 to G76 that do not bond to chemical formula 1 are either identical or different to each other and are independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted hydrocarbon ring group; or a substituted or unsubstituted heterocyclic group.

[0056] According to one embodiment of this specification, X1 is O. According to one embodiment of this specification, X2 is O. According to one embodiment of this specification, X3 is O. According to one embodiment of this specification, X4 is O.

[0057] According to one embodiment of this specification, X1 is S. According to one embodiment of this specification, X2 is S. According to one embodiment of this specification, X3 is S. According to one embodiment of this specification, X4 is S.

[0058] According to one embodiment of this specification, R1 and R3 are identical or different from each other and are independently a cyano group or a phenyl group substituted with a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic aryl group having 10 to 30 carbon atoms; a fused ring group of a substituted or unsubstituted monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms and a monocyclic or polycyclic aliphatic hydrocarbon ring having 3 to 30 carbon atoms; or a substituted or unsubstituted polycyclic heteroaryl group having 6 to 30 carbon atoms.

[0059] According to one embodiment of this specification, R1 and R3 are identical or different from each other and independently of each other: a phenyl group substituted with a cyano group or a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic aryl group having 10 to 30 carbon atoms substituted or unsubstituted with a cyano group, a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched alkenyl group having 2 to 30 carbon atoms, or a monocyclic or polycyclic heterocyclic heterocyclic group having 2 to 30 carbon atoms; a fused ring group of a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms and a monocyclic or polycyclic aliphatic hydrocarbon ring having 3 to 30 carbon atoms; or a polycyclic heteroaryl group having 6 to 30 carbon atoms.

[0060] According to one embodiment of this specification, R1 and R3 are identical or different from each other and are independently a phenyl group substituted with a cyano group or a methyl group; a naphthyl group substituted with or unsubstituted with a cyano group; a dihydroindene group; or a quinoline group.

[0061] According to one embodiment of this specification, R2 and R4 are identical or different from each other and are independently of each other: hydrogen; a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 6 to 30 carbon atoms; a substituted monocyclic aryl group having 6 to 30 carbon atoms; a substituted or unsubstituted polycyclic aryl group having 10 to 30 carbon atoms; a fused ring group of a substituted or unsubstituted monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms and a monocyclic or polycyclic aliphatic hydrocarbon ring having 3 to 30 carbon atoms; or a substituted or unsubstituted polycyclic heteroaryl group having 6 to 30 carbon atoms.

[0062] According to one embodiment of this specification, R2 and R4 are identical or different from each other and are independently of each other: hydrogen; a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 6 to 30 carbon atoms; a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms substituted or unsubstituted with a cyano group, a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched alkenyl group having 2 to 30 carbon atoms, or a monocyclic or polycyclic heterocyclic heterocyclic group having 2 to 30 carbon atoms; a fused ring group of a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms and a monocyclic or polycyclic aliphatic hydrocarbon ring having 3 to 30 carbon atoms; or a polycyclic heteroaryl group having 6 to 30 carbon atoms.

[0063] According to one embodiment of this specification, R2 and R4 are identical or different from each other and independently of each other, being a cyano group, a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched alkenyl group having 2 to 30 carbon atoms, or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms substituted or unsubstituted with a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms; a fused ring group of a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms and a monocyclic or polycyclic aliphatic hydrocarbon ring having 3 to 30 carbon atoms; or a polycyclic heteroaryl group having 6 to 30 carbon atoms.

[0064] According to one embodiment of this specification, R2 and R4 are identical or different from each other and are independently a cyano group, or a phenyl group substituted or unsubstituted with a methyl group; a cyano group substituted or unsubstituted with a naphthyl group; a dihydroindene group; or a quinoline group.

[0065] According to one embodiment of this specification, R5 and R6 are identical or different from each other and are independently substituted or unsubstituted linear or branched alkylene groups having 2 to 30 carbon atoms; or substituted or unsubstituted monocyclic or polycyclic cycloalkylene groups having 6 to 30 carbon atoms.

[0066] According to one embodiment of this specification, R5 and R6 are identical or different from each other and are independently a linear or branched alkylene group having 2 to 30 carbon atoms; or a monocyclic or polycyclic cycloalkylene group having 6 to 30 carbon atoms.

[0067] According to one embodiment of this specification, R5 and R6 are ethylene groups.

[0068] According to one embodiment of this specification, R11 and R12 are identical or different from each other and are independently substituted or unsubstituted linear or branched alkyl groups having 1 to 30 carbon atoms; substituted or unsubstituted monocyclic or polycyclic cycloalkyl groups having 6 to 30 carbon atoms; monocyclic or polycyclic aryl groups having 6 to 30 carbon atoms; or substituted or unsubstituted monocyclic or polycyclic heteroaryl groups having 2 to 30 carbon atoms, or are bonded to each other to form a substituted or unsubstituted polycyclic aromatic hydrocarbon ring having 10 to 30 carbon atoms.

[0069] According to one embodiment of this specification, R11 and R12 are identical or different from each other and are independently a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 6 to 30 carbon atoms; a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; or a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms, or are bonded to each other to form a polycyclic aromatic hydrocarbon ring having 10 to 30 carbon atoms.

[0070] According to one embodiment of this specification, R11 and R12 are methyl groups.

[0071] According to one embodiment of this specification, X11 to X14 are O, L'11 and L''11 are identical or different from each other, and each is independently a linear or branched alkylene group having 1 to 30 carbon atoms; or a linear or branched alkyl group having 1 to 30 carbon atoms; or a monocyclic or polycyclic arylene group having 6 to 50 carbon atoms, substituted or unsubstituted with a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms. Z11 and Z12 are identical or different from each other, and each is independently a linear or branched alkylene group having 1 to 30 carbon atoms.

[0072] According to one embodiment of this specification, L'11 and L''11 are identical or different from each other and are independently a linear or branched alkylene group having 1 to 30 carbon atoms; or a linear or branched alkyl group having 1 to 30 carbon atoms; or a monocyclic or polycyclic arylene group having 6 to 50 carbon atoms, substituted or unsubstituted with a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0073] According to one embodiment of this specification, L'11 and L''11 are identical or different from each other and are independently a linear or branched alkylene group having 1 to 20 carbon atoms; or a linear or branched alkyl group having 1 to 20 carbon atoms; or a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms, substituted or unsubstituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0074] According to one embodiment of this specification, L'11 and L''11 are identical or different from each other and are independently 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.

[0075] According to one embodiment of this specification, X11 is O. According to one embodiment of this specification, X12 is O. According to one embodiment of this specification, X13 is O. According to one embodiment of this specification, X14 is O.

[0076] According to one embodiment of this specification, Z11 and Z12 are identical or different from each other and are independently linear or branched alkylene groups having 1 to 30 carbon atoms.

[0077] According to one embodiment of this specification, Z11 and Z12 are identical or different from each other and are independently linear or branched alkylene groups having 1 to 20 carbon atoms.

[0078] According to one embodiment of this specification, Z11 and Z12 are ethylene groups.

[0079] According to one embodiment of this specification, a' is 1. According to one embodiment of this specification, b' is 1.

[0080] According to one embodiment of this specification, a' is 0. According to one embodiment of this specification, b' is 0.

[0081] According to one embodiment of this specification, the polycarbonate resin may have -OH;-SH;-Cl;-CO2CH3; or -OC6H5 as terminal groups.

[0082] In one embodiment of this specification, the weight-average molecular weight of the polycarbonate resin is 5,000 g / mol to 500,000 g / mol, preferably 6,000 g / mol to 300,000 g / mol, 7,000 g / mol to 250,000 g / mol, or 8,000 g / mol to 200,000 g / mol. More preferably 9,000 g / mol to 150,000 g / mol, 10,000 g / mol to 100,000 g / mol, 12,000 g / mol to 80,000 g / mol, or 13,000 g / mol to 60,000 g / mol.

[0083] When the polycarbonate resin satisfies the aforementioned weight-average molecular weight range, the polycarbonate resin can have optimal fluidity and processability.

[0084] In one embodiment of the present invention, the number-average molecular weight of the polycarbonate resin is 3,000 g / mol to 300,000 g / mol, preferably 3,500 g / mol to 200,000 g / mol, 4,000 g / mol to 150,000 g / mol, or 4,500 g / mol to 100,000 g / mol, and more preferably 5,000 g / mol to 80,000 g / mol.

[0085] In this specification, the weight-average molecular weight (Mw) of polycarbonate resins and oligomers used in their production can be measured by gel permeation chromatography (GPC) using a polystyrene standard (PS standard) with an Agilent 1200 series instrument. Specifically, the measurement can be performed using an Agilent 1200 series instrument with a Polymer Laboratories PLgel MIX-B 300 mm length column, at a measurement temperature of 40°C, with tetrahydrofuran (THF) as the solvent and a flow rate of 1 mL / min. Samples of polycarbonate resin or oligomers are prepared to a concentration of 10 mg / 10 mL, supplied in 10 μL quantities, and the weight-average molecular weight (Mw) value is derived using a calibration curve formed with a 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.

[0086] In one embodiment of this specification, the glass transition temperature (Tg) of the polycarbonate resin may be 90°C to 200°C, or 100°C to 200°C. It may also be 110°C to 190°C. Preferably, it may be 120°C to 180°C, 120°C to 170°C, 130°C to 160°C, or 131°C to 166°C.

[0087] When the polycarbonate resin satisfies the aforementioned glass transition temperature range, it exhibits excellent heat resistance and injection molding properties. When mixing it with a resin having a different glass transition temperature range to produce a polycarbonate resin composition, the glass transition temperature can be easily adjusted, and the properties intended in this specification can be achieved.

[0088] 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 a 5.5 mg to 8.5 mg polycarbonate resin sample to 270°C in a nitrogen atmosphere, then cooling it, and scanning it while heating it a second time at a heating rate of 10°C / min.

[0089] In one embodiment of this specification, the refractive index of the polycarbonate resin, measured at a wavelength of 587 nm, is 1.50 to 1.75. The refractive index may preferably be 1.65 to 1.712, and more preferably 1.661 to 1.720. When the resin satisfies the aforementioned refractive index, it is possible to manufacture thin and lightweight optical lenses when applied to molded products such as optical lenses.

[0090] In one embodiment of this 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 also be 14 to 20. Preferably, it may be 14.5 to 19.5, and more preferably 12.95 to 19.50. When the resin satisfies the aforementioned Abbe number range, applying the resin to molded products such as optical lenses results in less dispersion and higher clarity.

[0091] The Abbe number is specifically the refractive index (n) at wavelengths D (587 nm), F (486 nm), and C (656 nm) at 20°C. D , n F , n C By measuring each of these parameters, the Abbe number can be obtained using the following formula. Abbe number = (n D -1) / (n F -nC )

[0092] The refractive index and Abbe number measurements described above may also be performed on a film produced by spin-coating a solution prepared by dissolving the resin in a solvent onto a silicon wafer. The coated film can be measured at 20°C using an ellipsometer to obtain a result corresponding to the wavelength of light. The 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 can be appropriately used as long as it is capable of measuring the refractive index and Abbe number of the resin composition according to this specification. The solvent may be dimethylacetamide or 1,2-dichlorobenzene, and the solution can be prepared by dissolving the resin sample in 10% by weight based on the total weight of the solution.

[0093] One embodiment of this specification provides a method for producing a polycarbonate resin, comprising the step of polymerizing a composition for producing a polycarbonate resin comprising a compound of the following chemical formula 1a and a polycarbonate precursor. [ka] In the aforementioned chemical formula 1a, The definitions of m, n, R1-R6, R11, R12, R101, R102, r101, r102, and X1-X4 are the same as those in Chemical Formula 1 above.

[0094] According to one embodiment of this specification, the composition for producing polycarbonate resin further comprises one or more second compounds from any of the following chemical formulas 2a-1 to 2a-3, wherein the compound of chemical formula 1a and the second compound are present in amounts of 0.01 mol% to 100 mol%:99.99 mol% to 0 mol%. Specifically, they are present in amounts of 0.01 mol% to 99.99 mol%:99.99 mol% to 0.01 mol%. More specifically, they are present in amounts 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%. [ka] In the above chemical formulas 2a-1 to 2a-3, L'11 and L''11 are identical or different from each other, and independently of each other, are a substituted or unsubstituted alkylene group; a substituted or unsubstituted cycloalkylene group; or a substituted or unsubstituted arylene group. X11-X14 are either identical or different from each other, and each is independently O; or S. Z11 and Z12 are identical or different from each other, and independently of each other, are substituted or unsubstituted alkylene groups; or substituted or unsubstituted cycloalkylene groups. a' and b' are either identical or different from each other, and are independently integers between 0 and 10. If a' and b' are each 2 or greater, then the structures within each set of parentheses are either identical or different from each other.

[0095] When the compound of chemical formula 1a and the second compound are present in the aforementioned amounts, polymerization is readily achieved, and depending on the substituents, the refractive index has a range of various values ​​or a high refractive index, and a wide range of glass transition temperatures. Furthermore, the glass transition temperature (Tg) and refractive index can be adjusted, and the chain behavior of the polycarbonate resin can be made flexible, thus providing advantageous technical effects for injection molding of molded products.

[0096] One embodiment of this specification provides a method for producing a polycarbonate resin, comprising the step of polymerizing a composition for producing a polycarbonate resin comprising the compound of chemical formula 1a; the second compound; and a polycarbonate precursor. The compound of chemical formula 1a and the second compound are present in amounts of 0.01 mol% to 100 mol%:99.99 mol% to 0 mol%. Specifically, they are present in amounts of 0.01 mol% to 99.99 mol%:99.99 mol% to 0.01 mol%. More specifically, they are present in amounts 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%.

[0097] When the compound of chemical formula 1a and the second compound are present in the aforementioned amounts, polymerization is readily achieved, and depending on the substituents, the refractive index has a range of various values ​​or a high refractive index, and a wide range of glass transition temperatures. Furthermore, the glass transition temperature (Tg) and refractive index can be adjusted, and the chain behavior of the polycarbonate resin can be made flexible, thus providing advantageous technical effects for injection molding of molded products.

[0098] The aforementioned polycarbonate resin manufacturing composition may further contain a solvent.

[0099] The solvent may be, for example, diphenyl ether, dimethylacetamide, or methanol, but is not limited to these, and may be appropriately selected if applicable to the art.

[0100] The solvent may be included in an amount of 5 to 60 parts by weight per 100 parts by weight of the resin manufacturing composition.

[0101] The solvent may be included in an amount of 5 to 50 parts by weight, 7 to 45 parts by weight, or 8 to 40 parts by weight, per 100 parts by weight of the resin manufacturing composition.

[0102] According to one embodiment of this specification, the chemical formula 1a may be included in two or more cases. The two or more chemical formulas 1a may be the same or different from each other.

[0103] In one embodiment of this specification, the compound of chemical formula 1a may be any of the following compounds, but is not limited to them. [ka] [ka]

[0104] In one embodiment of this specification, the second compound may be one or more of the following compounds, but is not limited to them. [ka]

[0105] In one embodiment of this specification, the chemical formula 2a-1 is one of the following compounds. [ka]

[0106] In one embodiment of this specification, the chemical formula 2a-2 is one of the following compounds. [ka]

[0107] In one embodiment of this specification, the chemical formula 2a-3 is the following compound. [ka]

[0108] In one embodiment of this specification, the compound of chemical formula 1a may be included in an amount of 1 to 100 parts by weight per 100 parts by weight of the polycarbonate resin manufacturing composition.

[0109] More specifically, the compound of chemical formula 1a may be included in an amount of 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 per 100 parts by weight of the polycarbonate resin manufacturing composition.

[0110] In one embodiment of this specification, the second compound may be included in an amount of 0 to 99 parts by weight, or 1 to 99 parts by weight, per 100 parts by weight of the polycarbonate resin production composition.

[0111] The second compound may be included in an amount of 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 per 100 parts by weight of the polycarbonate resin manufacturing composition.

[0112] In one embodiment of this specification, the polycarbonate precursor may be included in an amount of 1 to 60 parts by weight per 100 parts by weight of the polycarbonate resin production composition.

[0113] The polycarbonate precursor may be included in an amount of 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 per 100 parts by weight of the polycarbonate resin production composition.

[0114] According to one embodiment of this specification, the polycarbonate precursor has the following chemical formula A. [ka] In the aforementioned chemical formula A, Rb1 and Rb2 are either identical or different from each other, and independently of each other, are a halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; or a substituted or unsubstituted aryl group. a1 and a2 are either 0 or 1, respectively.

[0115] According to one embodiment of this specification, Rb1 and Rb2 are identical or different from each other and are independently a halogen group; a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 6 to 30 carbon atoms; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0116] According to one embodiment of this specification, Rb1 and Rb2 are identical or different from each other and are independently a halogen group; a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 6 to 20 carbon atoms; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0117] According to one embodiment of this specification, Rb1 and Rb2 are identical or different from each other and are independently a halogen group; a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 6 to 30 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0118] According to one embodiment of this specification, Rb1 and Rb2 are identical or different from each other and are independently a halogen group; a linear or branched alkyl group having 1 to 20 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 6 to 20 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0119] According to one embodiment of this specification, Rb1 and Rb2 are identical or different from each other and are independently -Cl; methyl group; ethyl group; n-propyl group; n-butyl group; isopropyl group; isobutyl group; or phenyl group.

[0120] According to one embodiment of this specification, the chemical formula A is one selected from the following compounds. [ka]

[0121] The polycarbonate precursor plays a role in linking additional comonomers as needed. Other specific examples applicable to the compound of chemical formula A include phosgene, triphosgene, diphosgene, bromophosgene, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, or bishaloformate, and one or more of these may be used as a mixture.

[0122] In one embodiment of this specification, the polycarbonate resin is preferably polymerized from the compound of chemical formula 1a; the polycarbonate precursor of chemical formula A.

[0123] In one embodiment of this specification, the polycarbonate resin is preferably polymerized from the compound of chemical formula 1a; the second compound and the polycarbonate precursor of chemical formula A.

[0124] By polymerizing the compound of chemical formula 1a with the polycarbonate precursor of chemical formula A, the unit of chemical formula 1 described above can be formed, and by polymerizing the second compound with the polycarbonate precursor of chemical formula A, one or more units of chemical formulas 2-1 to 2-3 described above can be formed.

[0125] The compound of chemical formula 1a and the polycarbonate precursor of chemical formula A can be polymerized to form the unit of chemical formula 1 described above.

[0126] The compound of chemical formula 1a may be used in an amount of 1 mole to 100 moles, or 1 mole to 99 moles, per 100 moles of the total monomers constituting the polycarbonate resin containing the unit of chemical formula 1.

[0127] The polycarbonate precursor of chemical formula A may be used in an amount of 50 to 150 moles per 100 moles of the total monomer of the compound of chemical formula 1a that constitutes the resin.

[0128] By polymerizing the second compound with the polycarbonate precursor of chemical formula A, one or more units of the aforementioned chemical formulas 2-1 to 2-3 can be formed.

[0129] The second compound may be used in an amount of 1 mole to 100 moles, or 1 mole to 99 moles, per 100 moles of total monomers constituting the polycarbonate resin containing one or more units of the chemical formulas 2-1 to 2-3.

[0130] The polycarbonate precursor of chemical formula A may be used in an amount of 50 to 150 moles per 100 moles of the total monomer of the second compound constituting the resin.

[0131] The polymerization of resins according to this specification may be carried out using methods well known in the art.

[0132] The polymerization is preferably carried out by a melt polycondensation method.

[0133] The aforementioned melt polycondensation method may involve using the polycarbonate resin manufacturing composition, and optionally applying a catalyst, and may be carried out under heating, and further under atmospheric pressure or reduced pressure, while removing by-products by transesterification. The catalyst may be a substance commonly used in the art.

[0134] Specifically, in the melt polycondensation method, it is preferable to melt the compound of chemical formula 1a and the polycarbonate precursor in a reaction vessel, and then carry out the reaction while allowing the by-product compound to remain.

[0135] More specifically, the melt polycondensation method is preferably carried out after melting the compound of chemical formula 1a; the second compound; and the polycarbonate precursor in a reaction vessel, and then allowing the by-product compound to remain.

[0136] To retain the by-product compounds, the reaction apparatus may be blocked, or the pressure may be controlled by reducing or increasing the pressure.

[0137] The reaction time for this step is 20 minutes or more and 600 minutes or less, preferably 40 minutes or more and 450 minutes or less, and more preferably 60 minutes or more and 350 minutes or less.

[0138] In this process, if the by-product compounds are immediately removed by distillation after formation, the final resin obtained will have a low content of high molecular weight compounds. However, if the by-product compounds are allowed to remain in the reaction vessel for a certain period of time, the final resin obtained will have a high content of high molecular weight compounds.

[0139] The melt polycondensation method described above may be carried out in a continuous or batch manner. The reaction apparatus used for the reaction may be a vertical type equipped with soken-type impellers, anchor-type impellers, Maxblende impellers, helical ribbon-type impellers, etc., a horizontal type equipped with paddle impellers, grid impellers, spectacle impellers, etc., or an extruder type equipped with a screw. Furthermore, it is preferable to use a reaction apparatus that appropriately combines these reaction apparatuses, taking into consideration the viscosity of the polymer.

[0140] In the method for producing polycarbonate resin used herein, the catalyst may be removed or deactivated after the polymerization reaction is complete in order to maintain thermal stability and hydrolysis stability. A method of deactivating the catalyst by adding an acidic substance known in the art is preferably carried out.

[0141] Examples of the aforementioned acidic substances 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; phosphorous acid esters such as triphenyl phosphate, monophenyl phosphate, diphenyl phosphate, diethyl phosphate, di-n-propyl phosphate, di-n-butyl phosphate, di-n-hexyl phosphate, dioctyl phosphate, and monooctyl phosphate; triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and Phosphate esters such as monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonic acid esters such as diethyl phenylphosphonate; phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids such as boric acid and phenylboric acid; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate; organic halides such as stearate chloride, benzoyl chloride, and p-toluenesulfonic acid chloride; alkyl sulfates such as dimethyl sulfate; and organic halides such as benzyl chloride are preferably used.

[0142] The acidic substance may be used in an amount of 0.1 to 5 moles, preferably 0.1 to 1 mole, per 100 moles of the catalyst.

[0143] If the amount of the acidic substance is less than 0.1 moles, the deactivation effect will be insufficient, which is undesirable. Furthermore, if it exceeds 5 moles, the heat resistance of the resin will decrease, making the molded product more prone to discoloration, which is also undesirable.

[0144] After the catalyst is deactivated, a further step may be taken to defoliate the 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 apparatus equipped with stirring blades that have excellent surface renewal capabilities, such as paddle blades, lattice blades, or spectacle blades, or a thin-film evaporator is preferably used.

[0145] The resins described herein preferably contain as little foreign matter as possible, and filtration of the molten raw material and filtration of the catalyst solution are preferably carried out.

[0146] The mesh of the filter used for the filtration is preferably 5 μm or less, and more preferably 1 μm or less. Furthermore, filtration of the generated resin is preferably carried out using a polymer filter. The mesh of the polymer filter is preferably 100 μm or less, and more preferably 30 μm or less. In addition, the process of collecting the resin pellets must be carried out in a low-dust environment, preferably class 6 or lower, and more preferably class 5 or lower.

[0147] Furthermore, in addition to injection molding, other methods for molding molded articles containing the polycarbonate resin include, but are not limited to, compression molding, casting, roll processing, extrusion molding, and stretching.

[0148] Another embodiment of this specification provides a polycarbonate resin composition comprising the resin according to the embodiment described above.

[0149] In one embodiment of this specification, the polycarbonate resin may be included in an amount of 1 to 80 parts by weight based on 100 parts by weight of the polycarbonate resin composition.

[0150] In one embodiment of this specification, the polycarbonate resin composition may further contain a solvent. The solvent may be, for example, dimethylacetamide or 1,2-dichlorobenzene.

[0151] The solvent may be included in an amount of 20 to 99 parts by weight based on 100 parts by weight of the polycarbonate resin composition.

[0152] The polycarbonate resin composition may further contain additional monomers in addition to the compound of chemical formula 1a. The additional monomers are not particularly limited, and monomers commonly used in the art related to polycarbonates may be used as appropriate, as long as they do not change the main physical properties of the polycarbonate resin composition. The additional monomers may be used in amounts of 1 mole to 50 moles per 100 moles of the total monomers constituting the resin containing the unit of chemical formula 1.

[0153] In addition to the resin containing the unit of chemical formula 1, the polycarbonate resin composition may further optionally contain one or more additives selected from the group consisting of antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact reinforcers, fluorescent whitening agents, ultraviolet absorbers, inorganic additives, pigments, and dyes.

[0154] The additive may be included in an amount of 1 to 99 parts by weight based on 100 parts by weight of the polycarbonate resin composition.

[0155] The types of antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact reinforcers, fluorescent whitening agents, ultraviolet absorbers, inorganic additives, pigments, or dyes are not particularly limited, and those applicable to the art may be used as appropriate.

[0156] Another embodiment of this specification provides a molded article comprising a resin composition according to the embodiment described above.

[0157] In one embodiment of this specification, the molded article may be manufactured from the polycarbonate resin composition or a cured product thereof.

[0158] As an example of a method for manufacturing the molded article, the method may include the steps of thoroughly mixing a resin containing the unit of chemical formula 1 and one or more units from chemical formulas 2-1 to 2-3 with the additive in a mixer, extruding it in an extruder to produce pellets, and then injecting the pellets in an injection molding machine after drying them.

[0159] In one embodiment of this specification, the molded article is an optical lens.

[0160] In one embodiment of this specification, the thickness of the optical lens is 0.1 μm to 30 mm.

[0161] An optical lens according to one embodiment of this specification has a high refractive index, which allows for the realization of a thin optical lens.

[0162] The optical lens is manufactured using the polycarbonate resin, is thin, has a high refractive index and high transparency, and can preferably be applied to cameras, mobile devices, vehicles, and autonomous driving sensor lenses.

[0163] In one embodiment of this specification, the molded article is an optical fiber.

[0164] In one embodiment of this specification, the molded article is an optical film or optical thin film. The optical film or optical thin film is manufactured using the polycarbonate resin, is thin, has excellent light-gathering and light-diffusing effects, and can preferably be applied to backlight modules for liquid crystal displays, planar lenses, metalens, and the like.

[0165] In one embodiment of this specification, the thickness of the optical film or optical thin film is 0.1 nm to 10 mm.

[0166] In one embodiment of this specification, the molded article is an optical resin. The optical resin is manufactured using the polycarbonate resin, and is thin, has a high refractive index and low birefringence, and has low optical loss.

[0167] In one embodiment of this specification, the molded article is an LED encap. [Examples]

[0168] The following examples illustrate this specification in more detail.

[0169] Manufacturing Example 1 Monomer 1a (82.103 g (0.1 mol)) and diphenylcarbonate (21.422 g (0.1 mol)) were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a byproduct, and the degree of reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was complete, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and resin 1 was obtained as a polymerized molten polymer resin. [ka]

[0170] Manufacturing Example 2 Monomer 1a (41.052 g (0.05 mol)), monomers 2-3 (18.708 g (0.05 mol)), and 21.422 g (0.1 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a byproduct, and the degree of reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was complete, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and resin 2 was obtained as a polymerized molten polymer resin. [ka]

[0171] Manufacturing Example 3 Monomer 1a (28.736 g (0.035 mol)), monomer 2-1 (16.159 g (0.03 mmol)), monomer 2-3 (13.095 g (0.035 mol)), and 21.422 g (0.1 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a byproduct, and the degree of reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was complete, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and resin 3 was obtained as a polymerized molten polymer resin.

[0172] Manufacturing Example 4 Monomer 1a (24.631 g (0.03 mol)), monomer 2-2 (17.722 g (0.03 mmol)), monomer 2-3 (14.966 g (0.04 mol)), and 21.422 g (0.1 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a byproduct, and the degree of reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was complete, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and resin 4 was obtained as a polymerized molten polymer resin.

[0173] Manufacturing Example 5 Monomer 1a (24.631 g (0.03 mol)), monomer 2-3 (14.966 g (0.04 mol)), monomer 2-5 (13.156 g (0.03 mmol)), and 21.422 g (0.1 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a byproduct, and the degree of reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was complete, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and resin 5 was obtained as a polymerized molten polymer resin.

[0174] Manufacturing Example 6 Monomer 1a (16.421 g (0.02 mol)), monomer 2-3 (14.966 g (0.04 mol)), monomer 2-6 (3.964 g (0.02 mmol)), monomer 2-7 (7.008 g (0.02 mmol)), and 21.422 g (0.1 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a byproduct, and the degree of reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was complete, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and resin 6 was obtained as a polymerized polymer molten resin.

[0175] Manufacturing example 7 Monomer 1a (16.421 g (0.02 mol)), monomer 2-3 (14.966 g (0.04 mol)), monomer 2-6 (3.964 g (0.02 mmol)), monomer 2-8 (5.726 g (0.02 mmol)), and 21.422 g (0.1 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a byproduct, and the degree of reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was complete, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and resin 7 was obtained as a polymerized polymer molten resin.

[0176] Manufacturing Example 8 Monomer 1a (16.421 g (0.02 mol)), monomer 2-3 (14.966 g (0.04 mol)), monomer 2-6 (3.964 g (0.02 mmol)), monomer 2-9 (7.569 g (0.02 mmol)), and 21.422 g (0.1 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a byproduct, and the degree of reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was complete, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and resin 8 was obtained as a polymerized molten polymer resin.

[0177] Manufacturing Example 9 Monomer 1a (12.315 g (0.015 mol)), monomer 2-1 (21.546 g (0.04 mmol)), monomer 2-2 (2.954 g (0.005 mmol)), monomer 2-3 (14.966 g (0.04 mol)), and 21.422 g (0.1 mol) of diphenylcarbonate were melted and reacted at 250°C for 5 hours. As the reaction progressed, phenol was generated as a byproduct, and the degree of reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was complete, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, and resin 9 was obtained as a polymerized molten polymer resin.

[0178] Examples The molecular weight and molecular weight distribution (PDI = Mw / Mn) of the polymerized resin sample were confirmed by gel permeation chromatography (GPC), and a thermogram was obtained using differential scanning calorimeter (DSC) to investigate its thermal properties. To measure the refractive index and Abbe number, an ellipsometer was used after film formation to obtain results corresponding to the wavelength of light.

[0179] Molecular weight was determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF, stabilized with BHT (butylated hydroxytoluene)) as the solvent. The resin sample was dissolved in tetrahydrofuran at a concentration of 1.0 mg / 1 ml, filtered through a syringe filter, and the solution was injected and measured at 40°C. The results are shown in Table 2 below. A Waters RI detector was used, and two Agilent PLgel MIXED-B columns were used.

[0180] The glass transition temperature (Tg) of the resin was measured using a differential scanning calorimeter (DSC). Resin samples ranging from 5.5 mg to 8.5 mg were heated to 270°C under an N2 flow, then cooled. During the second heating, the glass transition temperature (Tg) was determined from the graph obtained by scanning while heating at a rate of 10°C / min, and the results are shown in Table 2 below.

[0181] To measure the refractive index and Abbe number of the resin, a polymer solution prepared by dissolving the obtained resin powder sample in a solvent, dimethylacetamide, to 10% by weight based on the total weight of the polymer solution was spin-coated onto a silicon wafer at a rotational speed of 220 rpm, and after forming a film with a thickness of 20 μm, a resultant value corresponding to the wavelength of light was obtained using an ellipsometer at 20°C, which is shown in Table 2 below. Specifically, the refractive index was measured at a wavelength of 587 nm, and the Abbe number was determined by measuring the refractive indices (n D , n F , n C ) at wavelengths D (587 nm), F (486 nm), and C (656 nm) respectively, and obtaining the Abbe number using the following calculation formula. Abbe number = (n D - 1) / (n F - n C )

[0182]

Table 1

[0183]

Table 2

[0184] In Table 2, Mn represents the number average molecular weight, Mw represents the weight average molecular weight, PDI represents the polydispersity index, RI represents the refractive index, and Tg represents the glass transition temperature. The refractive index is the value measured at a wavelength of 587 nm.

[0185] According to Table 1 and Table 2 above, the resins of Examples 1 - 9 contain the unit of Chemical Formula 1 according to the embodiments of the present specification. In particular, when substituted with electron-rich substituents such as R1 - R4 of the benzene ring of the bisphenol A core structure, the refractive index can be improved by increasing the electron density of the bisphenol A core structure.

[0186] Furthermore, by including one or more units from chemical formulas 2-1 to 2-3, the glass transition temperature (Tg) and refractive index can be adjusted, and the chain behavior of the polycarbonate resin can be made more flexible, thus providing advantageous technical effects for injection molding of molded products.

Claims

1. Polycarbonate resin containing the unit of chemical formula 1 below, and further containing two or more units from chemical formulas 2-1 to 2-3 below: 【Chemistry 1】 In the aforementioned chemical formula 1, X1 to X4 are either identical or different from each other, and each is independently either O or S. R1 and R3 are identical or different from each other, and independently of each other, they are a phenyl group substituted with a cyano group or a methyl group; a naphthyl group substituted with or unsubstituted with a cyano group; a dihydroindene group; or a quinoline group. R2 and R4 are either identical or different to each other, and independently of each other, they are a cyano group, or a phenyl group substituted or unsubstituted with a methyl group; a cyano group substituted or unsubstituted with a naphthyl group; a dihydroindene group; or a quinoline group. R5 and R6 are identical or different from each other, and independently are substituted or unsubstituted alkylene groups; or substituted or unsubstituted cycloalkylene groups. R11 and R12 are either identical or different from each other, and are independently linear or branched alkyl groups having 1 to 30 carbon atoms. R101 and R102 are either identical or different from each other, and independently of each other are hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group. r101 is 1 or 2, and if r101 is 2, the two R101s are either the same or different from each other. r102 is 1 or 2, and if r102 is 2, the two R102s are either the same or different from each other. m and n are integers from 0 to 6, p is an integer from 1 to 6, If m, n, and p are each 2 or more, the structures within each set of parentheses are either identical or different from each other. * indicates a part that is connected to the main chain of the resin. 【Chemistry 2】 In the aforementioned chemical formulas 2-1 to 2-3, L'11 and L''11 are identical or different from each other, and independently of each other, are a substituted or unsubstituted alkylene group; a substituted or unsubstituted cycloalkylene group; or a substituted or unsubstituted arylene group. X11 to X14 are either identical or different from each other, and each is independently O; or S. Z11 and Z12 are identical or different from each other, and independently of each other, are substituted or unsubstituted alkylene groups; or substituted or unsubstituted cycloalkylene groups. a' and b' are either identical or different, and are independently integers between 0 and 10. If a' and b' are each 2 or greater, then the structures within each set of parentheses are either identical or different. * indicates a part that is connected to the main chain of the resin.

2. The polycarbonate resin according to claim 1, wherein the aforementioned chemical formula 1 is the following chemical formula 1-1: 【Transformation 3】 In the above chemical formula 1-1, The definitions of *, m, n, p, R1-R6, R11, R12, and X1-X4 are the same as those in Chemical Formula 1 above.

3. The aforementioned X1 to X4 are either identical or different from each other, and each is independently O or S. The polycarbonate resin according to claim 1, wherein R5 and R6 are the same or different from each other and are independently a linear or branched alkylene group having 2 to 30 carbon atoms; or a monocyclic or polycyclic cycloalkylene group having 6 to 30 carbon atoms.

4. The above X11 to X14 are O, L'11 and L''11 are identical or different from each other, and each is independently a linear or branched alkylene group having 1 to 30 carbon atoms; or a linear or branched alkyl group having 1 to 30 carbon atoms; or a monocyclic or polycyclic arylene group having 6 to 50 carbon atoms, substituted or unsubstituted with a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms. The polycarbonate resin according to claim 1, wherein Z11 and Z12 are the same or different from each other, and each is independently a linear or branched alkylene group having 1 to 30 carbon atoms.

5. The polycarbonate resin according to claim 1, wherein the weight-average molecular weight (Mw) is 5,000 g / mol to 500,000 g / mol.

6. The polycarbonate resin according to claim 1, wherein the refractive index measured at a wavelength of 587 nm is 1.50 to 1.

75.

7. The polycarbonate resin according to claim 1, wherein the glass transition temperature (Tg) is 90°C to 200°C.

8. The polycarbonate resin according to claim 1, wherein the Abbe number measured at wavelengths of 486, 587, and 656 nm is 5 to 45.

9. Compounds of the following chemical formula 1a; and A method for producing a polycarbonate resin according to any one of claims 1 to 8, comprising the step of polymerizing a composition for producing a polycarbonate resin containing a polycarbonate precursor, wherein the composition for producing a polycarbonate resin further comprises two or more second compounds from any two of the following chemical formulas 2a-1 to 2a-3, and the compound of chemical formula 1a and the second compounds are contained in an amount of 0.01 mol% to 99.99 mol% and 99.99 mol% to 0.01 mol%: 【Chemistry 4】 In the aforementioned chemical formula 1a, The definitions of m, n, R1 to R6, R11, R12, R101, R102, r101, r102, and X1 to X4 are the same as the definitions in Chemical Formula 1 above. 【Transformation 5】 In the above chemical formulas 2a-1 to 2a-3, L'11 and L''11 are identical or different from each other, and independently of each other, are a substituted or unsubstituted alkylene group; a substituted or unsubstituted cycloalkylene group; or a substituted or unsubstituted arylene group. X11 to X14 are either identical or different from each other, and each is independently O; or S. Z11 and Z12 are identical or different from each other, and independently of each other, are substituted or unsubstituted alkylene groups; or substituted or unsubstituted cycloalkylene groups. a' and b' are either identical or different from each other, and are independently integers between 0 and 10. If a' and b' are each 2 or greater, then the structures within each set of parentheses are either identical or different from each other.

10. The method for producing a polycarbonate resin according to claim 9, wherein the polycarbonate precursor has the following chemical formula A: 【Transformation 6】 In the aforementioned chemical formula A, Rb1 and Rb2 are either identical or different from each other, and independently of each other, are a halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; or a substituted or unsubstituted aryl group. a1 and a2 are either 0 or 1, respectively.

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

12. A molded article comprising the polycarbonate resin composition described in claim 11.

13. The molded article according to claim 12, wherein the molded article is an optical lens.

14. The molded article according to claim 13, wherein the thickness of the optical lens is 0.1 μm to 30 mm.

Images