Polyester resin and preparation method thereof

Abstract

The present application relates to a polyester resin comprising a unit of Formula 1, a method for manufacturing the same, a polyester resin composition comprising the same, and a molded article comprising the polyester resin composition.

Description

Technology Field

[0001] This specification relates to a polyester resin and a method for manufacturing the same. Background Technology

[0002] If 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. Accordingly, the higher the refractive index of the optical material, the thinner and lighter the lens can be manufactured, which enables the miniaturization of various devices in which the lens is used.

[0003] Generally, as the refractive index of optical materials increases, there is a problem where the Abbe number decreases, and additionally, a certain level of transparency is required for use as an optical material. Prior art literature

[0004] Korean Published Patent Application No. 10-2020-0034523 The problem to be solved

[0005] One embodiment of the present specification aims to provide a polyester resin of a novel structure and a method for manufacturing the same.

[0006] Another embodiment of the present specification aims to provide a polyester resin composition comprising a polyester resin of a novel structure and a molded article made of said polyester resin composition. means of solving the problem

[0007] One embodiment of the present specification provides a polyester resin comprising a unit of the following chemical formula 1.

[0008] [Chemical Formula 1]

[0009]

[0010] In the above chemical formula 1,

[0011] R1 and R2 are distinct from each other and are each independently 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 hydroxyl group, a cyano group, an alkyl group, 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, and

[0012] r1 and r2 are each integers from 1 to 4, and if r1 is 2 or more, the 2 or more R1s are the same or different from each other, and if r2 is 2 or more, the 2 or more R2s are the same or different from each other, and

[0013] L1 and L2 are the same or different from each other, and are each independently substituted or unsubstituted arylene groups.

[0014] X1 to X5 are the same or different from each other, and each is independently O; or S,

[0015] Z1 to Z3 are the same or different from each other, and each is independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group, and

[0016] La is a substituted or unsubstituted arylene group, and

[0017] a, b, and q are equal to or different from each other, and each is an integer from 0 to 6 independently, and when a, b, and q are each 2 or greater, the structures inside each parenthesis are equal to or different from each other,

[0018] p is an integer from 1 to 6, and if p is 2 or greater, the structures inside the parentheses are the same or different from each other, and

[0019] * refers to the part connected to the main chain of the resin.

[0020] One embodiment of the present specification provides a method for manufacturing a polyester resin comprising the step of polymerizing a composition for manufacturing a polyester resin comprising a compound of the following formula 1a and a polyester precursor.

[0021] [Chemical Formula 1a]

[0022]

[0023] In the above chemical formula 1a,

[0024] The definitions of R1, R2, r1, r2, L1, L2, X1 to X4, a, b, Z1 and Z2 are the same as those defined in Chemical Formula 1 above.

[0025] Another embodiment of the present specification provides a polyester resin composition comprising a polyester resin according to the embodiment described above.

[0026] Another embodiment of the present specification provides a molded article comprising a polyester resin composition according to the above embodiment. Effects of the invention

[0027] Polyester resins according to one embodiment of the present specification have a high refractive index and high transparency.

[0028] By using a polyester resin according to one embodiment of the present specification, a thin, excellent optical lens, optical film, optical thin film, or optical resin can be obtained. Brief explanation of the drawing

[0029] Figure 1 is a figure showing the reduction rate of lens thickness according to the difference in refractive index. Specific details for implementing the invention

[0030] The present specification will be described in more detail below.

[0031] According to one embodiment of the present specification, a polyester resin comprising a unit of Formula 1 can be seen from the relationship between molecular structure and refractive index known by Lorentz-Lorenz's formula that the electron density of the molecule is increased and the molecular volume is reduced, thereby increasing the refractive index of the material composed of the molecule. In addition, since the substituents of the benzene rings on both sides of the fluorene structure of Formula 1 form an asymmetric structure and include R1 and R2 as substituents, the electron density is increased, thereby improving the refractive index of a molded article containing the polyester resin. Therefore, the polyester 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 it can have a thin thickness and exhibit excellent optical properties.

[0032] Throughout this specification, the term “combination thereof” included in the Markush-type expression means one or more mixtures or combinations selected from the group consisting of the components described in the Markush-type expression, and means including one or more selected from the group consisting of said components.

[0033] Examples of substituents in this specification are described below, but are not limited thereto.

[0034] In this specification, refers to the connected part.

[0035] In this specification, the term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the substitution location is not limited to the location where the hydrogen atom is substituted, that is, any location where a substituent can be substituted, and in the case of two or more substitutions, the two or more substituents may be the same or different from each other.

[0036] In this specification, the term “substituted or unsubstituted” means that it is substituted with one or more substituents selected from the group consisting of deuterium; halogen group; hydroxyl group; cyano group; alkyl group; cycloalkyl group; alkoxy group; alkenyl group; aryloxy group; arylthio group; alkylthio group; silyl group; aryl group; condensed ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; and heteroaryl group, or is substituted with a substituent in which two or more of the exemplified substituents are connected, or has no substituents.

[0037] In this specification, the connection of two or more substituents means that a hydrogen of one substituent is connected to another substituent. For example, the connection of two substituents means that a phenyl group and a naphthyl group are connected or It can be a substituent. In addition, the connection of three substituents includes not only the consecutive connection of (substituent 1)-(substituent 2)-(substituent 3), but also the connection of (substituent 2) and (substituent 3) to (substituent 1). For example, a phenyl group, a naphthyl group, and an isopropyl group are connected, , or It can be a substituent. The aforementioned definition applies equally to the connection of 4 or more substituents.

[0038] In this specification, examples of the halogen group include fluorine, chlorine, bromine, or iodine.

[0039] In the present 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 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, heptyl 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, There are, but are not limited to, 2,2-dimethylheptyl groups, 1-ethyl-propyl groups, 1,1-dimethyl-propyl groups, isohexyl groups, 2-methylpentyl groups, 4-methylhexyl groups, 5-methylhexyl groups.

[0040] In the present specification, the cycloalkyl group is not particularly limited, but is preferably 3 to 30 carbon atoms. Specifically, it includes, but is not limited to, 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, an adamantyl group, etc.

[0041] In the present specification, the alkoxy group may be a straight chain, a branched chain, or a cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but it is preferred to have 1 to 30 carbon atoms. Specifically, it may be 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, a p-methylbenzyloxy group, etc., but is not limited thereto.

[0042] In the present specification, the alkenyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include, butanely, 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, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, stilbenyl group, styrenyl group, etc., but are not limited thereto.

[0043] In the present specification, the aryl group is not particularly limited, but is preferably 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

[0044] When the above aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but it is preferable that the number of carbon atoms be 6 to 50. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.

[0045] When the above aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited, but it is preferable that the number of carbon atoms be 10 to 50. Specifically, the polycyclic aryl group may be a naphthyl group, anthracene group, phenanthrene group, triphenylene group, pyrene group, phenalene group, perylene group, chrysene group, fluorene group, etc., but is not limited thereto.

[0046] In the present specification, the fluorene group may be substituted, and adjacent groups may combine with each other to form a ring.

[0047] When the above fluorene group is substituted, , , , , , , and There are, but are not limited to, the following.

[0048] 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 located closest to the atom on which the substituent is substituted, 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 may be interpreted as "adjacent" groups to each other.

[0049] In the present specification, the heteroaryl group comprises one or more non-carbon atoms or heteroatoms, and specifically, the heteroatoms may comprise 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 it is preferable that the number of carbon atoms be 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, quinazolin, quinoxaline, phthalazine, pyridopyrimidine, pyridopyrazine, pyrazinopyrazine, isoquinoline, indole, carbazole, benzoxazole, benzimidazole, benzothiazole, benzocarbazole, benzothiophen, dibenzothiophen, benzofuran, phenanthridine, phenanthroline, isooxazole, and thiadiazole. There are, but are not limited to, dibenzofuran groups, dibenzosilol groups, phenoxanthine groups (phenoxathiine), phenoxazine groups, phenothiazine groups, dihydroindenocarbazole groups, spiroflurenxanthen groups, spiroflurentioxanthen groups, tetrahydronaphthothiophen groups, tetrahydronaphthofuran groups, tetrahydrobenzofuran groups, and tetrahydrobenzofuran groups.

[0050] In the present specification, the silyl group may be an alkylsilyl group, an arylsilyl group, an alkylarylsilyl group; a heteroarylsilyl group, etc. Among the alkylsilyl groups, the alkyl group may be an example of the alkyl group described above, among the arylsilyl groups, the aryl group may be an example of the aryl group described above, among the alkyl and aryl groups among the alkylarylsilyl groups, the alkyl and aryl groups may be an example of the alkyl and aryl groups described above, and among the heteroarylsilyl groups, the heteroaryl group may be an example of the heteroaryl group described above.

[0051] In the present specification, the hydrocarbon ring may be an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, or a condensation ring of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring, and may be selected from examples of the cycloalkyl group, aryl group, and combinations thereof, and the hydrocarbon ring may be 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, but is not limited thereto.

[0052] In this specification, the aryloxy group may be represented as -ORo, and the description of the aryl group described above applies to Ro.

[0053] In this specification, the arylthio group may be represented as -SRs1, and the description of the aryl group described above applies to Rs1.

[0054] In this specification, the alkylthio group may be represented as -SRs2, and the description of the alkyl group described above applies to Rs2.

[0055] In this specification, an alkylene group refers to a group having two bonding positions to an alkyl group, i.e., a divalent group. Except for the fact that each of these is a divalent group, the description of the alkyl group described above may apply.

[0056] In this specification, a cycloalkylene group refers to a cycloalkyl group having two bonding sites, i.e., a divalent group. Except for the fact that each of these is a divalent group, the description of the cycloalkyl group described above may apply.

[0057] In this specification, an arylene group refers to a group having two binding sites to an aryl group, i.e., a divalent group. Except for the fact that each of these is a divalent group, the description of the aryl group described above may apply.

[0058] In this specification, the condensation ring of a divalent aromatic hydrocarbon ring and an aliphatic hydrocarbon ring refers to a condensation ring of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring having two bonding sites, i.e., a divalent group. Except for the fact that they are each divalent groups, the description of the condensation ring of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring described above may be applied.

[0059] Preferred embodiments of the present invention are described in detail below. However, embodiments of the present invention may be modified in various forms, and the scope of the present invention is not limited to the embodiments described below.

[0060] According to one embodiment of the present specification, one or more units of the chemical formula 1 may be included in the polyester resin, and if two or more are included, each unit may be the same or different from each other.

[0061] According to one embodiment of the present specification, the polyester resin further comprises a unit of the following chemical formula 2.

[0062] [Chemical Formula 2]

[0063]

[0064] In the above chemical formula 2,

[0065] L11 is a substituted or unsubstituted alkylene group; a substituted or unsubstituted cycloalkylene group; a substituted or unsubstituted condensation ring of a divalent aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted arylene group,

[0066] l11 is an integer from 1 to 5, and if l11 is 2 or more, the 2 or more L11s are the same or different from each other, and

[0067] X11 to X15 are the same or different from each other, and each is independently O; or S,

[0068] Z11 to Z13 are the same or different from each other, and each is independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group, and

[0069] Lb is a substituted or unsubstituted arylene group, and

[0070] a', b', and q' are the same or different from each other and are each independently integers from 0 to 6, and when a', b', and q' are each 2 or greater, the structures inside each parenthesis are the same or different from each other,

[0071] p' is an integer from 1 to 6, and if p' is 2 or greater, the structures inside the parentheses are the same or different from each other, and

[0072] * refers to the part connected to the main chain of the resin.

[0073] By further including the unit of Formula 2 in the above polyester resin, the glass transition temperature (Tg) of the unit of Formula 1 can be supplemented, or the chain behavior of the unit of Formula 1 can be made flexible, and there is a technical effect advantageous for injection molding of the molded product.

[0074] One embodiment of the present specification provides a polyester resin comprising a unit of Formula 1; and a unit of Formula 2.

[0075] According to one embodiment of the present specification, r1 is 1.

[0076] According to one embodiment of the present specification, the formula 1 is any one of the following formulas 1-1 to 1-4.

[0077] [Chemical Formula 1-1]

[0078]

[0079] [Chemical Formula 1-2]

[0080]

[0081] [Chemical Formula 1-3]

[0082]

[0083] [Chemical Formula 1-4]

[0084]

[0085] In the above chemical formulas 1-1 to 1-4,

[0086] The definitions of Z1 to Z3, X1 to X5, a, b, p, q, L1, L2, La, and R1 are the same as those defined in Chemical Formula 1 above.

[0087] According to one embodiment of the present specification, R1 and R2 are different from each other and are each independently hydrogen; or an unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; L1 and L2 are the same or different from each other and are each independently monocyclic or polycyclic arylene groups having 6 to 30 carbon atoms; X1 to X5 are O; Z1 to Z3 are the same or different from each other and are each independently straight-chain or branched-chain alkylene groups having 1 to 30 carbon atoms; and La is a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms.

[0088] According to one embodiment of the present specification, R1 and R2 are different from each other and each independently hydrogen; or an unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0089] According to one embodiment of the present specification, R1 and R2 are different from each other and each independently hydrogen; or an unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0090] According to one embodiment of the present specification, R1 and R2 are different from each other and each independently hydrogen; or an unsubstituted polycyclic aryl group having 10 to 30 carbon atoms.

[0091] According to one embodiment of the present specification, R1 and R2 are different from each other and each independently hydrogen; or an unsubstituted polycyclic aryl group having 10 to 20 carbon atoms.

[0092] According to one embodiment of the present specification, R1 and R2 are different from each other and are each independently hydrogen; or naphthyl group.

[0093] According to one embodiment of the present specification, R1 is a naphthyl group.

[0094] According to one embodiment of the present specification, R2 is hydrogen.

[0095] According to one embodiment of the present specification, L1 and L2 are the same or different from each other and are each independently a single or polycyclic arylene group having 6 to 30 carbon atoms.

[0096] According to one embodiment of the present specification, L1 and L2 are the same or different from each other and are each independently a single or polycyclic arylene group having 6 to 20 carbon atoms.

[0097] According to one embodiment of the present specification, L1 and L2 are the same or different from each other and are each independently polycyclic arylene groups having 10 to 30 carbon atoms.

[0098] According to one embodiment of the present specification, L1 and L2 are the same or different from each other and are each independently polycyclic arylene groups having 10 to 20 carbon atoms.

[0099] According to one embodiment of the present specification, L1 and L2 are divalent naphthalene groups.

[0100] According to one embodiment of the present specification, X1 is O.

[0101] According to one embodiment of the present specification, X2 is O.

[0102] According to one embodiment of the present specification, X3 is O.

[0103] According to one embodiment of the present specification, X4 is O.

[0104] According to one embodiment of the present specification, X5 is O.

[0105] According to one embodiment of the present specification, Z1 to Z3 are the same or different from each other and are each independently straight-chain or branched-chain alkylene groups having 1 to 30 carbon atoms.

[0106] According to one embodiment of the present specification, Z1 to Z3 are the same or different from each other and are each independently straight-chain or branched-chain alkylene groups having 1 to 20 carbon atoms.

[0107] According to one embodiment of the present specification, Z1 to Z3 are ethylene groups.

[0108] According to one embodiment of the present specification, La is a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms.

[0109] According to one embodiment of the present specification, La is a single or polycyclic arylene group having 6 to 20 carbon atoms.

[0110] According to one embodiment of the present specification, La is a phenylene group; or a naphthylene group.

[0111] According to one embodiment of the present specification, a is 1.

[0112] According to one embodiment of the present specification, b is 1.

[0113] According to one embodiment of the present specification, p is 1.

[0114] According to one embodiment of the present specification, q is 1.

[0115] According to one embodiment of the present specification, a is 0.

[0116] According to one embodiment of the present specification, b is 0.

[0117] According to one embodiment of the present specification, q is 0.

[0118] According to one embodiment of the present specification, X11 to X15 are O, and

[0119] The above L11 is a monocyclic or polycyclic alkylene group having 1 to 30 carbon atoms, a straight-chain or branched-chain 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, and

[0120] The above Z11 to Z13 are the same or different from each other, and each is independently a straight-chain or branched-chain alkylene group having 1 to 30 carbon atoms, and

[0121] The above Lb is a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms.

[0122] According to one embodiment of the present specification, L11 is a monocyclic or polycyclic alkylene group having 1 to 30 carbon atoms; a condensation ring 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 straight-chain or branched-chain 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.

[0123] According to one embodiment of the present specification, L11 is a monocyclic or polycyclic alkylene group having 1 to 20 carbon atoms; a condensation ring 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 straight-chain or branched-chain 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.

[0124] According to one embodiment of the present specification, L11 is a methylene group substituted or unsubstituted with a methyl group; an isopropyl group; a phenylene group substituted or unsubstituted with a methyl group or a phenyl group; a divalent naphthalene group; or a divalent fluorene group.

[0125] According to one embodiment of the present specification, the l11 is 1.

[0126] According to one embodiment of the present specification, the l11 is 2, and the two L11s are the same or different from each other.

[0127] According to one embodiment of the present specification, the l11 is 3, and the three L11s are the same or different from each other.

[0128] According to one embodiment of the present specification, X11 is O.

[0129] According to one embodiment of the present specification, X12 is O.

[0130] According to one embodiment of the present specification, X13 is O.

[0131] According to one embodiment of the present specification, X14 is O.

[0132] According to one embodiment of the present specification, X15 is O.

[0133] According to one embodiment of the present specification, Z11 to Z13 are the same or different from each other and are each independently straight-chain or branched-chain alkylene groups having 1 to 30 carbon atoms.

[0134] According to one embodiment of the present specification, Z11 to Z13 are the same or different from each other and are each independently straight-chain or branched-chain alkylene groups having 1 to 20 carbon atoms.

[0135] According to one embodiment of the present specification, Z11 to Z13 are ethylene groups.

[0136] According to one embodiment of the present specification, Lb is a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms.

[0137] According to one embodiment of the present specification, Lb is a single or polycyclic arylene group having 6 to 20 carbon atoms.

[0138] According to one embodiment of the present specification, Lb is a phenylene group; or a naphthylene group.

[0139] According to one embodiment of the present specification, the a' is 1.

[0140] According to one embodiment of the present specification, b' is 1.

[0141] According to one embodiment of the present specification, p' is 1.

[0142] According to one embodiment of the present specification, the q' is 1.

[0143] According to one embodiment of the present specification, a' is 0.

[0144] According to one embodiment of the present specification, b' is 0.

[0145] According to one embodiment of the present specification, q' is 0.

[0146] According to one embodiment of the present specification, the polyester resin may have -OH; -SH; -CO2CH3; -Cl; or -OC6H5 as terminal groups, respectively.

[0147] In one embodiment of the present specification, the weight-average molecular weight of the polyester resin is 5,000 g / mol to 500,000 g / mol, preferably 8,000 g / mol to 400,000 g / mol, 10,000 g / mol to 350,000 g / mol, and 11,000 g / mol to 300,000 g / mol. More preferably 12,000 g / mol to 250,000 g / mol, 13,000 g / mol to 200,000 g / mol, 14,000 g / mol to 150,000 g / mol, and 15,000 g / mol to 100,000 g / mol.

[0148] In one embodiment of the present invention, the number average molecular weight of the polyester resin is 2,000 g / mol to 300,000 g / mol, 4,000 g / mol to 250,000 g / mol, 5,000 g / mol to 210,000 g / mol, 6,000 g / mol to 180,000 g / mol, 6,500 g / mol to 150,000 g / mol, 7,000 g / mol to 120,000 g / mol, 7,000 g / mol to 90,000 g / mol, preferably 8,000 g / mol to 60,000 g / mol.

[0149] When the above polyester resin satisfies the aforementioned ranges for weight-average molecular weight and number-average molecular weight, the polyester resin can have optimal fluidity and processability.

[0150] In this specification, the weight-average molecular weight (Mw) of the polyester resin and the oligomer used in its manufacture can be measured using gel permeation chromatography (GPC) with a polystyrene standard (PS standard) using an Agilent 1200 series. Specifically, the measurement can be performed using an Agilent 1200 series instrument with a Polymer Laboratories PLgel MIX-B 300 mm long column, at a measurement temperature of 40°C, with tetrahydrofuran (THF) as the solvent and a flow rate of 1 mL / min. Samples of the polyester resin or oligomer are prepared at a concentration of 10 mg / 10 mL, supplied in an amount of 10 μL, and the weight-average molecular weight (Mw) value is derived using a calibration curve formed with a polystyrene standard. At this time, nine types of polystyrene standard products 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.

[0151] In one embodiment of the present specification, the glass transition temperature (Tg) of the polyester resin may be 90°C to 200°C. Preferably, it may be 100°C to 190°C, 120°C to 170°C, 130°C to 160°C, 135°C to 191°C, or 152°C to 175°C. When the polyester resin satisfies the above glass transition temperature range, it has excellent heat resistance and injection moldability. When a polyester resin composition is prepared by mixing it with a resin having a glass transition temperature different from the above range, the glass transition temperature can be easily controlled, thereby satisfying the physical properties intended in the present specification.

[0152] 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 scanning a sample of 5.5 mg to 8.5 mg of the polyester resin heated to 270°C under a nitrogen atmosphere, then cooling it, and then heating it a second time at a heating rate of 10°C / min.

[0153] In one embodiment of the present specification, the refractive index of the polyester resin measured at a wavelength of 587 nm is 1.50 to 1.75. The refractive index is preferably 1.60 to 1.72, and more preferably 1.62 to 1.70, or 1.66 to 1.69. When the resin satisfies the refractive index, it is possible to manufacture a thin and lightweight optical lens when applied to a molded article such as an optical lens.

[0154] In one embodiment of this specification, the Abbe number measured and calculated at wavelengths 486, 587, and 656 nm of the resin may be 5 to 45. Preferably, it may be 10 to 25, more preferably 15.5 to 23.4, or 16.8 to 20.1. When the resin satisfies the above Abbe number range, when the resin is applied to a molded article such as an optical lens, it has the effect of having less dispersion and higher clarity. Specifically, the Abbe number is the refractive index (n) at wavelengths D (587 nm), F (486 nm), and C (656 nm) at 25°C. D , n F , n C By measuring each of the following, the Abbe number can be obtained using the formula below.

[0155] Abe number = (n D -1) / (n F - n C )

[0156] The above refractive index and Abbe number measurements can be performed on a film prepared by spin-coating a solution prepared by dissolving the resin in a solvent onto a silicon wafer, and the results according to the wavelength of light can be obtained and measured using an ellipsometer at 25°C. The spin-coating application can be performed at a rotational speed of 150 rpm to 300 rpm, and the thickness of the applied film can be 5 µm to 20 µm. The silicon wafer is not particularly limited and may be appropriately employed as long as it is capable of measuring 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% by weight based on the total weight of the solution.

[0157] One embodiment of the present specification provides a method for producing a polyester resin comprising the step of polymerizing a composition for producing a polyester resin comprising a compound of the following formula 1a and a polyester precursor.

[0158] [Chemical Formula 1a]

[0159]

[0160] In the above chemical formula 1a,

[0161] The definitions of R1, R2, r1, r2, L1, L2, X1 to X4, a, b, Z1 and Z2 are the same as those defined in Chemical Formula 1 above.

[0162] According to one embodiment of the present specification, the method for manufacturing the polyester resin further comprises a compound of Formula 2a below, wherein the compound of Formula 1a and Formula 2a are included in an amount of 0.01 mole% to 100 mole%: 99.99 mole% to 0 mole%. Specifically, they are included in an amount of 0.01 mole% to 99.99 mole%: 99.99 mole% to 0.01 mole%. More specifically, they are included in an amount of 0.1 mole% to 99.9 mole%: 99.9 mole% to 0.1 mole%, 1 mole% to 99 mole%: 99 mole% to 1 mole%, and 5 mole% to 90 mole%: 5 mole% to 90 mole%.

[0163] [Chemical Formula 2a]

[0164]

[0165] In the above chemical formula 2a,

[0166] L11 is a substituted or unsubstituted alkylene group; a substituted or unsubstituted cycloalkylene group; a substituted or unsubstituted condensation ring of a divalent aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted arylene group,

[0167] l11 is an integer from 1 to 5, and if l11 is 2 or more, the 2 or more L11s are the same or different from each other, and

[0168] X11 to X14 are the same or different from each other, and each is independently O; or S,

[0169] Z11 and Z12 are the same or different from each other, and each is independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group, and

[0170] a' and b' are the same or different from each other and are each independently integers from 0 to 10, and when a' and b' are each 2 or more, the structures inside each parenthesis are the same or different from each other.

[0171] One embodiment of the present specification provides a method for manufacturing a polyester resin comprising the step of polymerizing a composition for manufacturing a polyester resin comprising a compound of Formula 1a and a polyester precursor. When the compound of Formula 1a is included, polymerization is easy, and depending on the substituent, the composition has a refractive index of a wide range or a high refractive index and a wide range of glass transition temperatures.

[0172] One embodiment of the present specification provides a method for manufacturing a polyester resin comprising the step of polymerizing a composition for manufacturing a polyester resin comprising a compound of Formula 1a; a compound of Formula 2a; and a polyester precursor. The compound of Formula 1a and Formula 2a are included in an amount of 0.01 mole% to 100 mole%: 99.99 mole% to 0 mole%. Specifically, they are included in an amount of 0.01 mole% to 99.99 mole%: 99.99 mole% to 0.01 mole%. More specifically, they are included in an amount of 0.1 mole% to 99.9 mole%: 99.9 mole% to 0.1 mole%, 1 mole% to 99 mole%: 99 mole% to 1 mole%, and 5 mole% to 90 mole%: 5 mole% to 90 mole%.

[0173] When the above chemical formulas 1a and 2a are included in the above amounts, polymerization is easy, and depending on the substituents, the composition has a refractive index of a wide range or a high refractive index and a wide range of glass transition temperatures. In addition, the glass transition temperature (Tg) and refractive index can be controlled, and the chain behavior of the polyester resin can be made flexible, which provides a technical effect advantageous for injection molding of molded articles. The composition for manufacturing the polyester resin may further include a solvent.

[0174] The above solvent may be, for example, diphenyl ether, dimethylacetamide, or methanol, but is not limited thereto, and those applicable in the art may be appropriately employed.

[0175] The above solvent may be included in an amount of 5 to 60 parts by weight per 100 parts by weight of the resin manufacturing composition.

[0176] The above solvent may preferably 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 composition for manufacturing the resin.

[0177] In one embodiment of the present specification, the compound of Formula 1a may be used, but is not limited thereto.

[0178]

[0179] In one embodiment of the present specification, the compound of Formula 2a may be any one of the following compounds, but is not limited thereto.

[0180]

[0181] In one embodiment of the present specification, the compound of Formula 1a may be included in an amount of 1 to 100 parts by weight or 1 to 99 parts by weight per 100 parts by weight of the composition for manufacturing the polyester resin.

[0182] The compound of formula 1a above may preferably 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 with respect to 100 parts by weight of the composition for manufacturing the polyester resin.

[0183] In one embodiment of the present specification, the compound of Formula 2a may be included in an amount of 0 to 99 parts by weight and 1 to 99 parts by weight per 100 parts by weight of the composition for manufacturing the polyester resin.

[0184] The compound of formula 2a above may preferably 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 with respect to 100 parts by weight of the composition for manufacturing the polyester resin.

[0185] In one embodiment of the present specification, the polyester precursor may be included in an amount of 1 to 60 parts by weight per 100 parts by weight of the composition for manufacturing the polyester resin.

[0186] The polyester precursor may preferably 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 with respect to 100 parts by weight of the composition for manufacturing the polyester resin.

[0187] According to one embodiment of the present specification, the polyester precursor is the following chemical formula A.

[0188] [Chemical Formula A]

[0189]

[0190] In the above chemical formula A,

[0191] Ra1 and Ra2 are the same or different from each other, and each is independently a halogen group; a hydroxyl group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group, and

[0192] Ar1 is a substituted or unsubstituted arylene group, and

[0193] a1 and a2 are 0 or 1, respectively.

[0194] According to one embodiment of the present specification, Ra1 and Ra2 are the same or different from each other and are each independently a halogen group; a hydroxyl group; a substituted or unsubstituted straight-chain or branched-chain 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.

[0195] According to one embodiment of the present specification, Ra1 and Ra2 are the same or different from each other and are each independently a halogen group; a hydroxyl group; a substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0196] According to one embodiment of the present specification, Ra1 and Ra2 are the same or different from each other and are each independently a halogen group; a hydroxyl group; a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms substituted or unsubstituted with a hydroxyl group; or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0197] According to one embodiment of the present specification, Ra1 and Ra2 are the same or different from each other and are each independently a halogen group; a hydroxyl group; a straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with a hydroxyl group; or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0198] According to one embodiment of the present specification, Ra1 and Ra2 are the same or different from each other and are each independently -Cl; hydroxyl group; methyl group; ethyl group; n-propyl group; n-butyl group; isopropyl group; isobutyl group; hydroxyethyl group; or phenyl group.

[0199] According to one embodiment of the present specification, the definition of Ar1 may be applied to the definitions of La and Lb described above.

[0200] According to one embodiment of the present specification, the Ar1 is a single or polycyclic arylene group having 6 to 30 carbon atoms.

[0201] According to one embodiment of the present specification, Ar1 is a single or polycyclic arylene group having 6 to 20 carbon atoms.

[0202] According to one embodiment of the present specification, the Ar1 is a phenylene group; or a naphthylene group.

[0203] According to one embodiment of the present specification, the formula A is any one selected from the following compounds.

[0204]

[0205] In one embodiment of the present specification, the polyester resin is preferably polymerized from the compound of Formula 1a and the polyester precursor of Formula A.

[0206] In one embodiment of the present specification, the polyester resin is preferably polymerized from the compound of Formula 1a; the compound of Formula 2a; and the polyester precursor of Formula A.

[0207] The compound of Formula 1a above can be formed into a unit of Formula 1 above by polymerizing the polyester precursor of Formula A above, and the compound of Formula 2a above can be formed into a unit of Formula 2 above by polymerizing the polyester precursor of Formula A above.

[0208] It can be formed into a unit of the aforementioned formula 1 by polymerizing the compound of formula 1a and the polyester precursor of formula A.

[0209] The compound of the above chemical formula 1a may be used in an amount of 1 to 100 moles or 1 to 99 moles relative to 100 moles of the total monomer constituting the polyester resin containing the unit of the above chemical formula 1.

[0210] The polyester precursor of the above formula A may be used in an amount of 1 to 150 moles, or 50 to 150 moles, relative to 100 moles of the total monomer of the compound of formula 1a constituting the resin.

[0211] It can be formed into a unit of the aforementioned formula 2 by polymerizing the compound of formula 2a and the polyester precursor of formula A.

[0212] The compound of the above formula 2a may be used in an amount of 1 to 100 moles or 1 to 99 moles relative to 100 moles of the total monomer constituting the polyester resin containing the unit of the above formula 2.

[0213] The polyester precursor of the above formula A may be used in an amount of 1 to 150 moles, or 50 to 150 moles, relative to 100 moles of the total monomer of the compound of the above formula 2a constituting the resin.

[0214] The polymerization of the resin according to the present specification may utilize methods known in the art.

[0215] It is preferable to perform the above polymerization by melt polycondensation.

[0216] The above melt polycondensation method may be performed using the above polyester resin manufacturing composition, wherein a catalyst may be further applied as needed, and the melt polycondensation may be carried out under heating, additionally under atmospheric pressure or reduced pressure, while removing by-products through an ester exchange reaction. The catalyst may be a material generally applied in the art.

[0217] Specifically, the above melt polycondensation method is preferably carried out by melting the compound of formula 1a and the polyester precursor in a reaction vessel, and then retaining the byproduct compound.

[0218] More specifically, the above melt polycondensation method is preferably carried out by melting the compound of formula 1a; formula 2a; and the polyester precursor in a reaction vessel, and then retaining the byproduct compound.

[0219] In order to retain the above-mentioned byproduct compound, the pressure can be controlled by blocking the reaction device, reducing the pressure, or increasing the pressure.

[0220] The reaction time of this process 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 300 minutes or less.

[0221] In this case, if the byproduct compound is removed by distillation immediately after generation, the final resin obtained has a low content of high molecular weight compounds. However, if the byproduct compound is allowed to remain in the reaction vessel for a certain period of time, the final resin obtained has a high content of high molecular weight compounds.

[0222] The above-mentioned melt polycondensation method may be carried out in a continuous manner or in a batch manner. The reaction apparatus used to carry out the reaction may be of a vertical type equipped with an anchor-type stirring blade, a Max Blend stirring blade, a helical ribbon-type stirring blade, etc., may be of a horizontal type equipped with a paddle blade, a grid blade, a spectral blade, etc., or may be of an extruder type equipped with a screw. In addition, it is preferable to use a reaction apparatus that appropriately combines these reaction apparatuses, taking into account the viscosity of the polymer.

[0223] In the method for manufacturing a polyester 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 hydrolysis stability. A method of deactivating the catalyst by adding an acidic substance known in the art may be preferably implemented.

[0224] The above acidic substances include, for example, esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as butyl p-toluenesulfonic acid, hexyl p-toluenesulfonic acid; phosphates such as phosphoric acid, phosphoric acid, and phosphonic acid; phosphate esters such as triphenyl phosphate, monophenyl phosphate, diphenyl phosphate, diethyl phosphate, din-propyl phosphate, din-butyl phosphate, din-hexyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphate esters such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; and phosphonic acid esters such as diethyl phenylphosphonic acid. Phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids such as boric acid and phenylboric acid; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonic acid; organic halides such as chloride stearate, benzoyl chloride, and p-toluenesulfonic acid chloride; alkyl sulfates such as dimethyl sulfate; and organic halides such as benzyl chloride are preferably used.

[0225] The above 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.

[0226] If the above acidic substance is less than 0.1 molar part, the deactivation effect becomes insufficient and is undesirable. In addition, if it exceeds 5 molar part, the heat resistance of the resin decreases and the molded article becomes prone to discoloration, which is undesirable.

[0227] After catalyst deactivation, a degassing process can be further performed on the low-boiling point compound in the resin at a pressure of 0.1 mmHg to 1 mmHg and a temperature of 200°C to 350°C. For this process, a horizontal device equipped with stirring blades having excellent surface renewal ability, such as paddle blades, grid blades, or spectral blades, or a thin-film evaporator is preferably used.

[0228] The resin of this specification preferably has a minimum amount of foreign substances, and the filtration of the molten raw material and the filtration of the catalyst liquid are preferably carried out.

[0229] The mesh of the filter used for the above filtration is preferably 5 μm or less, and more preferably 1 μm or less. In addition, filtration of the generated resin by a polymer filter is preferably carried out. 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 in a low-dust environment, preferably Class 6 or less, and more preferably Class 5 or less.

[0230] In addition, molding methods for a molded article containing the above polyester resin include, in addition to injection molding, compression molding, molding, roll processing, extrusion molding, and stretching, but are not limited thereto.

[0231] Another embodiment of the present specification provides a polyester resin composition comprising a resin according to the embodiments described above.

[0232] In one embodiment of the present specification, the polyester resin may be included in an amount of 1 to 80 parts by weight based on 100 parts by weight of the polyester resin composition.

[0233] In one embodiment of the present specification, the polyester resin composition may further include a solvent. The solvent may be, for example, dimethylacetamide or 1,2-dichlorobenzene.

[0234] The above solvent may be included in an amount of 20 to 99 parts by weight based on 100 parts by weight of the polyester resin composition.

[0235] The polyester resin composition may further include additional monomers in addition to the compound of Formula 1a. The additional monomers are not particularly limited, and monomers generally applied in the art related to polyester may be appropriately employed within a range that does not alter the major physical properties of the polyester resin composition. The additional monomers may be used in an amount of 1 to 50 moles relative to 100 moles of total monomers constituting the resin containing the unit of Formula 1.

[0236] In addition to the resin comprising the unit of Formula 1, the polyester resin composition may additionally include, if necessary, one or more additives selected from the group consisting of antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent whitening agents, ultraviolet absorbers, pigments, and dyes.

[0237] The above additive may be included in an amount of 1 to 99 parts by weight based on 100 parts by weight of the polyester resin composition.

[0238] The types of the above antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent whitening agents, ultraviolet absorbers, pigments, or dyes are not particularly limited, and those applicable in the field of technology may be appropriately adopted.

[0239] Another embodiment of the present specification provides a molded article comprising a resin composition according to the embodiments described above.

[0240] In one embodiment of the present specification, the molded article may be manufactured from the polyester resin composition or a cured product thereof.

[0241] As an example of a method for manufacturing the above-mentioned molded article, the method may include the step of thoroughly mixing the resin containing the unit of Chemical Formula 1 and the additive using a mixer, then extruding the mixture into pellets using an extruder, drying the pellets, and then injecting them using an injection molding machine.

[0242] In one embodiment of the present specification, the molded article is an optical lens.

[0243] In one actual photographic state of the present specification, the thickness of the optical lens is 0.1 μm to 30 mm.

[0244] The above optical lens causes the position of the focal point where light is formed to change depending on the difference in refractive index in a lens of the same thickness. This is illustrated in FIG. 1. This changes the position of the focal point formed between a camera lens and an image sensor, and between an eyeglass lens and a human pupil. In order to achieve the same focal point, the thickness of the lens and film becomes thinner as the refractive index increases. An optical lens according to one embodiment of the present specification can realize a thin optical lens with a high refractive index.

[0245] The above optical lens is manufactured using the above polyester resin, has a thin thickness, high refractive index and high transparency, and preferably can be applied to a camera.

[0246] In one embodiment of the present specification, the molded article is an optical film or an optical thin film. The optical film or optical thin film is manufactured using the polyester resin, has a thin thickness, excellent light-gathering and light-diffusing effects, and preferably can be applied to a backlight module of a liquid crystal display, a flat lens, a metalens, etc.

[0247] In one embodiment of the present specification, the thickness of the optical film or optical thin film is 0.1 nm to 10 mm.

[0248] In one aspect of the present specification, the molded article is an optical resin. The optical resin is manufactured using the polyester resin, has a thin thickness, high refractive index and low birefringence, and low optical loss.

[0249] An optical resin according to one embodiment of the present specification has a high refractive index and a low birefringence, resulting in low optical loss. An optical resin according to one embodiment of the present specification has a glass transition temperature of 90°C to 200°C, which is neither very high nor very low compared to conventional general optical materials, making it easy to process and exhibiting excellent heat resistance. If the glass transition temperature exceeds 200°C, the melt flow index increases, making processing difficult; if the glass transition temperature is less than 90°C, the low heat resistance results in reduced weather resistance due to the external environment. Accordingly, there are few optical resins according to one embodiment of the present specification that possess appropriate thermal characteristics and achieve a high refractive index.

[0250] The present specification is further illustrated in detail below through examples.

[0251] Preparation Example 1. Preparation of Resin 1

[0252] Monomer 1-1 (66.48 g (100 mmol)) and terephthaloyl chloride (TPC) (19.42 g (100 mmol)) were melted and reacted at 250°C for 5 hours. As the reaction proceeded, methanol was generated as a byproduct, and to remove it, the reduced pressure was adjusted to a maximum of 1 Torr. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, thereby obtaining resin 1, which is a polymerized molten polymer resin.

[0253] Monomer 1-1:

[0254] Preparation Example 2. Preparation of Resin 2

[0255] Monomer 1-1 (66.48 g (100 mmol)), terephthaloyl chloride (TPC) (9.71 g (50 mmol)), and isophthaloyl chloride (IPC) (9.71 g (50 mmol)) were melted and reacted at 250°C for 5 hours. As the reaction proceeded, methanol was generated as a byproduct, and the reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, thereby obtaining resin 2, which is a polymerized molten polymer resin.

[0256] Preparation Example 3. Preparation of Resin 3

[0257] Monomer 1-1 (36.56 g (55 mmol)), monomer 2-3 (16.84 g (45 mmol)), and terephthaloyl chloride (TPC) (19.42 g (100 mmol)) were melted and reacted at 250°C for 5 hours. As the reaction proceeded, methanol was generated as a byproduct, and the reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, thereby obtaining resin 3, which is a polymerized molten polymer resin.

[0258]

[0259] Preparation Example 4. Preparation of Resin 4

[0260] Monomer 1-1 (39.89 g (60 mmol)), monomer 2-3 (14.97 g (40 mmol)), terephthaloyl chloride (TPC) (9.71 g (50 mmol)), and isophthaloyl chloride (IPC) (9.71 g (50 mmol)) were melted and reacted at 250°C for 5 hours. As the reaction proceeded, methanol was generated as a byproduct, and the reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, thereby obtaining resin 4, which is a polymerized molten polymer resin.

[0261] Preparation Example 5. Preparation of Resin 5

[0262] Monomer 1-1 (19.94 g (30 mmol)), monomer 2-1 (16.16 g (30 mmol)), monomer 2-3 (14.97 g (40 mmol)), and terephthaloyl chloride (TPC) (19.42 g (100 mmol)) were melted and reacted at 250°C for 5 hours. As the reaction proceeded, methanol was generated as a byproduct, and the reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, thereby obtaining resin 5, which is a polymerized molten polymer resin.

[0263] Preparation Example 6. Preparation of Resin 6

[0264] Monomer 1-1 (19.94 g (30 mmol)), monomer 2-2 (11.81 g (20 mmol)), monomer 2-3 (18.71 g (50 mmol)), and terephthaloyl chloride (TPC) (19.42 g (100 mmol)) were melted and reacted at 250°C for 5 hours. As the reaction proceeded, methanol was generated as a byproduct, and the reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, thereby obtaining resin 6, which is a polymerized molten polymer resin.

[0265] Preparation Example 7. Preparation of Resin 7

[0266] Monomer 1-1 (19.94 g (30 mmol)), monomer 2-3 (18.71 g (50 mmol)), monomer 2-4 (4.57 g (20 mmol)), and terephthaloyl chloride (TPC) (19.42 g (100 mmol)) were melted and reacted at 250°C for 5 hours. As the reaction proceeded, methanol was generated as a byproduct, and the reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, thereby obtaining resin 7, which is a polymerized molten polymer resin.

[0267] Preparation Example 8. Preparation of Resin 8

[0268] Monomer 1-1 (19.94 g (30 mmol)), monomer 2-3 (18.71 g (50 mmol)), monomer 2-5 (8.77 g (20 mmol)), and terephthaloyl chloride (TPC) (19.42 g (100 mmol)) were melted and reacted at 250°C for 5 hours. As the reaction proceeded, methanol was generated as a byproduct, and the reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, thereby obtaining resin 8, which is a polymerized molten polymer resin.

[0269] Preparation Example 9. Preparation of Resin 9

[0270] Monomer 1-1 (19.94 g (30 mmol)), monomer 2-3 (18.71 g (50 mmol)), monomer 2-6 (3.96 g (20 mmol)), and terephthaloyl chloride (TPC) (19.42 g (100 mmol)) were melted and reacted at 250°C for 5 hours. As the reaction proceeded, methanol was generated as a byproduct, and the reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, thereby obtaining resin 9, which is a polymerized molten polymer resin.

[0271] Preparation Example 10. Preparation of Resin 10

[0272] Monomer 1-1 (19.94 g (30 mmol)), monomer 2-3 (22.45 g (60 mmol)), monomer 2-7 (3.50 g (10 mmol)), and terephthaloyl chloride (TPC) (19.42 g (100 mmol)) were melted and reacted at 250°C for 5 hours. As the reaction proceeded, methanol was generated as a byproduct, and the reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, thereby obtaining resin 10, which is a polymerized molten polymer resin.

[0273] Preparation Example 11. Preparation of Resin 11

[0274] Monomer 1-1 (19.94 g (30 mmol)), monomer 2-3 (22.45 g (60 mmol)), monomer 2-8 (2.86 g (10 mmol)), terephthaloyl chloride (TPC) (15.54 g (80 mmol)), and isophthaloyl chloride (IPC) (3.88 g (20 mmol)) were melted and reacted at 250°C for 5 hours. As the reaction proceeded, methanol was generated as a byproduct, and the reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, thereby obtaining resin 11, which is a polymerized molten polymer resin.

[0275] Preparation Example 12. Preparation of Resin 12

[0276] Monomer 1-1 (19.94 g (30 mmol)), monomer 2-3 (22.45 g (60 mmol)), monomer 2-9 (3.78 g (10 mmol)), terephthaloyl chloride (TPC) (15.54 g (80 mmol)), and isophthaloyl chloride (IPC) (3.88 g (20 mmol)) were melted and reacted at 250°C for 5 hours. As the reaction proceeded, methanol was generated as a byproduct, and the reduced pressure was adjusted to a maximum of 1 Torr to remove it. After the reaction was completed, nitrogen was blown into the reactor to create an atmospheric pressure atmosphere, thereby obtaining resin 12, which is a polymerized molten polymer resin.

[0277] Example.

[0278] The molecular weight and molecular weight distribution (PDI=Mw / Mn) of the polymerized resin samples were confirmed via gel permeation chromatography (GPC), and a thermogram was obtained using differential scanning calorimetry (DSC) to investigate thermal properties. To measure the refractive index and Abbe number, an ellipsometer was used after film formation to obtain results based on the wavelength of light.

[0279] Molecular weight by gel permeation chromatography (GPC) was obtained by using tetrahydrofuran (THF, stabilized with BHT (butylated hydroxytoluene))) as a solvent, dissolving the resin sample in tetrahydrofuran at a concentration of 1.0 mg / 1 ml, filtering the solution through a syringe filter, and then injecting the solution to measure at 40°C. The results are listed in Table 2 below. A Waters RI detector was used, and two Agilent PLgel MIXED-B columns were used.

[0280] Differential scanning calorimetry (DSC) was used to determine the glass transition temperature (Tg) of the resin. 5.5 mg to 8.5 mg of resin samples were heated to 270°C under N2 flow, cooled, and then heated a second time at a heating rate of 10°C / min. The glass transition temperature (Tg) was determined from the graph obtained by scanning, and the results are listed in Table 2 below.

[0281] To measure the refractive index and Abbe number of the resin, a polymer solution prepared by dissolving a polymerized resin powder sample in the solvent dimethylacetamide at 10 wt% based on the total weight of the polymer solution was applied to a silicon wafer by spin-coating at a rotation speed of 220 rpm to form a film with a thickness of 20 μm. The results were obtained according to the wavelength of light using an ellipsometer at 25°C and are listed in Table 2 below. Specifically, the refractive index was measured at a wavelength of 587 nm, and the Abbe number was the refractive index (n) at wavelengths D (587 nm), F (486 nm), and C (656 nm). D , n F , n C The Abbe numbers were obtained by measuring each of the following formulas.

[0282] Abe number = (n D -1) / (n F - n C )

[0283] Monomer 1-1 Monomer 2-1 Monomer 2-2 Monomer 2-3 Monomer 2-4 Monomer 2-5 Monomer 2-6 Monomer 2-7 Monomer 2-8 Monomer 2-9 TPC IPC Example 1 Suzy 1 100 100 Example 2 Suzy 2 100 50 50 Example 3 Suzy 3 55 45 100 Example 4 Suzy 4 60 40 50 50 Example 5 Suzy 5 30 30 40 100 Example 6 Suzy 6 30 20 50 100 Example 7 Suzy 7 30 50 20 100 Example 8 Suzy 8 30 50 20 100 Example 9 Suzy 9 30 50 20 100 Example 10 Suzy 10 30 60 10 100 Example 11 Suji 11 30 60 10 80 20 Example 12 Suji 12 30 60 10 80 20

[0284] Table 1 above lists the mole% of each monomer included in resins 1 to 12 of Examples 1 to 12. Additionally, TPC is terephthaloyl chloride, and IPC is isophthaloyl chloride.

[0285] Refractive index (RI) Tg(℃) Abesu Mn Mw PDI Example 1 Suzy 1 1.69 175 16.8 29000 48000 1.65 Example 2 Suzy 2 1.69 166 17.1 30000 52000 1.71 Example 3 Suzy 3 1.68 158 17.1 21000 38000 1.85 Example 4 Suzy 4 1.68 152 16.9 23000 41000 1.75 Example 5 Suzy 5 1.68 157 17.5 18000 33000 1.83 Example 6 Suzy 6 1.67 157 19.1 19000 32000 1.69 Example 7 Suzy 7 1.66 153 20.1 20000 35000 1.77 Example 8 Suzy 8 1.67 155 18.8 18000 31000 1.71 Example 9 Suzy 9 1.67 138 18.5 16000 29000 1.85 Example 10 Suzy 10 1.67 165 17.9 18000 34000 1.88 Example 11 Suji 11 1.68 159 18.5 13000 24000 1.88 Example 12 Suji 12 1.67 168 18.3 13000 26000 1.98

[0286] In Table 2 above, 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, and the refractive index is the value measured at a wavelength of 587 nm.

[0287] According to Table 2 above, the polyester resin according to the embodiment of the present invention comprises a unit of Formula 1, and in particular, the benzene ring of the fluorene core structure of Formula 1 is substituted with an electron-rich R2 substituent, so that the electron density of the fluorene core structure is high, and the polyester resin containing this has an improved refractive index.

[0288] In addition, by further including the unit of Chemical Formula 2 in the unit of Chemical Formula 1, it is possible to control the glass transition temperature (Tg) and refractive index, and the chain behavior of the polyester resin can be made flexible, thereby providing a technical effect advantageous for injection molding of molded products.

Claims

Claim 1 Polyester resin containing units of the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R1 is an unsubstituted aryl group, R2 is hydrogen, r1 is an integer from 1 to 4, and when r1 is 2 or more, the 2 or more R1s are the same or different from each other, r2 is 4, L1 and L2 are the same or different from each other and are each independently substituted or unsubstituted arylene groups, X1 to X5 are the same or different from each other and are each independently O; or S, and Z1 to Z3 are the same or different from each other and are each independently substituted or unsubstituted alkylene groups; or is a substituted or unsubstituted cycloalkylene group, La is a substituted or unsubstituted arylene group, a, b, and q are the same or different from each other and are each independently integers from 0 to 6, and when a, b, and q are each 2 or more, the structures in each parenthesis are the same or different from each other, p is an integer from 1 to 6, and when p is 2 or more, the structures in the parenthesis are the same or different from each other, and * means a portion connected to the main chain of the resin. Claim 2 The polyester resin of claim 1, wherein the polyester resin further comprises a unit of the following chemical formula 2: [Chemical Formula 2] In the above chemical formula 2, L11 is a substituted or unsubstituted alkylene group; a substituted or unsubstituted cycloalkylene group; a substituted or unsubstituted condensation ring of a divalent aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted arylene group; l11 is an integer from 1 to 5, and if l11 is 2 or more, the 2 or more L11s are the same or different from each other, X11 to X15 are the same or different from each other and are each independently O; or S, and Z11 to Z13 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or is a substituted or unsubstituted cycloalkylene group, Lb is a substituted or unsubstituted arylene group, a', b' and q' are the same or different from each other and are each independently integers from 0 to 6, and when a', b' and q' are each 2 or more, the structures in each parenthesis are the same or different from each other, p' is an integer from 1 to 6, and when p' is 2 or more, the structures in the parenthesis are the same or different from each other, and * means a portion connected to the main chain of the resin. Claim 3 A polyester resin according to claim 1, wherein R1 is an unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, R2 is hydrogen, L1 and L2 are the same or different from each other and are each independently monocyclic or polycyclic arylene groups having 6 to 30 carbon atoms, X1 to X5 are O, Z1 to Z3 are the same or different from each other and are each independently straight-chain or branched-chain alkylene groups having 1 to 30 carbon atoms, and La is a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms. Claim 4 A polyester resin according to claim 1, wherein the weight-average molecular weight (Mw) of the polyester resin is 5,000 g / mol to 500,000 g / mol. Claim 5 A polyester resin according to claim 1, wherein the refractive index of the polyester resin measured at a wavelength of 587 nm is 1.50 to 1.

75. Claim 6 A polyester resin according to claim 1, wherein the glass transition temperature (Tg) of the polyester resin is 90°C to 200°C. Claim 7 A polyester resin according to claim 1, wherein the Abbe numbers measured at wavelengths of 486, 587, and 656 nm are 5 to 45. Claim 8 A method for manufacturing a polyester resin according to any one of claims 1 to 7, comprising the step of polymerizing a composition for manufacturing a polyester resin comprising a compound of the following chemical formula 1a; and a polyester precursor: [Chemical formula 1a] In the above chemical formula 1a, the definitions of R1, R2, r1, r2, L1, L2, X1 to X4, a, b, Z1 and Z2 are the same as those defined in the above chemical formula 1. Claim 9 A method for manufacturing a polyester resin according to claim 8, wherein the method further comprises a compound of the following formula 2a, and wherein the compound of formula 1a and the compound of formula 2a are included in an amount of 0.01 mole% to 99.99 mole% : 99.99 mole% to 0.01 mole%: [Formula 2a] In the above formula 2a, L11 is a substituted or unsubstituted alkylene group; a substituted or unsubstituted cycloalkylene group; a substituted or unsubstituted condensation ring of a divalent aromatic hydrocarbon ring and an aliphatic hydrocarbon ring; or a substituted or unsubstituted arylene group, and L11 is an integer from 1 to 5, and when L11 is 2 or more, the 2 or more L11s are the same or different from each other, X11 to X14 are the same or different from each other and are each independently O; or S, Z11 and Z12 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group, and a' and b' are the same or different from each other and are each independently integers from 0 to 6, and when a' and b' are each 2 or more, the structures in each parenthesis are the same or different from each other. Claim 10 A method for manufacturing a polyester according to claim 8, wherein the polyester precursor is of the following chemical formula A: [Chemical formula A] In the above formula A, Ra1 and Ra2 are the same or different from each other and are each independently a halogen group; a hydroxyl group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group, Ar1 is a substituted or unsubstituted arylene group, and a1 and a2 are each 0 or 1. Claim 11 A polyester resin composition comprising a polyester resin according to any one of claims 1 to 7. Claim 12 A molded article comprising a polyester resin composition according to claim 11.

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