Thermoplastic resins and optical components

Abstract

The present invention provides a thermoplastic resin that can provide balance among a high refractive index, high heat resistance, and low birefringence, and also provides an optical member that contains this thermoplastic resin. The thermoplastic resin according to the present invention contains a repeat unit represented by formula (1). (In the formula, the rings Z (which may be the same or may differ) each represent a polycyclic aromatic hydrocarbon in which at least three benzene rings are bonded; R1, R2, R3, and R4 each independently are a hydrogen atom or a halogen atom or represent a C1-C20 substituent which may contain an aromatic group; L1 and L2 each independently represent a divalent linking group; j and k each independently represent an integer equal to or greater than 1; m and n each independently represent 0 or 1; and W is at least one selection from the group represented by formula (2) and formula (3).) (In the formula, X represents a divalent linking group.)

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic resin that can balance a high refractive index, high heat resistance, and low birefringence. [Background technology]

[0002] Imaging modules are used in cameras, video cameras, camera-equipped mobile phones, videophones, camera-equipped door phones, and the like. In recent years, there has been a particular demand for miniaturization of the optical systems used in these imaging modules. As optical systems become more compact, chromatic aberration in the optical system becomes a major problem. It is known that chromatic aberration can be corrected by combining an optical lens material with a high refractive index and a small Abbe number for high dispersion with an optical lens material with a low refractive index and a large Abbe number for low dispersion.

[0003] Glass, which has traditionally been used as a material for optical systems, is capable of achieving various required optical properties and has excellent environmental resistance, but suffers from poor processability. In response to this, resins, which are less expensive and more processable than glass materials, have been used for optical components. Resins having a fluorene skeleton or a binaphthalene skeleton are particularly used due to their high refractive index. For example, Patent Documents 1 and 2 describe a high-refractive-index resin with a refractive index of 1.64 that uses 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene. However, depending on the optical lens used, this refractive index is insufficient, and a higher refractive index is desired. Patent Document 3 also describes a thermoplastic resin containing 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene.

[0004] Furthermore, in order to achieve a high refractive index, Patent Documents 4 and 5 describe thermoplastic resins in which aromatic rings are introduced into the fluorene skeleton using coupling technology. While achieving a high refractive index and high heat resistance, there is a problem in that the expansion of conjugation centered on the fluorene moiety increases the refractive index and birefringence as well. In addition, the raw materials used in the coupling reaction increase in cost, and the additional process steps lead to a longer manufacturing process.

[0005] Therefore, an object of the present invention is to provide a thermoplastic resin having an excellent balance of high refractive index, high heat resistance, and low birefringence, and an optical member containing the same. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2007 / 142149 [Patent Document 2] Japanese Patent Application Publication No. 7-198901 [Patent Document 3] Japanese Patent Application Laid-Open No. 2015-86265 [Patent Document 4] International Publication No. 2019 / 044214 [Patent Document 5] Japanese Patent Publication No. 2020-12094 Summary of the Invention [Problem to be solved by the invention]

[0007] The problem to be solved by the present invention is to provide a thermoplastic resin that can balance high refractive index, high heat resistance, and low birefringence, and an optical member containing the same. [Means for solving the problem]

[0008] As a result of intensive research conducted by the present inventors to achieve this object, they discovered that a thermoplastic resin containing a specific compound incorporating a polycyclic aromatic hydrocarbon having three or more benzene rings can solve the above-mentioned problems, and thus arrived at the present invention. That is, the present invention is as follows.

[0009] <<Aspect 1>> A thermoplastic resin containing a repeating unit represented by the following formula (1): [ka] (wherein ring Z represents a polycyclic aromatic hydrocarbon having three or more benzene rings (the same or different) bonded thereto; R 1 , R 2 , R 3 , and R 4 each independently represents a hydrogen atom or a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group; L 1 and L 2 each independently represents a divalent linking group, j and k each independently represents an integer of 1 or more, m and n each independently represents 0 or 1, and W is at least one selected from the group represented by the following formula (2) or (3): [ka] [ka] (In the formula, X represents a divalent linking group.)

[0010] <<Aspect 2>> The thermoplastic resin according to embodiment 1, wherein the repeating unit represented by formula (1) is at least one selected from the group represented by formulas (1a) to (1d): [ka] [ka] [ka] [ka] (wherein ring Z is a polycyclic aromatic hydrocarbon having three or more benzene rings (the same or different) bonded thereto; R 1 , R 2 , R 3 , and R 4 each independently represents a hydrogen atom or a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group; L 1 and L 2 each independently represents a divalent linking group, j and k each independently represents an integer of 1 or more, m and n each independently represents 0 or 1, and W is at least one selected from the group represented by formula (2) or (3).

[0011] <Aspect 3> Aspect 3. The thermoplastic resin according to aspect 2, wherein the formula (1) is the formula (1b).

[0012] <<Aspect 4>> A thermoplastic resin according to any one of aspects 1 to 3, wherein in formula (1), ring Z is a phenacene-type polycyclic aromatic hydrocarbon.

[0013] <Aspect 5> A thermoplastic resin according to any one of aspects 1 to 4, wherein ring Z in formula (1) is phenanthrene.

[0014] Aspect 6 The thermoplastic resin according to any one of aspects 1 to 5, wherein the repeating unit represented by formula (1) is represented by formula (4): [ka] (In the formula, R 3 and R 4 each independently represents a hydrogen atom or a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group; L 1 and L 2each independently represents a divalent linking group, m and n each independently represent 0 or 1, and W is at least one selected from the group represented by formula (2) or (3).

[0015] Aspect 7 In the formula (1), R 3 and R 4 7. The thermoplastic resin according to any one of aspects 1 to 6, wherein represents a hydrogen atom, a methyl group, a phenyl group, a naphthyl group, or a phenanthryl group.

[0016] Eighth Aspect In the formula (1), R 3 and R 4 The thermoplastic resin according to any one of aspects 1 to 7, wherein is a hydrogen atom.

[0017] <Aspect 9> The thermoplastic resin according to any one of aspects 1 to 8, wherein X in formula (3) contains at least one repeating unit selected from the group consisting of a phenylene group, a naphthalenediyl group, a group represented by the following formula (5), and a group represented by the following formula (6): [ka] (In the formula, R 5 and R 6 are each independently a hydrogen atom or a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may contain an aromatic group. [ka]

[0018] <Aspect 10> The thermoplastic resin according to any one of aspects 1 to 9, comprising at least one repeating unit selected from the group consisting of units represented by the following formulas (7) to (10): [ka] (In the formula, R 7 and R 8are each independently a hydrogen atom or a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may contain an aromatic group. [ka] (In the formula, R 9 and R 10 are each independently a hydrogen atom or a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group. [ka] (In the formula, R 11 and R 12 are each independently a hydrogen atom or a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group. [ka] (In the formula, R 13 and R 14 are each independently a hydrogen atom or a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group, and U is a single bond or a divalent linking group.

[0019] <<Aspect 11>> Aspect 11. The thermoplastic resin according to any one of aspects 1 to 10, having a specific viscosity of 0.12 to 0.40. <Aspect 12>

[0020] 12. The thermoplastic resin according to any one of aspects 1 to 11, having a refractive index of 1.65 to 1.80.

[0021] <Aspect 13> 13. The thermoplastic resin according to any one of aspects 1 to 12, having a glass transition temperature of 130 to 190°C.

[0022] <Aspect 14> The absolute value of orientation birefringence is 6.0 × 10 -3 14. The thermoplastic resin according to any one of aspects 1 to 13, wherein:

[0023] <Aspect 15> An optical member made of the thermoplastic resin according to any one of embodiments 1 to 14.

[0024] Aspect 16 16. The optical member according to embodiment 15, which is an optical lens. [Effects of the Invention]

[0025] The thermoplastic resin of the present invention has an excellent balance of high refractive index, high heat resistance, and low birefringence, and can therefore be used for optical components such as optical lenses, prisms, optical disks, transparent conductive substrates, optical cards, sheets, films, optical fibers, optical films, optical filters, and hard coat films. It is particularly useful for optical lenses for use in mobile phones, smartphones, tablet terminals, personal computers, digital cameras, video cameras, vehicle-mounted cameras, or surveillance cameras, and therefore has exceptional industrial effects. [Brief explanation of the drawings]

[0026] [Figure 1] 1H NMR of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene obtained in Reference Example 1. [Figure 2] 1H NMR of the polycarbonate resin obtained in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0027] The present invention will now be described in more detail. <Thermoplastic resin> As the thermoplastic resin of the present invention, a thermoplastic resin containing a repeating unit represented by the following formula (1) is used. [ka] (wherein ring Z is a polycyclic aromatic hydrocarbon having three or more benzene rings (the same or different) bonded thereto; R 1 , R 2 , R 3, and R 4 each independently represents a hydrogen atom or a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group; L 1 and L 2 each independently represents a divalent linking group, j and k each independently represents an integer of 1 or more, m and n each independently represents 0 or 1, and W is at least one selected from the group represented by the following formula (2) or (3): [ka] [ka] (In the formula, X represents a divalent linking group.)

[0028] In the formula (1), the rings Z (the same or different) are polycyclic aromatic hydrocarbon groups having three or more fused benzene rings, preferably polycyclic aromatic hydrocarbons having three or four fused benzene rings, and more preferably polycyclic aromatic hydrocarbons having three fused benzene rings.

[0029] In the formula (1), the polycyclic aromatic hydrocarbon of ring Z preferably has a structure in which a benzene ring is fused to an acene type or a phenacene type, and more preferably has a structure in which a phenacene type is fused.

[0030] In the formula (1), ring Z is preferably anthracene, phenanthrene, pyrene, or chrysene, more preferably anthracene or phenanthrene, and even more preferably phenanthrene from the viewpoint of stability due to differences in frontier orbitals when the number of fused rings increases.

[0031] In the formula (1), R 1 and R 2 are each independently a hydrogen atom or a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group, and are preferably a hydrogen atom, a methyl group, a phenyl group, or a naphthyl group, more preferably a hydrogen atom, a methyl group, or a phenyl group, still more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0032] In the formula (1), R 3 and R 4 are each independently a hydrogen atom or a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group, and are preferably a hydrogen atom, a methyl group, a phenyl group, a naphthyl group, or a phenanthryl group, more preferably a hydrogen atom, a phenyl group, a naphthyl group, or a phenanthryl group, still more preferably a hydrogen atom, a phenyl group, or a naphthyl group, and particularly preferably a hydrogen atom.

[0033] R 3 and R 4 The bonding positions of each of the above are preferably the 1st and 8th positions (the following formula (1a)), the 2nd and 7th positions (the following formula (1b)), the 3rd and 6th positions (the following formula (1c)), or the 4th and 5th positions (the following formula (1d)) of the fluorene skeleton, more preferably the 2nd and 7th positions, the 3rd and 6th positions, or the 4th and 5th positions, and even more preferably the 2nd and 7th positions. [ka] [ka] [ka] [ka] (In the formula, rings Z, R 1 , R 2 , R 3 , R 4 , L 1 , L 2 , j, k, m, n, and W are the same as in formula (1).

[0034] In the formula (1), L 1 , L 2 L each independently represents a divalent linking group, and is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and even more preferably an ethylene group. 1 , L 2By adjusting the length of the linking group, the glass transition temperature (Tg) of the resin can be adjusted.

[0035] In the formula (1), W is at least one selected from the group represented by the formula (2) or (3). When W is the formula (2), the formula (1) becomes a carbonate unit, and when W is the formula (3), the formula (1) becomes an ester unit.

[0036] The repeating unit represented by the formula (1) can be obtained from a dihydroxy compound and a carbonate precursor such as a carbonate ester, or from a dihydroxy compound and a dicarboxylic acid or an ester-forming derivative thereof.

[0037] In the formula (1), m and n each independently represent 0 or 1, and are more preferably 1.

[0038] In the formula (1), j and k each independently represent an integer of 1 or more, preferably an integer of 1 to 4, and more preferably 1.

[0039] The repeating unit represented by the formula (1) is preferably a repeating unit represented by the following formula (11). [ka] (In the formula, R 3 and R 4 , L 1 and L 2 , m, n, and W are the same as in formula (1).

[0040] In the formula (11), the combinations of the bonding positions from the phenanthrene skeleton to the fluorene skeleton and the bonding positions of the linking group containing an oxygen atom in the phenanthrene skeleton are preferably the 1st and 6th positions, the 3rd and 6th positions, the 3rd and 9th positions (the following formula (4)), and the 3rd and 10th positions, respectively, more preferably the 3rd and 9th positions, the 3rd and 10th positions, and even more preferably the 3rd and 9th positions. [ka] (In the formula, R 3 and R 4 , L 1 and L 2 , m, n, and W are the same as in formula (1).

[0041] Furthermore, it is more preferable that the repeating unit represented by the formula (1) is a repeating unit represented by the following formula (12). [ka] (In the formula, L 1 and L 2 , m, n, and W are the same as in formula (1).

[0042] In the formula (3), X represents a divalent linking group, and is preferably a substituent having 1 to 30 carbon atoms which may contain an aromatic group, and more preferably a phenylene group, a naphthalenediyl group, a group represented by the following formula (5), or a group represented by the following formula (6). [ka] (In the formula, R 5 and R 6 are each independently a hydrogen atom or a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may contain an aromatic group. [ka]

[0043] In the formula (5), R 5 and R 6 are each independently a hydrogen atom or a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group, and are preferably a hydrogen atom, a methyl group, a phenyl group, or a naphthyl group, more preferably a hydrogen atom, a methyl group, or a phenyl group, still more preferably a hydrogen atom or a phenyl group, and particularly preferably a hydrogen atom.

[0044] The reason why the present invention can achieve a high balance of high refractive index, high heat resistance, and low birefringence is considered to be as follows. Patent Document 5 describes a thermoplastic resin obtained using a compound in which an aromatic group having 6 to 10 carbon atoms is introduced into the side chain of a fluorene skeleton, such as 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-diphenylfluorene (hereinafter also referred to as "BNDP2") having the following formula: [ka]

[0045] Furthermore, Patent Document 4 describes that the refractive index and birefringence are both improved by the extension of the conjugation between the introduced aromatic group and the fluorene moiety.

[0046] The present inventors have discovered that a polymer having a polycyclic aromatic hydrocarbon group in the main chain, in which three or more benzene rings are fused, can suppress an increase in birefringence and increase the refractive index. This is believed to resolve the trade-off between the effect of improving the refractive index and the increase in birefringence, which has been an issue in conventional technologies.

[0047] The Lorentz-Lorenz equation, which describes the relationship between molecular structure and refractive index, indicates that increasing the electron density of a molecule and decreasing its molecular volume increases the refractive index of a substance. Based on this theory, conventional resins with a fluorene skeleton have been made to have a high refractive index by incorporating many aromatic groups into the molecule. However, when aromatic groups are introduced into the fluorene side chain, the conjugated structure expands, increasing the electron density and resulting in an increased refractive index. However, the difference in refractive index between the main chain (orientation direction) and the side chain (perpendicular direction) also increases, worsening the resin's birefringence. In other words, increasing the refractive index requires simultaneously suppressing birefringence.

[0048] The polymers developed in this invention have a polycyclic aromatic hydrocarbon group in the main chain, with three or more fused benzene rings, and in particular the polymers incorporating phenacene groups, which have a bent structure, resulting in little orientation in the main chain direction and achieving an increase in refractive index while suppressing the polymer's birefringence. Among these, the phenanthryl group provided an excellent balance between refractive index and birefringence.

[0049] Furthermore, the thermoplastic resin of the present invention has many aromatic groups introduced therein, which makes it possible to improve heat resistance and balance moldability.

[0050] The thermoplastic resin of the present invention represented by formula (1) may contain the repeating unit represented by formula (1) at 5 mol% or more, 10 mol% or more, 15 mol% or more, 20 mol% or more, 25 mol% or more, or 30 mol% or more, or at 100 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, or 50 mol% or less. The resin of the present invention may contain the repeating unit represented by formula (1) at preferably 10 mol% to 100 mol%, more preferably 20 mol% to 100 mol%, even more preferably 20 mol% to 80 mol%, and particularly preferably 20 mol% to 70 mol%. When the repeating unit represented by formula (1) is in the above range, an excellent balance of refractive index, heat resistance, and moldability is achieved, which is preferable.

[0051] The thermoplastic resin of the present invention may contain at least one repeating unit selected from the group consisting of units represented by the following formulas (7) to (10). [ka] (In the formula, R 7 and R 8 is R in the above formula (5) 5 and R 6 is the same as [ka] (In the formula, R 9 and R10 is R in the above formula (5) 5 and R 6 is the same as [ka] (In the formula, R 11 and R 12 is R in the above formula (5) 5 and R 6 is the same as [ka] (In the formula, R 13 and R 14 is R in the above formula (5) 5 and R 6 where U represents a single bond or a divalent linking group.

[0052] The molar ratio of the repeating unit represented by formula (1) to the group consisting of units represented by formulas (7) to (10) is preferably 95:5 to 5:95, more preferably 80:20 to 20:80, and even more preferably 70:30 to 30:70.

[0053] It is preferable that the molar ratio of the repeating unit represented by the formula (1) to at least one repeating unit selected from the group consisting of units represented by the formulas (7) to (10) is within the above range, since this not only provides a high refractive index but also an excellent balance of moldability.

[0054] <Physical properties of thermoplastic resin> The specific viscosity of the thermoplastic resin of the present invention is preferably 0.12 to 0.40, more preferably 0.14 to 0.35, and even more preferably 0.16 to 0.30. A specific viscosity within the above range is preferred because it provides an excellent balance between moldability and mechanical strength.

[0055] The specific viscosity is measured by dissolving 0.7 g of the thermoplastic resin in 100 ml of methylene chloride, measuring the specific viscosity (ηSP) at 20° C. with an Ostwald viscometer, and calculating from the following formula. Specific viscosity (ηSP)=(t-t0) / t0 [t0 is the number of seconds it takes for methylene chloride to fall, and t is the number of seconds it takes for the sample solution to fall]

[0056] The refractive index of the thermoplastic resin of the present invention, when measured at a temperature of 20°C and a wavelength of 587.56 nm, is 1.65 or more, and may be 1.66 or more, 1.67 or more, 1.68 or more, 1.69 or more, or 1.70 or more, or may be 1.80 or less, 1.79 or less, 1.78 or less, 1.77 or less, 1.76 or less, or 1.75 or less. It is preferably 1.65 to 1.80, more preferably 1.66 to 1.80, even more preferably 1.67 to 1.80, particularly preferably 1.68 to 1.80, and most preferably 1.69 to 1.80. When the refractive index is equal to or greater than the lower limit, the spherical aberration of the optical lens can be reduced, and the focal length of the optical lens can be shortened.

[0057] The thermoplastic resin of the present invention has a high refractive index, but it is preferable that it also has a low Abbe number.

[0058] The Abbe number of the thermoplastic resin of the present invention may be 5 or more, 7 or more, 9 or more, 10 or more, 12 or more, or 14 or more, or may be 24 or less, 23 or less, 22 or less, 21 or less, 20 or less, 19 or less, or 18 or less. The Abbe number (νd) is preferably 5 to 22, more preferably 7 to 22, and even more preferably 10 to 21.

[0059] Here, the Abbe number is calculated using the following formula from the refractive indexes at a temperature of 20° C. and wavelengths of 486.13 nm, 587.56 nm, and 656.27 nm: νd=(nd-1) / (nF-nC) nd: refractive index at a wavelength of 587.56 nm, nF: refractive index at a wavelength of 486.13 nm, nC: Refractive index at a wavelength of 656.27 nm.

[0060] The thermoplastic resin of the present invention may have a glass transition temperature (Tg) of 130°C or higher, 135°C or higher, 140°C or higher, 145°C or higher, or 150°C or higher, or 190°C or lower, 185°C or lower, 180°C or lower, 175°C or lower, or 170°C or lower. The Tg is preferably 130 to 190°C, more preferably 140 to 185°C, and even more preferably 140 to 180°C. A glass transition temperature within the above range is preferred because it provides an excellent balance between heat resistance and moldability.

[0061] The thermoplastic resin of the present invention has an absolute value of orientation birefringence (|Δn|) of 6.0×10 -3 is less than or equal to 5.0 x 10 -3 Preferably, it is 4.5 x 10 or less. -3 More preferably, it is 4.0×10 or less. -3 More preferably, it is 3.5×10 or less. -3 It is particularly preferable that the value is 3.0 × 10 or less. -3 It is most preferable that |Δn| is within the above range, since the optical distortion of the optical lens is reduced.

[0062] The absolute value of orientation birefringence (|Δn|) is calculated by stretching a 100 μm thick film obtained from the thermoplastic resin of the present invention to 2 times its original size at a temperature of Tg+10° C., measuring the retardation at a wavelength of 589 nm, and then using the following formula: |Δn|=|Re / d| Δn: Orientation birefringence Re: Phase difference (nm) d: thickness (nm)

[0063] The thermoplastic resin of the present invention preferably has a water absorption rate of 0.25% by mass or less, and more preferably 0.20% by weight or less, after immersion for 24 hours in water at 23° C. A water absorption rate within the above range is preferred because changes in optical properties due to water absorption are small.

[0064] <Raw material for thermoplastic resin> (Diol component of formula (1)) The diol component used as the raw material of formula (1) is mainly a diol component represented by formula (a), and may be used alone or in combination of two or more kinds. [ka]

[0065] In the formula (a), the rings Z and R 1 and R 2 , R 3 , R 4 , L 1 and L 2 , j and k, m and n are the same as those in the formula (1).

[0066] Representative examples of the dihydroxy compound represented by the formula (a) are shown below, but the raw materials used in the formula (1) of the present invention are not limited to these.

[0067] Ring Z is phenanthrene and R 3 , R 4 When is a hydrogen atom, examples include 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene represented by the following formula (a-1) and 9,9-bis(3-hydroxyphenanthryl)fluorene represented by (a-2). [ka] [ka]

[0068] Ring Z is phenanthrene and R 3 , R 4When is a phenyl group, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-1,8-diphenylfluorene, 9,9-bis(3-hydroxyphenanthryl)-1,8-diphenylfluorene, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-2,7-diphenylfluorene, 9,9-bis(3-hydroxyphenanthryl)-2,7-diphenylfluorene, and Examples thereof include diphenylfluorene, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-3,6-diphenylfluorene, 9,9-bis(3-hydroxyphenanthryl)-3,6-diphenylfluorene, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-4,5-diphenylfluorene, and 9,9-bis(3-hydroxyphenanthryl)-4,5-diphenylfluorene. [ka]

[0069] Ring Z is phenanthrene and R 3 , R 4 When the compound is 1-naphthalene, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-1,8-di(1-naphthyl)fluorene, 9,9-bis(3-hydroxyphenanthryl)-1,8-di(1-naphthyl)fluorene, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-2,7-di(1-naphthyl)fluorene, 9,9-bis(3-hydroxyphenanthryl)-2,7-di(1-naphthyl)fluorene, and the like are represented by the following formula (a-4): -naphthyl)fluorene, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-3,6-di(1-naphthyl)fluorene, 9,9-bis(3-hydroxyphenanthryl)-3,6-di(1-naphthyl)fluorene, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-4,5-di(1-naphthyl)fluorene, and 9,9-bis(3-hydroxyphenanthryl)-4,5-di(1-naphthyl)fluorene. [ka]

[0070] Ring Z is phenanthrene and R 3 , R 4 When the compound is 2-naphthalene, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-1,8-di(2-naphthyl)fluorene, 9,9-bis(3-hydroxyphenanthryl)-1,8-di(2-naphthyl)fluorene, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-2,7-di(2-naphthyl)fluorene, 9,9-bis(3-hydroxyphenanthryl)-2,7-di(2-naphthyl)fluorene, and the like are represented by the following formula (a-5): -naphthyl)fluorene, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-3,6-di(2-naphthyl)fluorene, 9,9-bis(3-hydroxyphenanthryl)-3,6-di(2-naphthyl)fluorene, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-4,5-di(2-naphthyl)fluorene, and 9,9-bis(3-hydroxyphenanthryl)-4,5-di(2-naphthyl)fluorene. [ka]

[0071] Ring Z is phenanthrene and R 3 , R 4When the compound is phenanthrene, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-1,8-di(9-phenanthryl)fluorene, 9,9-bis(3-hydroxyphenanthryl)-1,8-di(9-phenanthryl)fluorene, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-2,7-di(9-phenanthryl)fluorene, 9,9-bis(3-hydroxyphenanthryl)-2,7-di(9-phenanthryl)fluorene, and the like are represented by the following formula (a-6): 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-3,6-di(9-phenanthryl)fluorene, 9,9-bis(3-hydroxyphenanthryl)-3,6-di(9-phenanthryl)fluorene, 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-4,5-di(9-phenanthryl)fluorene, 9,9-bis(3-hydroxyphenanthryl)-4,5-di(9-phenanthryl)fluorene. [ka]

[0072] Among them, the following formulas (a'-1) to (a'-5) are preferred: The following formula (a'-1): 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene, The following formula (a'-2): 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-2,7-diphenylfluorene, The following formula (a'-3): 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-2,7-di(1-naphthyl)fluorene, The following formula (a'-4): 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-2,7-di(2-naphthyl)fluorene, The following formula (a'-5): 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]-2,7-di(9-phenanthryl)fluorene These may be used alone or in combination of two or more.

[0073] [ka] [ka] [ka] [ka] [ka]

[0074] (Carbonate component of formula (1)) Examples of carbonate components used in the units represented by formula (1) of the thermoplastic resin of the present invention include phosgene and carbonate esters. Examples of carbonate esters include esters of optionally substituted aryl groups or aralkyl groups having 6 to 10 carbon atoms, or alkyl groups having 1 to 4 carbon atoms. Specific examples include diaryl carbonates such as diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, bis(m-cresyl)carbonate, and dinaphthyl carbonate; dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate; alkylaryl carbonates such as ethylphenyl carbonate and cyclohexylphenyl carbonate; and dialkenyl carbonates such as divinyl carbonate, diisopropenyl carbonate, and dipropenyl carbonate. Of these, diaryl carbonates are preferred, and diphenyl carbonate is more preferred.

[0075] (Dicarboxylic acid component of the above formula (1)) The dicarboxylic acid component used in the unit represented by formula (1) of the thermoplastic resin of the present invention is preferably a dicarboxylic acid represented by formula (b) or an ester-forming derivative thereof. [ka] In the formula (b), X represents a divalent linking group, and the same applies as explained in the formula (3).

[0076] Representative examples of the dicarboxylic acid represented by the formula (b) or its ester-forming derivatives are shown below, but the raw materials used in the formula (b) of the present invention are not limited to these.

[0077] The dicarboxylic acid component used in the thermoplastic resin of the present invention includes, as the raw materials of the formula (6), 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, 6,6'-diphenyl-2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, 6,6'-dibromo-2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, and 9,9-bis(2-carboxyethyl)fluorene, as well as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, ethyl malonic acid, ethyl methyl ... aliphatic dicarboxylic acid components such as malonic acid, monocyclic aromatic dicarboxylic acid components such as phthalic acid, isophthalic acid, and terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, 9,9-bis(carboxymethyl)fluorene, 9,9-bis(1-carboxyethyl)fluorene, and 9,9-bis(1-carboxypropyl)fluorene. polycyclic aromatic dicarboxylic acid components such as fluorene, 9,9-bis(2-carboxypropyl)fluorene, 9,9-bis(2-carboxy-1-methylethyl)fluorene, 9,9-bis(2-carboxy-1-methylpropyl)fluorene, 9,9-bis(2-carboxybutyl)fluorene, 9,9-bis(2-carboxy-1-methylbutyl)fluorene, 9,9-bis(5-carboxypentyl)fluorene, and 9,9-bis(carboxycyclohexyl)fluorene; biphenyldicarboxylic acid components such as 2,2'-biphenyldicarboxylic acid; Examples of the dicarboxylic acid component include alicyclic dicarboxylic acid components such as phenyldicarboxylic acid components, 1,4-cyclohexanedicarboxylic acid, and 2,6-decalindicarboxylic acid. Preferred are isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, and 9,9-bis(2-carboxyethyl)fluorene, and more preferred are 2,6-naphthalenedicarboxylic acid, 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, and 9,9-bis(2-carboxyethyl)fluorene. These may be used alone or in combination of two or more.As the ester-forming derivative, acid chlorides and esters such as methyl esters, ethyl esters and phenyl esters may be used. (Components of the above formulas (7) to (10))

[0078] The thermoplastic resin of the present invention may further have repeating units of the formulae (7) to (10), and the dihydroxy compound components that serve as raw materials for the formulae (7) to (10) are shown below. These may be used alone or in combination of two or more.

[0079] Examples of the dihydroxy compound component that serves as the raw material for the above formula (7) of the present invention include 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-3,3'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-7,7'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-3,3'-dimethyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-dimethyl-1,1'-binaphthyl, and 2,2'-bis(2-hydroxyethoxy)-7,7'-dimethyl-1,1'-binaphthyl.

[0080] Examples of dihydroxy compound components that serve as raw materials for the compound of formula (8) of the present invention include 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, and 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, with 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene being particularly preferred. These compounds may be used alone or in combination.

[0081] Examples of dihydroxy compound components that serve as raw materials for the compound of formula (9) of the present invention include 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene and 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-diphenylfluorene. The dihydroxy compound components used as raw materials for the formula (10) of the present invention include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)decane, bis(4-hydroxyphenyl)diphenylmethane, ... Examples include 9,9-bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)sulfide, biphenol, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, bis(4-hydroxyphenyl)sulfone, 10,10-bis(4-hydroxyphenyl)anthrone, etc., with 2,2-bis(4-hydroxyphenyl)propane and bis(4-hydroxyphenyl)sulfide being particularly preferred. These may be used alone or in combination of two or more.

[0082] Among the compounds represented by formulas (7) to (10), 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene, and 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-diphenylfluorene are particularly preferred because they can achieve a good balance between a high refractive index, high heat resistance, and low birefringence.

[0083] The thermoplastic resin of the present invention can be produced, for example, by a method of reacting a dihydroxy compound component with a carbonate precursor such as phosgene or a carbonate diester, or by a method of reacting a diol component with a dicarboxylic acid or its ester-forming derivative. Specific examples are shown below.

[0084] <Manufacturing method> (Manufacturing method of polycarbonate resin) When the thermoplastic resin of the present invention is a polycarbonate resin, it can be obtained by a reaction method known per se, such as interfacial polymerization or melt polymerization, of a dihydroxy compound component and a carbonate precursor. In producing the polycarbonate resin, a catalyst, a terminal terminator, an antioxidant, etc. may be used as necessary.

[0085] (Method of producing polyester resin) When the thermoplastic resin of the present invention is a polyester resin, a reaction method known per se may be used, for example, an esterification reaction or an ester exchange reaction between a dihydroxy compound component and a dicarboxylic acid or an ester-forming derivative thereof, and the resulting reaction product may be subjected to a polycondensation reaction to form a polymer having a desired molecular weight.

[0086] (Method for producing polyester carbonate resin) When the thermoplastic resin of the present invention is a polyester carbonate resin, it can be produced by reacting a dihydroxy compound component and a dicarboxylic acid or its ester-forming derivative with a carbonate precursor such as phosgene or a carbonate ester. The polymerization method can be the same as that for the polycarbonate resin or polyester resin.

[0087] <Optical components> The optical member of the present invention contains the above-mentioned thermoplastic resin. Such optical members are not particularly limited as long as they are used for optical applications in which the above-mentioned thermoplastic resin is useful, and examples thereof include optical lenses, optical disks, transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, optical films, substrates, optical filters, and hard coat films.

[0088] The optical member of the present invention may be composed of a resin composition containing the above-mentioned thermoplastic resin, and the resin composition may contain additives such as a heat stabilizer, a plasticizer, a light stabilizer, a polymerized metal deactivator, a flame retardant, a lubricant, an antistatic agent, a surfactant, an antibacterial agent, an ultraviolet absorber, a mold release agent, and an antioxidant, as needed.

[0089] Antioxidants include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert- butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, and 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane. The amount of the antioxidant to be blended is preferably 0.50 parts by mass or less, more preferably 0.05 to 0.40 parts by mass, even more preferably 0.05 to 0.20 parts by mass or 0.10 to 0.40 parts by mass, and particularly preferably 0.20 to 0.40 parts by mass, per 100 parts by mass of the thermoplastic resin composition.

[0090] <Optical lenses> The optical member of the present invention can particularly include an optical lens, such as an optical lens for a mobile phone, a smartphone, a tablet terminal, a personal computer, a digital camera, a video camera, an in-vehicle camera, or a surveillance camera.

[0091] The optical lens of the present invention can be molded and processed by any method such as injection molding, compression molding, injection compression molding, melt extrusion molding, casting, etc., but injection molding is particularly preferred.

[0092] The molding conditions for injection molding are not particularly limited, but the cylinder temperature of the molding machine is preferably 180 to 320° C., more preferably 220 to 300° C., and particularly preferably 240 to 290° C. The mold temperature is preferably 70 to 130° C., more preferably 80 to 125° C., and particularly preferably 90 to 120° C. The injection pressure is preferably 5 to 170 MPa, more preferably 50 to 160 MPa, and particularly preferably 100 to 150 MPa.

[0093] The present invention will be explained in more detail in the following examples, but the present invention is not limited thereto. [Example]

[0094] [Reference Example 1] Synthesis of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene Under a nitrogen atmosphere, 5.00 g of fluorenone, 10.78 g of 9-phenanthrol, 0.20 g of 1-octanethiol, 0.09 g of phosphotungstic acid, 20 ml of toluene, and 5 ml of γ-butyrolactone were added to a flask equipped with a stirrer, condenser, and thermometer, and the mixture was allowed to react at 100°C and 50 kPa for 10 hours. After cooling, 100 ml of toluene was added, and the reaction mixture was transferred to a separatory funnel and neutralized with aqueous NaOH. The mixture was then washed with distilled water until neutral. HPLC analysis of the organic layer after washing confirmed that the content was 78% 9,9-bis(3-hydroxyphenanthryl)fluorene, 6% 9-phenanthrol, 9% fluorenone, and 7% other unknown components.

[0095] This organic layer, 4.62 g of ethylene carbonate, and 0.35 g of potassium carbonate were placed in a flask equipped with a stirrer, a condenser, and a thermometer under a nitrogen atmosphere, and the reaction solution was bubbled with nitrogen for 10 minutes. The reaction was then allowed to proceed at 110°C for 18 hours. After cooling the reaction solution, 300 ml of toluene was added, and the reaction solution was transferred to a separatory funnel. The reaction solution was washed with an aqueous NaOH solution, and then washed with distilled water until neutral. Hexane was then added to the organic layer for recrystallization. The resulting crystals were recovered, dissolved in toluene, recrystallized by adding hexane, and dried under reduced pressure for 4 hours to obtain crystals of 9,9-bis[9-(2-hydroxyethoxy)-3-phenanthryl]fluorene (hereinafter sometimes abbreviated as BPhEF) (purity: 96%, yield: 4.8 g). Furthermore, the obtained BPhEF 1 The 1 H NMR chart is shown in Figure 1.

[0096] [Example 1] 12.78 parts by mass (20 mol%) of BPhEF, 35.08 parts by mass (80 mol%) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter sometimes abbreviated as BPEF), 21.53 parts by mass (100.5 mol%) of diphenyl carbonate (hereinafter sometimes abbreviated as DPC), and 8.40 × 10 sodium bicarbonate at a concentration of 100 mmol / L as a catalyst. -4 Parts by mass (1.00×10 -4 % (mol) of phenol was added and heated to 180°C under a nitrogen atmosphere to melt it. The vacuum was then adjusted to 20 kPa over 5 minutes. The temperature was raised to 250°C at a rate of 60°C / hr, and once the amount of phenol effluent had reached 70%, the pressure was reduced to 60 kPa / hr and the polymerization reaction was carried out until the specified power was reached. After the reaction was completed, the resin was removed from the flask.

[0097] The obtained polycarbonate resin is 1 Analysis by H NMR confirmed that the BPhEF component was introduced at 20 mol % of the total monomers, and the BPEF component was introduced at 80 mol % of the total monomers. The copolymerization ratio, refractive index, Abbe number, Tg, and Δn of the obtained polycarbonate resin were evaluated, and the results are shown in Table 1.1 The 1 H NMR chart is shown in Figure 1.

[0098] [Example 2] A polycarbonate resin was produced in the same manner as in Example 1, except that the amount of BPhEF was changed to 19.16 parts by mass (30 mol%) and the amount of BPEF was changed to 30.7 parts by mass (70 mol%). The copolymerization ratio, refractive index, Abbe number, Tg, and Δn of the polycarbonate resin were evaluated, and the results are shown in Table 1.

[0099] [Example 3] A polycarbonate resin was produced in the same manner as in Example 1, except that the amount of BPhEF was changed to 63.88 parts by mass (100 mol). The copolymerization ratio, refractive index, Abbe number, Tg, and Δn of the polycarbonate resin were evaluated, and the results are shown in Table 1.

[0100] [Example 4] 15.97 parts by mass (25 mol%) of BPhEF, 11.23 parts by mass (30 mol%) of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (hereinafter sometimes abbreviated as BHEB), 18.11 parts by mass (45 mol%) of 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl (hereinafter sometimes abbreviated as BCMB), 2.19 parts by mass (10.2 mol%) of DPC, and 3.4 × 10 titanium tetrabutoxide as a catalyst. -2 Part of mass (1.0×10 -3 A polyester carbonate resin was produced in the same manner as in Example 1, except that a copolymerization ratio, refractive index, Abbe number, Tg, and Δn of the polyester carbonate resin were evaluated. The results are shown in Table 1.

[0101] [Example 5] A polycarbonate resin was produced in the same manner as in Example 1, except that the amount of BPhEF was changed to 36.4 parts by mass (25 mol%) and the amount of BHEB was changed to 63.6 parts by mass (75 mol%). The copolymerization ratio, refractive index, Abbe number, Tg, and Δn of the polycarbonate resin were evaluated, and the results are shown in Table 1.

[0102] [Comparative Example 1] A polycarbonate resin was produced in the same manner as in Example 1, except that 43.85 parts by mass (100 mol%) of BPEF was used instead of BPhEF. The copolymerization ratio, refractive index, Abbe number, Tg, and Δn of the polycarbonate resin were evaluated, and the results are shown in Table 1.

[0103] Comparative Example 2 A polycarbonate resin was produced in the same manner as in Example 1, except that 53.86 parts by mass (100 mol%) of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (hereinafter sometimes abbreviated as BNEF) was used instead of BPhEF. The copolymerization ratio, refractive index, Abbe number, Tg, and Δn of the polycarbonate resin were evaluated, and the results are shown in Table 1.

[0104] Comparative Example 3 A polycarbonate resin was produced in the same manner as in Example 1, except that 55.27 parts by mass (20 mol%) of 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-diphenylfluorene (hereinafter sometimes abbreviated as BNDP2) and 35.08 parts by mass (80 mol%) of BPEF were used instead of BPhEF. The copolymerization ratio, refractive index, Abbe number, Tg, and Δn of the polycarbonate resin were evaluated, and the results are shown in Table 1. The obtained thermoplastic resin was evaluated by the following methods.

[0105] Comparative Example 4 A polycarbonate resin was produced in the same manner as in Example 1, except that 69.08 parts by mass (100 mol%) of 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-diphenylfluorene (hereinafter sometimes abbreviated as BNDP2) was used instead of BPhEF. The copolymerization ratio, refractive index, Abbe number, Tg, and Δn of the polycarbonate resin were evaluated, and the results are shown in Table 1.

[0106] The obtained thermoplastic resin was evaluated by the following methods.

[0107] <Copolymerization ratio> The obtained resin was subjected to a centrifugation using JNM-ECZ400S manufactured by JEOL Ltd. 1 The composition ratio of each polymer was calculated by H NMR measurement. CDCl3 was used as the solvent.

[0108] <Optical properties> (refractive index) A 3 mm thick test piece of each polymer was prepared and polished, and then the refractive index nd (587.56 nm) at 20° C. was measured using a Kalnew precision refractometer KPR-2000 manufactured by Shimadzu Corporation.

[0109] (Abbe number) The Abbe number was calculated from the refractive indexes at 486.13 nm, 587.56 nm, and 656.27 nm using the following formula: νd=(nd-1) / (nF-nC) nd: refractive index at a wavelength of 587.56 nm, nF: refractive index at a wavelength of 486.13 nm, nC: Refractive index at a wavelength of 656.27 nm.

[0110] (Absolute value of orientation birefringence) The thermoplastic resin was dissolved in methylene chloride, cast onto a glass dish, and thoroughly dried to prepare a 100 μm thick cast film. The film was stretched twice at Tg+10°C, and the retardation (Re) at 589 nm was measured using an Ellipsometer M-220 manufactured by JASCO Corporation. The absolute value of orientation birefringence (|Δn|) was calculated using the following formula: |Δn|=|Re / d| Δn: Orientation birefringence Re: Phase difference (nm) d: thickness (nm)

[0111] <Glass transition temperature (Tg)> The obtained resin was measured at a heating rate of 20°C / min using a Discovery DSC25Auto model manufactured by TA Instruments Japan Co., Ltd. Samples weighing 5 to 10 mg were used.

[0112] ≪Results≫ The evaluation results of specific examples of thermoplastic resins are shown in Table 1. 1 The 1 H NMR spectrum of the thermoplastic resin in Example 1 is shown in FIG. 1 The 1 H NMR spectrum is shown in Figure 2.

[0113] [Table 1]

[0114] It is clear that Examples 1 to 5 using BPhEF have a high refractive index and are able to balance heat resistance and birefringence, making them excellent optical lenses.

[0115] Although Example 1 and Comparative Example 3, and Example 3 and Comparative Example 4 have the same copolymerization partners and copolymerization ratios, the difference in birefringence is large. The phenanthryl group, which is classified as a phenacene group with a bent structure, increases the refractive index while suppressing an increase in birefringence in the main chain direction, demonstrating its excellent suitability for optical material applications. Furthermore, if you want to increase the refractive index or reduce birefringence, it is believed that introducing an aromatic group into the fluorene skeleton is effective. [Industrial Applicability]

[0116] The thermoplastic resin of the present invention is suitable for use in optical materials, and specifically can be used for optical members such as optical lenses, optical disks, transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, optical films, substrates, optical filters, and hard coat films, and is particularly useful for optical lenses.

Claims

1. A thermoplastic resin containing a repeating unit represented by the following formula (1): 【Chemical 1】 (wherein ring Z (the same or different) represents a polycyclic aromatic hydrocarbon having three or more benzene rings bonded thereto; R １ , R ２ , R ３ , and R ４ each independently represents a hydrogen atom, a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group; L １ and L ２ each independently represents a divalent linking group, j and k each independently represents an integer of 1 or more, m and n each independently represents 0 or 1, and W is at least one selected from the group represented by the following formulas (2) and (3): 【Chemistry 2】 【Chemistry 3】 (In the formula, X represents a divalent linking group.)

2. The thermoplastic resin according to claim 1, wherein the repeating unit represented by the formula (1) is at least one selected from the group represented by the following formulas (1a) to (1d): 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 (wherein ring Z is a polycyclic aromatic hydrocarbon having three or more benzene rings (the same or different) bonded thereto; R １ , R ２ , R ３ , and R ４ each independently represents a hydrogen atom or a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group; L １ and L ２ each independently represents a divalent linking group, j and k each independently represents an integer of 1 or more, m and n each independently represents 0 or 1, and W is at least one selected from the group represented by the formulas (2) and (3).

3. The thermoplastic resin according to claim 2, wherein the formula (1) is the formula (1b).

4. The thermoplastic resin according to any one of claims 1 to 3, wherein ring Z in formula (1) is a phenacene-type polycyclic aromatic hydrocarbon.

5. The thermoplastic resin according to any one of claims 1 to 3, wherein ring Z in formula (1) is phenanthrene.

6. The thermoplastic resin according to claim 1, wherein the repeating unit represented by formula (1) is represented by the following formula (4): 【Chemistry 8】 (In the formula, R ３ and R ４ each independently represents a hydrogen atom, a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group; L １ and L ２ each independently represents a divalent linking group, m and n each independently represent 0 or 1, and W is at least one selected from the group represented by formulas (2) and (3).

7. In the formula (1), R ３ and R ４ The thermoplastic resin according to any one of claims 1 to 3, wherein represents a hydrogen atom, a methyl group, a phenyl group, a naphthyl group, or a phenanthryl group.

8. In the formula (1), R ３ and R ４ The thermoplastic resin according to any one of claims 1 to 3, wherein is a hydrogen atom.

9. The thermoplastic resin according to any one of claims 1 to 3, wherein X in the formula (3) is one selected from the group consisting of a phenylene group, a naphthalenediyl group, a group represented by the following formula (5), and a group represented by the following formula (6): 【Chemistry 9】 (In the formula, R ５ and R ６ are each independently a hydrogen atom or a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may contain an aromatic group. 【Chemistry 10】

10. The thermoplastic resin according to any one of claims 1 to 3, comprising at least one repeating unit selected from the group consisting of units represented by the following formulas (7) to (10): 【Chemistry 11】 (In the formula, R ７ and R ８ are each independently a hydrogen atom or a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may contain an aromatic group. 【Chemistry 12】 (In the formula, R ９ and R １０ are each independently a hydrogen atom or a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group. 【Chemistry 13】 (In the formula, R １１ and R １２ are each independently a hydrogen atom or a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group. 【Chemistry 14】 (In the formula, R １３ and R １４ are each independently a hydrogen atom or a halogen atom, or a substituent having 1 to 20 carbon atoms which may contain an aromatic group, and U is a single bond or a divalent linking group.

11. The thermoplastic resin according to any one of claims 1 to 3, having a specific viscosity of 0.12 to 0.

40.

12. The thermoplastic resin according to any one of claims 1 to 3, having a refractive index of 1.65 to 1.

80.

13. The thermoplastic resin according to any one of claims 1 to 3, having a glass transition temperature of 130 to 190°C.

14. The absolute value of orientation birefringence is 6.0 × 10 －３ The thermoplastic resin according to any one of claims 1 to 3, wherein:

15. An optical member made of the thermoplastic resin according to any one of claims 1 to 3.

16. The optical member according to claim 15, which is an optical lens.

Images